CN104492803A - Cleaning method for repairing heavy metal contaminated soil - Google Patents
Cleaning method for repairing heavy metal contaminated soil Download PDFInfo
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Abstract
The invention discloses a cleaning method for repairing heavy metal contaminated soil. The method is characterized by comprising the following steps: (1) adding water and an oxidant to heavy metal contaminated soil, wherein the oxidant is hydrogen peroxide; (2) adding an acid and a salt to the mixture obtained from the step (1), wherein the acid is any one or combination of hydrochloric acid and sulfuric acid; the salt is any one or combination of CaCl2 or FeCl3; and (3) carrying out solid-liquid separation on the mixture obtained from the step (2), adjusting the pH value of the obtained liquid to be 8-9, adding a flocculant, standing, participating and separating, wherein the flocculant is any one or combination of polyacrylamide and aluminum polychlorid. The repairing method disclosed by the invention has the advantages of being easily available in raw material, proper in cost, simple in preparation, good in repairing effect and the like; the combined adding ratio of medicines is determined according to the soil contamination degree and the physicochemical property, so that waste of the medicines caused by excessive repair is avoided; and the risk of secondary pollution is reduced.
Description
Technical field
The invention belongs to environment remediation engineering field, be specifically related to a kind of cleaning method of restoration of soil polluted by heavy metal.
Background technology
Along with propelling and the industrial and agricultural development of national urbanization process, plurality of heavy metal contaminated site is left in industrial enterprise's resettlement, the dirty filling of agricultural causes a large amount of farmland soil heavy metals to be polluted, huge threat is all caused to land transformation recycling and grain edible quality safety, heavy metal pollution event takes place frequently, the phenomenon ubiquity of various heavy combined contamination soil, therefore people pay close attention to more to the repairing and treating being subject to combined contamination soil.
The common method of restoration of soil polluted by heavy metal mainly contains following several:
1 soil replacement method and soil moved in improve the original method: soil replacement method is scooped away by contaminated soil to dispose, then insert clean soil at excavation regions; Soil moved in improve the original method is mixed in contaminated soil by clean soil, increases soil amount dilution pollutant to reduce pollution concentration.Wherein, can take the engineering mode of soil removal and replacement for high concentration heavy-metal contaminated soil, can take the engineering mode of soil moved in improve the original for middle low-concentration heavy metal contaminated soil, these two kinds of methods can both be repaired fast and effectively and be polluted plot soil.These two kinds of technical disadvantages are: because clean soil is expensive, be only applicable to little quantities contaminated soil remediation; Agricultural land soil focuses on the maintenance of its ecological functions, and soil replacement method and soil moved in improve the original method all can spoiled soil structures, affect agricultural land soil production capacity.
2 curing/stabilizing methods: this kind of method uses the method for physics or chemistry to be fixed up by the toxic heavy metal in soil, or heavy metal is changed into the inactive form of chemical property, stop it to move in the environment, the process such as diffusion, thus reduce the recovery technique of the murder by poisoning degree of heavy metal.Curing/stabilizing method construction technology is simple, material is easy to get and advantage of lower cost, but the pharmaceutical quantities that the method is added according to soil contamination grade is huge, larger to contaminated soil increase-volume; To Heavy Metals in Contaminated Soils total amount not abatement, in complex environment condition, there is environmental risk in curing/stabilizing.
3 electro reclamation methods: the method is at contaminated soil region electrode insertion, electric field is formed after applying direct current, heavy metal contaminants in soil is directional migration under the effect of DC electric field, abdominal muscle at electrode zone, then is removed by additive method (plating, precipitation/co-precipitation, extraction, ion exchange resin etc.).Electro reclamation method is better for the removal effect of close-grained soil, and the method is in-situ immobilization, does not need a large amount of soil excavations.But, there are some restrictive conditions in electro reclamation method, because the dissolving of heavy metal in soil ion and precipitation are subject to the impact of soil pH value, can in soil, add acid to improve heavy metal removing rate thus cause soil acidification, the depolarizing agent added to remove electrode polarization may produce secondary pollution to soil; In contaminated soil when salt content, mineral matter or content of organic matter height, repairing effect can obviously decline.
4 phytoremediations: utilize Phytoremediation of Soils Contaminated by Heavy Metals mainly to utilize super enriching plant root system can absorb one or more heavy metals from soil at present, and shifted, be stored to aerial part, by gathering in aboveground vegetation part thus removing the heavy metal in soil, then the plant of harvesting is centrally disposed.This kind of method rehabilitation cost is lower, and substantially there is not secondary pollution in repair process, but the uptake of plant restoration method heavy metal is limited, and plant growth is not suitable in high concentration heavy-metal contaminated soil environment, for super enriching plant screening and cultivate also there is regional difference, the phytoremediation cycle is long, is difficult to reach engine request.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of cleaning method of restoration of soil polluted by heavy metal.
The cleaning method of restoration of soil polluted by heavy metal provided by the invention, comprises the steps:
1) in heavy-metal contaminated soil, add water and oxidant, (soak, stir or concussion), described oxidant is hydrogen peroxide;
2) add acid and salt in the mixture obtained to step 1), (soak, stir or concussion), described acid is any one or two kinds of combinations of hydrochloric acid, sulfuric acid, and described salt is CaCl
2, FeCl
3one or its combination;
3) by step 2) the mixture Separation of Solid and Liquid that obtains, the pH value obtaining liquid is adjusted to 8 ~ 9, adds flocculant, leave standstill, precipitation, be separated, described flocculant is any one or its combination of polyacrylamide, aluminium polychloride.
Preferably, also comprise the steps: before step 1) to detect Heavy Metals in Contaminated Soils to be repaired composition, content and soil physico-chemical property.
Preferably, in step 1), the weight ratio of heavy-metal contaminated soil and water is 1:5 ~ 10, is preferably 1:6.
Preferably, the addition of oxidant described in step 1) is 0.5 ~ 1% of the quality of water.
Preferably, step 2) in add described acid for adjusting pH≤6, the addition of described salt counts calcium chloride 0.1 ~ 0.2mol/L or iron chloride 0.05 ~ 0.1mol/L with the volume of the water added in step 1).
Preferably, in step 3), the addition of flocculant counts polyacrylamide 2 ~ 5mg/L or aluminium polychloride 50 ~ 100mg/L with the volume of the water added in step 1).
Preferably, described heavy metal refers to As ion, Cd ion, Cr ion, Cu ion, Hg ion, Ni ion, one of them or its combination of Pb ion or Zn ion.
Compared with prior art, reparation cleaning method of the present invention has the advantages such as raw material is easy to get, cost is suitable, preparation is simple, repairing effect is good, and pharmaceutical agent combinations adding proportion is determined according to soil contamination grade and physicochemical property, avoid excessively repairing the medicament waste caused, reduce secondary pollution risk.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, can better understand the present invention and can be implemented, but illustrated embodiment is not as a limitation of the invention to make those skilled in the art.
Compound Heavy Metals soil in the following embodiment of the present invention takes from mining area, Hunan Province periphery polluted farmland soil aggregate sample, wherein heavy metal lead, zinc and cadmium etc. exceed country " standard of soil environment quality " (GB15618-1995) grade III Standard, utilize following method of the present invention to clean soil:
1) Heavy Metals in Contaminated Soils to be repaired composition, content and soil physico-chemical property is detected.
2) in heavy-metal contaminated soil, add water and oxidant, soak, stir or concussion, wherein, oxidant is hydrogen peroxide;
3) to step 2) add cleaning agent (acid and salt) in the mixture that obtains, soak, stir or concussion, acid is any one or two kinds of combinations of hydrochloric acid, sulfuric acid, and salt is CaCl
2, FeCl
3one or its combination;
4) mixture Separation of Solid and Liquid step 3) obtained, is adjusted to 8 ~ 9 by the pH value of the liquid obtained (cleaning fluid), adds flocculant, leave standstill, precipitation, be separated, flocculant be polyacrylamide, aluminium polychloride any one or its combination.
After testing, see the following form for the heavy-metal contaminated soil physicochemical property tried and content of beary metal:
Table 1 is for examination soil physico-chemical property
| pH | Moisture content | Unit weight | Organic | Soil types |
| 6.52 | 27% | 0.89g/cm 3 | 11.3g/kg | Opaque, chiltern |
Table 2 is for examination heavy metal-polluted soil concentration mg/kg
| Pb | Zn | Cr | Cd | Cu | |
| For examination soil | 723 | 978 | 751 | 2.7 | 821 |
| Standard | 500 | 500 | 400 | 1.0 | 400 |
For subsequent use after test soil (above-mentioned heavy-metal contaminated soil) ground 50 mesh sieves, get and test with native 50g in the washer bottle of tool lid, be placed in reciprocating oscillator.According to cleaning liquid-solid ratio=6:1, add 300mL clear water.Each process repeats for 3 times.The following embodiment of cleaning agent Combination Design is utilized according to for examination soil property:
Embodiment 1.
Oxidant is selected as hydrogen peroxide (commercially available, concentration 30%), adds 5mL in 300mL water, concussion 0.5h; Cleaning agent selects hydrochloric acid (commercially available, concentration 37%) 2.5mL+calcium chloride (commercially available 3.3g, concussion 1h; After Separation of Solid and Liquid cleaning fluid (242mL), add pH adjusting agent in cleaning fluid, select NaOH (10mol/L, 6.5mL), pH value is adjusted to 8-9, flocculant selects polyacrylamide PAM(commercially available) 0.6mg, leave standstill.
Embodiment 2.
Oxidant is selected as hydrogen peroxide (commercially available, concentration 30%), adds 8mL in 300mL water, concussion 0.5h; Cleaning agent selects hydrochloric acid (commercially available, concentration 37%) 5mL+calcium chloride (commercially available 6.6g, concussion 1h; Add pH adjusting agent in cleaning fluid (240mL) after Separation of Solid and Liquid, select NaOH (10mol/L, 6.7mL), pH value is adjusted to 8-9, PB1 gene (commercially available) 15mg selected by flocculant, leaves standstill.
Embodiment 3.
Oxidant is selected as hydrogen peroxide (commercially available, concentration 30%), adds 5mL in 300mL water, concussion 0.5h; Cleaning agent selects sulfuric acid (commercially available, concentration 98%) 2mL+iron chloride (commercially available) 2.5g, concussion 1h; Add pH adjusting agent in cleaning fluid (245mL) after Separation of Solid and Liquid and select NaOH (10mol/L, 7mL), pH value is adjusted to 8-9, flocculant selects PAM(commercially available) 1.5mg, leave standstill.
Embodiment 4.
Oxidant is selected as hydrogen peroxide (commercially available, concentration 30%), adds 10mL in 300mL water, concussion 0.5h; Cleaning agent selects sulfuric acid (commercially available, concentration 98%) 5mL+iron chloride (commercially available) 4.8g, concussion 1h; Add pH adjusting agent in cleaning fluid (242mL) after Separation of Solid and Liquid and select NaOH (10mol/L, 7.3mL), pH value is adjusted to 8-9, flocculant selects PAC(commercially available) 30mg, leave standstill.
Embodiment 5.
Oxidant is selected as hydrogen peroxide (commercially available, concentration 30%), adds 8mL in 300mL water, concussion 0.5h; Cleaning agent selects hydrochloric acid (commercially available, concentration 37%) 4mL+calcium chloride (commercially available) 5.0g, concussion 1h; After Separation of Solid and Liquid cleaning fluid (246mL), add pH adjusting agent in cleaning fluid, select NaOH (10mol/L, 6.5mL), pH value is adjusted to 8-9, flocculant selects polyacrylamide PAM(commercially available) 1.0mg, leave standstill.
Embodiment 6.
Oxidant is selected as hydrogen peroxide (commercially available, concentration 30%), adds 8mL in 300mL water, concussion 0.5h; Cleaning agent selects sulfuric acid (commercially available, concentration 98%) 4mL+iron chloride (commercially available) 3.0g, concussion 1h; Add pH adjusting agent in cleaning fluid (242mL) after Separation of Solid and Liquid and select NaOH (10mol/L, 7.3mL), pH value is adjusted to 8-9, flocculant selects PAC(commercially available) 20mg, leave standstill.
CK: only add 300mL water, continuous oscillation 1.5h.
All effectively can remove various heavy after utilizing 6 kinds of embodiments and check experiment to clean Compound Heavy Metals soil, reach quality standards requirement, the results are shown in following table:
Table 3 cleans rear heavy metal in soil content (average is got in parallel processing) mg/kg
| Pb | Zn | Cr | Cd | Cu | |
| For examination soil | 723 | 978 | 751 | 2.7 | 821 |
| Standard | 500 | 500 | 400 | 1.0 | 400 |
| CK | 716 | 947 | 732 | 2.7 | 817 |
| Embodiment 1 | 275 | 389 | 301 | 0.5 | 303 |
| Embodiment 2 | 218 | 327 | 251 | 0.4 | 236 |
| Embodiment 3 | 248 | 364 | 277 | 0.4 | 262 |
| Embodiment 4 | 204 | 325 | 234 | 0.3 | 218 |
| Embodiment 5 | 222 | 372 | 268 | 0.3 | 278 |
| Embodiment 6 | 209 | 331 | 253 | 0.3 | 246 |
Supernatant after Separation of Solid and Liquid process is detected, performs " integrated wastewater discharge standard " (GB8978-1996) secondary standard.Testing result sees the following form:
Table 4 processes pollutant levels mg/L in rear supernatant
Known by the detection soil after process and supernatant being carried out to target contaminant, heavy metal in soil can clean in national standard by method of the present invention, and supernatant reaches discharge standard, can be used for cleaning fluid reuse or sewage discharge.
The above embodiment is only that protection scope of the present invention is not limited thereto in order to absolutely prove the preferred embodiment that the present invention lifts.The equivalent alternative or conversion that those skilled in the art do on basis of the present invention, all within protection scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (9)
1. a cleaning method for restoration of soil polluted by heavy metal, is characterized in that, comprises the steps:
1) in heavy-metal contaminated soil, add water and oxidant, described oxidant is hydrogen peroxide;
2) add acid and salt in the mixture obtained to step 1), described acid is any one or two kinds of combinations of hydrochloric acid, sulfuric acid, and described salt is CaCl
2or FeCl
3one or both combination;
3) by step 2) the mixture Separation of Solid and Liquid that obtains, the pH value obtaining liquid is adjusted to 8 ~ 9, adds flocculant, leave standstill, precipitation, be separated, described flocculant is any one or its combination of polyacrylamide and aluminium polychloride.
2. cleaning method according to claim 1, is characterized in that, also comprises the steps: to detect Heavy Metals in Contaminated Soils to be repaired composition, content and soil physico-chemical property before step 1).
3. cleaning method according to claim 1, is characterized in that, in step 1), the weight ratio of heavy-metal contaminated soil and water is 1:5 ~ 10.
4. cleaning method according to claim 3, is characterized in that, in step 1), the weight ratio of heavy-metal contaminated soil and water is 1:6.
5. cleaning method according to claim 3, is characterized in that, the addition of oxidant described in step 1) is 0.5 ~ 1% of the quality of water.
6. cleaning method according to claim 3, is characterized in that, step 2) in add described acid for adjusting pH≤6, the addition of described salt counts calcium chloride 0.1 ~ 0.2mol/L or iron chloride 0.05 ~ 0.1mol/L with the volume of the water added in step 1).
7. cleaning method according to claim 3, is characterized in that, in step 3), the addition of flocculant counts polyacrylamide 2 ~ 5mg/L or aluminium polychloride 50 ~ 100mg/L with the volume of the water added in step 1).
8. cleaning method according to claim 1, is characterized in that, with NaOH, pH value is adjusted to 8 ~ 9 in step 3).
9. cleaning method according to claim 1, is characterized in that, described heavy metal refers to As ion, Cd ion, Cr ion, Cu ion, Hg ion, Ni ion, one of them or its combination of Pb ion or Zn ion.
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| CN105149334A (en) * | 2015-10-12 | 2015-12-16 | 山东师范大学 | Oxidation-chelation leaching combined remediation method for Cr-contaminated soil |
| CN106190169A (en) * | 2016-09-22 | 2016-12-07 | 北京新源环境有限公司 | A kind of eluent for Compound Heavy Metals soil remediation |
| CN107350284A (en) * | 2017-08-16 | 2017-11-17 | 航天凯天环保科技股份有限公司 | A kind of efficient restorative procedure of mercury contaminated soil |
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| CN107457258A (en) * | 2017-08-16 | 2017-12-12 | 航天凯天环保科技股份有限公司 | A kind of method that mercury contaminated soil is efficiently repaired by eluting and elution medicament |
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| CN111842471A (en) * | 2020-07-24 | 2020-10-30 | 中国科学院广州地球化学研究所长沙矿产资源勘查中心 | Method for restoring farmland soil heavy metal substances by combining chemical activation and electric ionization |
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| CN105013812A (en) * | 2015-07-08 | 2015-11-04 | 广东省生态环境与土壤研究所 | Technology for rapidly restoring heavy metal pollution of farmland |
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| CN106190169A (en) * | 2016-09-22 | 2016-12-07 | 北京新源环境有限公司 | A kind of eluent for Compound Heavy Metals soil remediation |
| CN107569811A (en) * | 2017-08-16 | 2018-01-12 | 航天凯天环保科技股份有限公司 | A kind of method of mercurous dangerous waste residue Whote-wet method high-efficiency mercury removal |
| CN107457258A (en) * | 2017-08-16 | 2017-12-12 | 航天凯天环保科技股份有限公司 | A kind of method that mercury contaminated soil is efficiently repaired by eluting and elution medicament |
| CN107350284A (en) * | 2017-08-16 | 2017-11-17 | 航天凯天环保科技股份有限公司 | A kind of efficient restorative procedure of mercury contaminated soil |
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| CN107569811B (en) * | 2017-08-16 | 2020-02-04 | 航天凯天环保科技股份有限公司 | Method for efficiently removing mercury from mercury-containing hazardous waste residue by using full-wet method |
| CN107413839A (en) * | 2017-09-29 | 2017-12-01 | 北京军秀咨询有限公司 | A kind of efficient heavy metal soil-repairing agent and its restorative procedure |
| CN108311538A (en) * | 2018-01-30 | 2018-07-24 | 湖南新九方科技有限公司 | A kind of elution processing method of heavy-metal contaminated soil |
| CN111842471A (en) * | 2020-07-24 | 2020-10-30 | 中国科学院广州地球化学研究所长沙矿产资源勘查中心 | Method for restoring farmland soil heavy metal substances by combining chemical activation and electric ionization |
| CN111842471B (en) * | 2020-07-24 | 2022-04-05 | 中国科学院广州地球化学研究所长沙矿产资源勘查中心 | Method for restoring farmland soil heavy metal substances by combining chemical activation and electric ionization |
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