CN105363769A - Method for restoring cadmium-contaminated farmland soil - Google Patents
Method for restoring cadmium-contaminated farmland soil Download PDFInfo
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- CN105363769A CN105363769A CN201510945995.3A CN201510945995A CN105363769A CN 105363769 A CN105363769 A CN 105363769A CN 201510945995 A CN201510945995 A CN 201510945995A CN 105363769 A CN105363769 A CN 105363769A
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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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- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a method for restoring cadmium-contaminated farmland soil. The method comprises the specific steps that cadmium in the contaminated soil is transferred and removed through a chemical elution mode, a mixed water solution of ferric chloride and ammonium chloride is adopted as an eluting agent during chemical elution, the mass concentration of ferric chloride ranges from 0.8% to 2.0%, and the mass concentration of ammonium chloride ranges from 0.5% to 1.5%. Ferric chloride and ammonium chloride are compounded to serve as the eluting agent, the cadmium removal rate is high, and especially when the cadmium-contaminated farmland soil with the cadmium content smaller than or equal to 1.1 mg/kg is restored, the content of cadmium in the restored soil can conform to the secondary standard GB15618-1995. The environmental pollution risk of the cadmium-contaminated farmland soil is thoroughly eliminated, and safety production of agricultural products is ensured. In addition, the prepared eluting agent can effectively protect the integrity of the soil structure, and the probability that the restored soil can be used for farming is ensured.
Description
Technical field
The present invention relates to the restorative procedure of contaminated soil, be specifically related to a kind of method of remediating heavy metal Cd-polluted farmland soil.
Background technology
China's Cadmium Pollution in Soils event takes place frequently in recent years, and as Hunan " cadmium rice " event, attract wide attention socially, the repairing and treating of heavy metal pollution agricultural land soil is extremely urgent.Cadmium is one of heavy metal toxicity maximum " five poisonous creatures: scorpion, viper, centipede, house lizard, toad ", has latency, persistence and irreversibility, and bio-toxicity is large, is easier to be absorbed by crops, enters food chain, be detrimental to health in soil than other heavy metal.
At present, two research directions are mainly comprised to the repairing and treating of Cd-polluted farmland soil: one is the cadmium transfer in soil removed by the mode such as chemical leaching, plant extraction, thus reaches the object reducing Cadmium in Soil content; Two is the modes by curing/stabilizing, is the stable forms such as residual form by the existing forms of Cadmium in Soil from water-soluble state, exchangeable species isoreactivity Forms Transformation, reduces the activity of cadmium, reduces crops to the absorption of cadmium.
The existing repairing and treating method to Cd-polluted farmland soil is a lot, as: publication number is a kind of method that the patent of invention of CN102513340A discloses remediating heavy metal cadmium pollution soil, concrete employing plant and microbial association restorative procedure process cadmium pollution soil, result shows that cadmium clearance is 64.2%, and the method exists the deficiencies such as repairing efficiency length, later stage plant collection and complex treatment process.Publication number is the restorative procedure that the patent of invention of CN102615098A discloses the plumbous combined pollution calacareous soil of a kind of cadmium, specifically adopts Al
2(SO
4)
318H
2o and bodied ferric sulfate (PFS) carry out drip washing to cadmium pollution soil, the result of embodiment shows that in contaminated soil, the clearance of available Cd reaches 84%, but after repairing, the content of soil available Cd is 0.93mg/kg, is still in intermediate pollution level.Publication number is that the patent of invention of CN104650921A discloses and a kind ofly reduces Cadmium in Soil, the renovation agent of plumbous bio-available Zn concentration and using method thereof and application, wherein adopt quick lime, calcium sulfate, charcoal, iron chloride and water to prepare passivator to be cured cadmium pollution soil, the result of embodiment shows that repairing rear Cadmium in Soil bio-available Zn concentration drops to 0.28mg/kg from 0.73mg/kg, and rate of descent is 61.6%.Publication number is that the patent of invention of CN103143556A discloses a kind of passivator and the using method thereof that reduce acid vegetable field soil cadmium activity, this invention uses lime, humic acid and rice husk carbon to be cured cadmium pollution soil as passivator, the curing degree that the result of embodiment shows to repair rear cadmium is 30 ~ 40%, but do not reduce by the content of the Cadmium in Soil after the described method reparation of this invention, and just change the existing forms of cadmium in soil, the risk again changing into cadmium available state is there is when natural environment is changeable.Therefore, adopt efficient eluent to carry out drip washing to Cd-polluted farmland soil, reduce the content of Cadmium in Soil, make it meet standard of soil environment quality, fundamentally could solve the problem of Cd-polluted farmland soil.
Summary of the invention
The technical problem to be solved in the present invention is to provide and a kind ofly operates method that is simple and easy and the remediating heavy metal Cd-polluted farmland soil that cadmium clearance is high.When adopting the method for the invention to repair the heavy metal cadmium agricultural land soil that cadmium content is less than or equal to 1.1mg/kg, the cadmium content after can making reparation in soil meets GB15618-1995 (" standard of soil environment quality ") secondary standard (0.3mg/kg).
The method of remediating heavy metal Cd-polluted farmland soil of the present invention, the mode of chemical leaching is specifically adopted the cadmium transfer in contaminated soil to be removed, the eluent adopted when chemical leaching is the mixed aqueous solution of iron chloride and ammonium chloride, wherein, chlorination iron speciation is 0.8 ~ 2.0%, and the mass concentration of ammonium chloride is 0.5 ~ 1.5%.
The more specifically method of remediating heavy metal Cd-polluted farmland soil, is be placed in reaction vessel by the contaminated soil fragmentation of drying, adds eluent and carry out drip washing, carry out Separation of Solid and Liquid after drip washing completes, obtain the soil after drip washing; In the soil after drip washing, add limestone powder, mix, leave standstill moisture-keeping maintaining, obtain cleaning soil.
In said method, when the content of heavy metal cadmium Cadmium in Soil is less than or equal to 1.1mg/kg, in eluent, chlorination iron speciation is preferably 0.8 ~ 1.5%, and the mass concentration of ammonium chloride is preferably 0.5 ~ 1.0%; In preferred eluent, chlorination iron speciation is 0.8 ~ 1.0% further, and the mass concentration of ammonium chloride is 0.5 ~ 0.8%.When adopting the eluent of said ratio to be less than or equal to cadmium content to repair in the heavy metal cadmium soil of 1.10mg/kg, cadmium clearance reaches more than 80%, and the cadmium content after repairing in soil meets GB15618-1995 secondary standard.
In said method, the addition of described eluent usually adds 3 ~ 10 milliliters of eluents by every gram of dry contaminated soil and calculates, and preferably adds 4 ~ 6 milliliters of eluents by every gram of dry contaminated soil and calculates.Described drip washing is carried out usually under agitation, and the speed of stirring is same as the prior art, is generally 150 ~ 180r/min.
In said method, the addition of described lime stone usually adds 0.05 ~ 0.1 gram of lime stone by every gram of dry contaminated soil and calculates, and preferably adds 0.05 ~ 0.8 gram of lime stone by every gram of dry contaminated soil and calculates.
In said method, the time of described drip washing is same as the prior art, is generally 0.5 ~ 2 hour.
In said method, the granularity of limestone powder is normally less than 100 orders.
In said method, the time of described standing moisture-keeping maintaining is generally and is more than or equal to 1 day, is preferably 1 ~ 4 day.Described standing moisture-keeping maintaining leaves standstill under the condition of the plastic film covering of plastic sheeting or other material, can ensure the humidity of soil like this, effectively regulate soil pH.
Compared with prior art, the present invention adopt iron chloride and ammonium chloride composite as eluent, composition is simple, there is when carrying out soil remediation higher cadmium clearance, particularly cadmium content is less than or equal to when repairing in the heavy metal cadmium soil of 1.1mg/kg, cadmium content after can making reparation in soil meets GB15618-1995 secondary standard, thoroughly eliminates the risk of environmental pollution of Cd-polluted farmland soil, guarantees the safety in production of agricultural product; On the other hand, utilize the buffering coordinative role of ammonium chloride to avoid the strong oxidizing property of iron chloride to the direct destruction of soil texture, the integrality of available protecting soil texture, guarantee that the soil after repairing can be used in the possibility of agro-farming.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, and to understand content of the present invention better, but the present invention is not limited to following examples.
Embodiment 1
(1) will Guangxi Lin Pb-Zn ore district periphery agricultural land soil (content of Cd is 1.1mg/kg, pH=6.5) natural air drying be picked up from, grind by 10 order analysis sieves, remove the non-native impurity such as bulky grain stone, root system of plant in soil;
(2) get iron chloride and ammonium chloride to add water and be mixed with eluent, wherein, the concentration of iron chloride and ammonium chloride is respectively 1.0% (w/w) and 0.5% (w/w);
(3) take 20g contaminated soil and put into 250ml triangular flask, the ratio being 5ml:1g according to liquid-solid ratio adds the eluent that 100ml prepares, and at room temperature use agitator to carry out stirring reaction 1.0h, stir speed (S.S.) controls at 150r/min;
(4) carry out suction filtration to washed off soil, complete Separation of Solid and Liquid, after soil and leacheate complete and be separated, suction filtration limit, limit slowly adds 30ml distilled water in soil, and cleaning remains in the eluent of soil surface;
(5) add 1.0g limestone powder (100 order) in the soil after drip washing, repeatedly stir and mix, leave standstill moisture-keeping maintaining 1d.
Comparative example 1
(1) will Guangxi Lin Pb-Zn ore district periphery agricultural land soil (content of Cd is 1.10mg/kg, pH=6.5) natural air drying be picked up from, grind by 10 order analysis sieves, remove the non-native impurity such as bulky grain stone, root system of plant in soil;
(2) get iron chloride to add water and be mixed with eluent, wherein the concentration of iron chloride is 1.0% (w/w);
(3) take 20g contaminated soil and put into 250ml triangular flask, the ratio being 5ml:1g according to liquid-solid ratio adds the eluent that 100ml prepares, and at room temperature use agitator to carry out stirring reaction 1.0h, stir speed (S.S.) controls at 180r/min;
(4) carry out suction filtration to washed off soil, complete Separation of Solid and Liquid, after soil and leacheate complete and be separated, suction filtration limit, limit slowly adds 30ml distilled water in soil, and cleaning remains in the eluent of soil surface;
(5) add 1.0g limestone powder in the soil after drip washing, repeatedly stir and mix, leave standstill moisture-keeping maintaining 1d.
Be 0.19mg/kg by the Cadmium in Soil content after method reparation described in embodiment 1, cadmium clearance reaches 82.73%, and soil pH is 6.3.And in comparative example 1, the Cadmium in Soil content after reparation is 0.25mg/kg, cadmium clearance reaches 77.27%, but soil pH is 4.3, and soil is in acid.Although two kinds of methods can make the content of Cadmium in Soil reach " standard of soil environment quality " (GB15618-1995) secondary standard (0.3mg/kg), but from soil pH, in embodiment 1, soil after reparation can meet soil acidity or alkalinity and require (6 ~ 9), and in comparative example 1, the serious slant acidity of soil, soil receives impact as the normal use of agro-farming.Therefore, in embodiment 1, use iron chloride and ammonium chloride composite as eluent, the clearance of Cadmium in Soil can not only be improved, under the buffering coordinative role of ammonium chloride, the soil after reparation can also be enable to be directly used in proportion of crop planting, not affect the normal usage function of agricultural land soil.
Embodiment 2
(1) will mining area, Yang Shuo, Guangxi periphery agricultural land soil (content of Cd is 0.83mg/kg, pH=6.5) natural air drying be picked up from, grind by 10 order analysis sieves, remove the non-native impurity such as bulky grain stone, root system of plant in soil;
(2) get iron chloride and ammonium chloride to add water preparation eluent, wherein, the concentration of iron chloride and ammonium chloride is respectively 1.0% (w/w) and 0.5% (w/w);
(3) take 20g contaminated soil and put into 250ml triangular flask, the ratio being 8ml:1g according to liquid-solid ratio adds the eluent that 100ml prepares, and at room temperature use agitator to carry out stirring reaction 1.0h, stir speed (S.S.) controls at 170r/min;
(4) carry out suction filtration to washed off soil, complete Separation of Solid and Liquid, after soil and leacheate complete and be separated, suction filtration limit, limit slowly adds 30ml distilled water in soil, and cleaning remains in the eluent of soil surface;
(5) add 1.0g limestone powder in the soil after drip washing, repeatedly stir and mix, leave standstill moisture-keeping maintaining 1d.
Be 0.16mg/kg by the Cadmium in Soil content after method reparation described in above-described embodiment 2, cadmium clearance reaches 80.72%, and soil pH is 6.5.
Embodiment 3
(1) will Nandan County, Guangxi polluted farmland soil (content of Cd is 5.50mg/kg, pH=6.0) natural air drying be picked up from, grind by 10 order analysis sieves, remove the non-native impurity such as bulky grain stone, root system of plant in soil;
(2) use iron chloride and ammonium chloride is composite makes eluent, the concentration of iron chloride and ammonium chloride is respectively 1.0% (w/w) and 0.5% (w/w);
(3) take 20g contaminated soil and put into 250ml triangular flask, the ratio being 5ml:1g according to liquid-solid ratio adds the eluent that 100ml prepares, and at room temperature use agitator to carry out stirring reaction 1.0h, stir speed (S.S.) controls at 160r/min;
(4) carry out suction filtration to washed off soil, complete Separation of Solid and Liquid, after soil and leacheate complete and be separated, suction filtration limit, limit slowly adds 30ml distilled water in soil, and cleaning remains in the eluent of soil surface;
(5) add 1.0g limestone powder in the soil after drip washing, repeatedly stir and mix, leave standstill moisture-keeping maintaining 1d.
Be 1.24mg/kg by the Cadmium in Soil content after method reparation described in above-described embodiment 3, cadmium clearance reaches 77.45%, and soil pH is 6.0.
Embodiment 4
(1) by picking up from large new certain mining area periphery agricultural land soil (content of Cd is 30mg/kg, the pH=6.5) natural air drying in Guangxi, grinding by 10 order analysis sieves, removing the non-native impurity such as bulky grain stone, root system of plant in soil;
(2) get iron chloride and ammonium chloride to add water and be mixed with eluent, wherein the concentration of iron chloride and ammonium chloride is respectively 1.5% (w/w) and 1.0% (w/w);
(3) take 20g contaminated soil and put into 250ml triangular flask, the ratio being 5ml:1g according to liquid-solid ratio adds the eluent that 100ml prepares, and at room temperature use agitator to carry out stirring reaction 1.0h, stir speed (S.S.) controls at 160r/min;
(4) carry out suction filtration to washed off soil, complete Separation of Solid and Liquid, after soil and leacheate complete and be separated, suction filtration limit, limit slowly adds 30ml distilled water in soil, and cleaning remains in the eluent of soil surface;
(5) add 1.5g limestone powder in the soil after drip washing, repeatedly stir and mix, leave standstill moisture-keeping maintaining 2d.
Be 2.53mg/kg by the Cadmium in Soil content after method reparation described in above-described embodiment 4, cadmium clearance reaches 91.56%, and soil pH is 6.3.
Embodiment 5
(1) will Guangxi Lin Pb-Zn ore district periphery agricultural land soil (content of Cd is 1.1mg/kg, pH=6.5) natural air drying be picked up from, grind by 10 order analysis sieves, remove the non-native impurity such as bulky grain stone, root system of plant in soil;
(2) get iron chloride and ammonium chloride to add water and be mixed with eluent, wherein, the concentration of iron chloride and ammonium chloride is respectively 1.5% (w/w) and 0.5% (w/w);
(3) take 20g contaminated soil and put into 250ml triangular flask, the ratio being 10ml:1g according to liquid-solid ratio adds the eluent that 100ml prepares, and at room temperature use agitator to carry out stirring reaction 1.0h, stir speed (S.S.) controls at 150r/min;
(4) carry out suction filtration to washed off soil, complete Separation of Solid and Liquid, after soil and leacheate complete and be separated, suction filtration limit, limit slowly adds 30ml distilled water in soil, and cleaning remains in the eluent of soil surface;
(5) add 1.0g limestone powder (100 order) in the soil after drip washing, repeatedly stir and mix, leave standstill moisture-keeping maintaining 1d.
Be 0.18mg/kg by the Cadmium in Soil content after method reparation described in above-described embodiment 5, cadmium clearance reaches 83.64%, and soil pH is 6.0.
Embodiment 6
(1) will mining area, Yang Shuo, Guangxi periphery agricultural land soil (content of Cd is 0.83mg/kg, pH=6.5) natural air drying be picked up from, grind by 10 order analysis sieves, remove the non-native impurity such as bulky grain stone, root system of plant in soil;
(2) get iron chloride and ammonium chloride to add water preparation eluent, wherein, the concentration of iron chloride and ammonium chloride is respectively 0.8% (w/w) and 1.0% (w/w);
(3) take 20g contaminated soil and put into 250ml triangular flask, the ratio being 3ml:1g according to liquid-solid ratio adds the eluent that 100ml prepares, and at room temperature use agitator to carry out stirring reaction 1.0h, stir speed (S.S.) controls at 170r/min;
(4) carry out suction filtration to washed off soil, complete Separation of Solid and Liquid, after soil and leacheate complete and be separated, suction filtration limit, limit slowly adds 50ml distilled water in soil, and cleaning remains in the eluent of soil surface;
(5) add 1.0g limestone powder in the soil after drip washing, repeatedly stir and mix, still aging 4d.
Be 0.15mg/kg by the Cadmium in Soil content after method reparation described in above-described embodiment 6, cadmium clearance reaches 86.36%, and soil pH is 6.2.
Visible, in conjunction with the embodiments 1, use iron chloride and ammonium chloride is composite carries out middle low concentration Cd-polluted farmland soil remediation as eluent, the cadmium in soil can be reduced to satisfied " standard of soil environment quality " (GB15618-1995) secondary standard (0.3mg/kg); And for high concentration Cd-polluted farmland soil, also there is higher clearance, carry out contrast with embodiment 4 to find, after the concentration increasing iron chloride and ammonium chloride in eluent, the removal efficiency increasing cadmium can be continued, greatly can reduce agricultural land soil for pollution of agricultural products risk during proportion of crop planting.
Above-described embodiment is only the preferred embodiment of the present invention, and protection scope of the present invention is also not only confined to above-described embodiment.All technical schemes belonged under thinking of the present invention all belong to protection scope of the present invention.It is noted that for those skilled in the art, distortion under the premise without departing from the principles of the invention and improvement, the protection domain that claims of the present invention is determined all should be considered as.
Claims (9)
1. the method for a remediating heavy metal Cd-polluted farmland soil, it is characterized in that: it adopts the mode of chemical leaching the cadmium transfer in contaminated soil to be removed, the eluent adopted when chemical leaching is the mixed aqueous solution of iron chloride and ammonium chloride, wherein, chlorination iron speciation is 0.8 ~ 2.0%, and the mass concentration of ammonium chloride is 0.5 ~ 1.5%.
2. method according to claim 1, is characterized in that: be placed in reaction vessel by the contaminated soil fragmentation of drying, adds eluent and carries out drip washing, carry out Separation of Solid and Liquid after drip washing completes, obtain the soil after drip washing; In the soil after drip washing, add limestone powder, mix, leave standstill moisture-keeping maintaining, obtain cleaning soil.
3. method according to claim 1 and 2, is characterized in that: when the content of heavy metal cadmium Cadmium in Soil is less than or equal to 1.1mg/kg, and in eluent, chlorination iron speciation is 0.8 ~ 1.5%, and the mass concentration of ammonium chloride is 0.5 ~ 1.0%.
4. method according to claim 1 and 2, is characterized in that: when the content of heavy metal cadmium Cadmium in Soil is less than or equal to 1.1mg/kg, and in eluent, chlorination iron speciation is 0.8 ~ 1.0%, and the mass concentration of ammonium chloride is 0.5 ~ 0.8%.
5. method according to claim 1 and 2, is characterized in that: the addition of described eluent adds 3 ~ 10 milliliters of eluents by every gram of dry contaminated soil and calculates.
6. method according to claim 1 and 2, is characterized in that: the addition of described lime stone adds 0.05 ~ 0.1 gram of lime stone by every gram of dry contaminated soil and calculates.
7. method according to claim 1 and 2, is characterized in that: the time of described drip washing is 0.5 ~ 2 hour.
8. method according to claim 1 and 2, is characterized in that: the time of described standing moisture-keeping maintaining is for being more than or equal to 1 day.
9. method according to claim 1 and 2, is characterized in that: the time of described standing moisture-keeping maintaining is 1 ~ 4 day.
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| CN201510945995.3A CN105363769A (en) | 2015-12-17 | 2015-12-17 | Method for restoring cadmium-contaminated farmland soil |
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Cited By (8)
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| CN106694532A (en) * | 2016-12-26 | 2017-05-24 | 湖南金旅环保股份有限公司 | Method for repairing cadmium-polluted farmland soil |
| CN107138511A (en) * | 2017-05-11 | 2017-09-08 | 南京大学 | A kind of method of renovation of heavy metal polluted soil with combined |
| CN107737803A (en) * | 2017-11-24 | 2018-02-27 | 湖南新九方科技有限公司 | A kind of restorative procedure in heavy metal cadmium arable land |
| 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 |
| CN109877146A (en) * | 2019-03-11 | 2019-06-14 | 深圳市铁汉生态环境股份有限公司 | A kind of As polluted soil repairs structure and restorative procedure |
| CN111014272A (en) * | 2019-11-19 | 2020-04-17 | 清华苏州环境创新研究院 | Method for removing heavy metals in soil or plants by using triethylamine bisulfate ionic liquid |
| CN112852434A (en) * | 2020-12-21 | 2021-05-28 | 华南理工大学 | Preparation and application of environment-friendly heavy metal composite contaminated soil remediation eluent |
| CN113020234A (en) * | 2021-01-04 | 2021-06-25 | 大连理工大学 | Environment-friendly chemical leaching method for Cd-polluted soil |
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| CN112852434A (en) * | 2020-12-21 | 2021-05-28 | 华南理工大学 | Preparation and application of environment-friendly heavy metal composite contaminated soil remediation eluent |
| CN113020234A (en) * | 2021-01-04 | 2021-06-25 | 大连理工大学 | Environment-friendly chemical leaching method for Cd-polluted soil |
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Application publication date: 20160302 |