CN104289515A - Heavy metal contaminated soil washing method - Google Patents
Heavy metal contaminated soil washing method Download PDFInfo
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- CN104289515A CN104289515A CN201410567612.9A CN201410567612A CN104289515A CN 104289515 A CN104289515 A CN 104289515A CN 201410567612 A CN201410567612 A CN 201410567612A CN 104289515 A CN104289515 A CN 104289515A
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Abstract
The invention provides a heavy metal contaminated soil washing method. The method comprises the following steps: compounding organic acid and aids into a washing solution; fully mixing the washing solution and heavy metal contaminated soil in a stirring reactor for a long time, removing heavy metals in the washed liquid waste by virtue of an adsorbent, and recycling the residual liquid waste which serves as a washing solution. According to the method, desorption and solubilization of the heavy metals in the soil can be facilitated by compounding the organic acid and aids, the application range of the washing solution is widened, and secondary pollution to the environment is avoided. The heavy metal contaminated soil washing method disclosed by the invention has the advantages of simple process, simplicity in operation, environment friendliness, high removal efficiency, washing solution recyclability, agent and water resource conservation, and the like.
Description
Technical field
The invention belongs to heavy metal pollution of soil and administer field, especially relate to a kind of ELUTION METHOD of heavy-metal contaminated soil.
Background technology
The soil of China's heavy metal pollution accounts for about 1/6 of total cultivated area, and grain contaminated by heavy metals is every year especially up to millions of tons.Present Ni metal, Pb, Zn etc. in part contaminated site to coexist combined pollution feature, and pollution concentration is higher more.Due to high cumulative bad, the feature such as disguise and bio-refractory of heavy metal, not only cause a large amount of soils to cultivate and lie on the table, but also by food chain effect, the health of human body can be jeopardized.
The improvement of heavy-metal contaminated soil that is that research both at home and abroad at present relates to and that be applied in actual process mainly contains solidification and removes 2 kinds of approach.In recent years, different control measures and method is developed around these two kinds of approach, as solidification, reduction, agricultural regulation and control, biological prosthetic and phytoremediation etc., but these methods have not thorough, the consuming time length of process, easily produce high malicious mesostate and the shortcoming such as to be of limited application, and thus not yet apply in engineering.In current engineering, main method has following several: method of improving the soil, electro reclamation method, heat treating process, sparkling technology and soil washing.Compared with soil washing, method of improving the soil, electro reclamation method, heat treating process and vitrification or there is secondary pollution or the scope of application is little or expensive, all have comparatively obviously wait not enough.
Soil leaching technology be an application strong, thoroughly can remove the controlled and fireballing soil remediation Treatment process of pollutant, processing procedure, be usually used in the repairing and treating of contaminated site, be widely used in contaminated site reparation abroad, and achieve good repairing effect.Wherein the selection of eluent is the key of recovery technique.The heavy metal eluent reported is surfactant and acids eluent mainly.Surfactant divides the complexing agent of Prof. Du Yucang (EDTA etc.), biosurfactant (comprising rhamnolipid, sophorolipid, husky of ancient India graceful and saponin etc.).EDTA can be combined into stable chelate with most of metal ion because of it, to the Cu in soil, Zn, Pb, Hg, Cd and Cr etc. have higher removal efficiency, thus are widely used in the reparation of heavy-metal contaminated soil, but EDTA exists the problems such as expensive, biological degradability is poor, recovery is difficult.In recent years, people start biosurfactant to replace EDTA to be used for Soil leaching, but biosurfactant output is lower, and production cost is higher.Therefore, the plant-scale application of current biosurfactant does not have advantage.Acids eluent mainly comprises inorganic acid solution (HC1 and HNO
3deng), natural organic acids solution (citric acid, malic acid, oxalic acid, malonic acid, humic acid and fulvic acid etc.).Heavy metal in the maximized removal soil of inorganic acid energy, and cheap, but after drip washing, easily cause the physicochemical property of soil to change, make soil present acid, it is comparatively suitable for the soil of Industrial Wasteland serious pollution.Natural organic acids heavy metal has good Scavenging activity, and acid gentle, biological degradability is good, does not pollute environment, is the environmentally friendly eluent having very much application prospect.The research that current employing organic acid carries out single type metallic pollution soil remediation has achieved certain result, and utilize organic acid and additive combination composite with the process of the research and ring waste of repairing multiple metal soil also rarely seen report.Meanwhile, eluent loss of effective components is comparatively large, recovery time is long, reclaim concentrated pollutant is difficult to thorough elimination, easily causes pollutant entered environment system again, causes secondary pollution.
Summary of the invention
The problem to be solved in the present invention is to provide that a kind of heavy metal clearance is high, leacheate can reuse, take into account the ELUTION METHOD of the heavy-metal contaminated soil of environment friendly and low cost.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of ELUTION METHOD of heavy-metal contaminated soil, organic acid is become leacheate with additive compound, then leacheate is fully mixed in stirred reactor for a long time with heavy-metal contaminated soil, waste liquid after drip washing removes wherein heavy metal by adsorbent, and residual waste solution recycles as leacheate.
Preferably, in described compound drip washing liquid, organic acid is any one or more in citric acid, malic acid, oxalic acid, malonic acid, Humic acids and fulvic acids.
Preferably, in described compound drip washing liquid, auxiliary agent is sodium chloride.
Further, the mass ratio 5:1 ~ 2:1 of organic acid and auxiliary agent in described compound drip washing liquid.
Preferably, described adsorbent is any one or more in active carbon, tourmaline, flyash.
Further, the liquid-solid ratio of described waste liquid and adsorbent is 20:1 ~ 5:1.
The advantage that the present invention has and good effect are: owing to adopting technique scheme, the desorb solubilising of heavy metal in soil is promoted by organic acid and a small amount of additive compound, widen the scope of application of leacheate, leacheate is separated easily through adsorbent with the combination of heavy metal, and secondary pollution not being caused to environment, the spread being especially applicable to moderate heavy-metal contaminated soil uses.The present invention has that leacheate heavy metal clearance is high, leacheate can reuse, take into account the factor such as environment friendly and low cost.
Detailed description of the invention
For a better understanding of the present invention, below in conjunction with specific embodiment, the present invention is conducted further description.
Embodiment 1
The lead-contaminated soil of 5g is put in 250ml conical flask, adopt the eluent of citric acid and sodium chloride mixture, the mass ratio of citric acid and sodium chloride is 2:1, the liquid-solid ratio of eluent and soil is 20:1, then place it on magnetic stirring apparatus and stir 2h, respectively the supernatant after stirring is taken out about 4ml with pipette afterwards and put into clean centrifuge tube, centrifuge is set to rotating speed 5000r/min, centrifugal 10 minutes, carry out Separation of Solid and Liquid.Take out filtration, dilution again, measure the concentration of heavy metal in solution with Atomic Absorption Spectrometer.Using vavuum pump suction filtration, air-dry rear scales/electronic balance weighing, micro-wave digestion by remaining soil in conical flask simultaneously, measuring the concentration of heavy metal in pedotheque with Atomic Absorption Spectrometer.Clearance plumbous after recording drip washing reaches 56.1%, higher than the removal efficiency 44.9% of independent citric acid as lead during eluent.Put into active carbon by liquid-solid ratio 20:1 in waste liquid after drip washing, after charcoal absorption, in waste liquid, the lead of 93.5% is removed.
Embodiment 2
The cadmium pollution soil of 5g is put in 250ml conical flask, adopt the eluent of citric acid and sodium chloride mixture, citric acid and sodium chloride mass ratio are 5:1, the liquid-solid ratio of eluent and soil is 20:1, then place it on magnetic stirring apparatus and stir 2h, respectively the supernatant after stirring is taken out about 4ml with pipette afterwards and put into clean centrifuge tube, centrifuge is set to rotating speed 5000r/min, centrifugal 10 minutes, carry out Separation of Solid and Liquid.Take out filtration, dilution again, measure the concentration of heavy metal in solution with Atomic Absorption Spectrometer.Using vavuum pump suction filtration, air-dry rear scales/electronic balance weighing, micro-wave digestion by remaining soil in conical flask simultaneously, measuring the concentration of heavy metal in pedotheque with Atomic Absorption Spectrometer.Clearance plumbous after recording drip washing reaches 94.3%, higher than the removal efficiency 44.9% of independent citric acid as lead during eluent.Put into flyash by liquid-solid ratio 5:1 in waste liquid after drip washing, after Powder ash adsorption, in waste liquid, the lead of 84.4% is removed.
Embodiment 3
The cadmium pollution soil of 5g is put in 250ml conical flask, adopt the eluent of oxalic acid and sodium chloride mixture, oxalic acid and sodium chloride mass ratio are 4:1, the liquid-solid ratio of eluent and soil is 20:1, then place it on magnetic stirring apparatus and stir 2h, respectively the supernatant after stirring is taken out about 4ml with pipette afterwards and put into clean centrifuge tube, centrifuge is set to rotating speed 5000r/min, centrifugal 10 minutes, carry out Separation of Solid and Liquid.Take out filtration, dilution again, measure the concentration of heavy metal in solution with Atomic Absorption Spectrometer.Using vavuum pump suction filtration, air-dry rear scales/electronic balance weighing, micro-wave digestion by remaining soil in conical flask simultaneously, measuring the concentration of heavy metal in pedotheque with Atomic Absorption Spectrometer.Clearance plumbous after recording drip washing reaches 91.2%, higher than the removal efficiency 60.7% of independent oxalic acid as lead during eluent.Put into tourmaline powder by liquid-solid ratio 10:1 in waste liquid after drip washing, after tourmaline powder absorption, in waste liquid, the lead of 87.7% is removed.
Above embodiments of the invention have been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the present patent application scope change and improve, and all should still belong within patent covering scope of the present invention.
Claims (6)
1. the ELUTION METHOD of a heavy-metal contaminated soil, it is characterized in that: organic acid is become leacheate with additive compound, then leacheate is fully mixed in stirred reactor for a long time with heavy-metal contaminated soil, waste liquid after drip washing removes wherein heavy metal by adsorbent, and residual waste solution recycles as leacheate.
2. the ELUTION METHOD of heavy-metal contaminated soil according to claim 1, is characterized in that: in described compound drip washing liquid, organic acid is any one or more in citric acid, malic acid, oxalic acid, malonic acid, Humic acids and fulvic acids.
3. the ELUTION METHOD of heavy-metal contaminated soil according to claim 1 and 2, is characterized in that: in described compound drip washing liquid, auxiliary agent is sodium chloride.
4. the ELUTION METHOD of heavy-metal contaminated soil according to claim 3, is characterized in that: the mass ratio 5:1 ~ 2:1 of organic acid and auxiliary agent in described compound drip washing liquid.
5. the ELUTION METHOD of the heavy-metal contaminated soil according to any one of claim 1,2 or 4, is characterized in that: described adsorbent is any one or more in active carbon, tourmaline, flyash.
6. the ELUTION METHOD of heavy-metal contaminated soil according to claim 5, is characterized in that: the liquid-solid ratio of described waste liquid and adsorbent is 20:1 ~ 5:1.
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| CN201410567612.9A CN104289515A (en) | 2014-10-22 | 2014-10-22 | Heavy metal contaminated soil washing method |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105728450A (en) * | 2016-05-05 | 2016-07-06 | 四川农业大学 | Method for removing lead, zinc and cadmium in soil by increasing low-molecular organic acids by virtue of nano materials |
| CN106269832A (en) * | 2016-09-18 | 2017-01-04 | 天津北洋百川生物技术有限公司 | A kind of restorative procedure of lower valency heavy-metal contaminated soil |
| CN106493164A (en) * | 2016-08-24 | 2017-03-15 | 天津市北方创业园林股份有限公司 | A kind of method that utilization citric acid extracts drip washing restoration of soil polluted by heavy metal |
| CN107674679A (en) * | 2017-08-21 | 2018-02-09 | 武汉和尔环保科技有限公司 | A kind of cadmium pollution soil renovation agent |
| CN108579669A (en) * | 2018-04-24 | 2018-09-28 | 太原科技大学 | For the regenerated regenerative agent of heavy-metal contaminated soil ring waste and preparation method and application |
| 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 |
| CN109807165A (en) * | 2019-02-12 | 2019-05-28 | 四川省地质矿产勘查开发局成都综合岩矿测试中心（国土资源部成都矿产资源监督检测中心） | Heavy metal leaching and reducing method for cadmium-polluted 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 |
| CN110976497A (en) * | 2019-12-17 | 2020-04-10 | 河南省地质环境规划设计院有限公司 | Method for treating polluted soil of waste industrial and mining sites |
| CN111073654A (en) * | 2018-10-19 | 2020-04-28 | 南京化学工业园环保产业协同创新有限公司 | Heavy metal contaminated soil composite eluting agent |
| CN111662724A (en) * | 2020-06-12 | 2020-09-15 | 广州润方环保科技有限公司 | Heavy metal contaminated soil eluting agent and preparation method and application thereof |
| CN111957734A (en) * | 2020-07-03 | 2020-11-20 | 广东省生态环境技术研究所 | Method for in-situ remediation of soil heavy metal pollution |
| CN113736469A (en) * | 2021-08-06 | 2021-12-03 | 华东理工大学 | Leaching agent suitable for high-concentration arsenic-antimony composite polluted soil and preparation and application thereof |
| CN114479875A (en) * | 2022-02-23 | 2022-05-13 | 生态环境部南京环境科学研究所 | Eluting agent for restoring pesticide chemical polluted soil and preparation process thereof |
| CN115747522A (en) * | 2022-10-21 | 2023-03-07 | 广西博世科环保科技股份有限公司 | Method for recycling and cyclically utilizing soil heavy metal oxalic acid leaching waste liquid |
-
2014
- 2014-10-22 CN CN201410567612.9A patent/CN104289515A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105728450B (en) * | 2016-05-05 | 2019-01-29 | 四川农业大学 | The method that nano material promotes low molecular organic acids removal Pb in Soil, zinc and cadmium |
| CN105728450A (en) * | 2016-05-05 | 2016-07-06 | 四川农业大学 | Method for removing lead, zinc and cadmium in soil by increasing low-molecular organic acids by virtue of nano materials |
| CN106493164A (en) * | 2016-08-24 | 2017-03-15 | 天津市北方创业园林股份有限公司 | A kind of method that utilization citric acid extracts drip washing restoration of soil polluted by heavy metal |
| CN106269832A (en) * | 2016-09-18 | 2017-01-04 | 天津北洋百川生物技术有限公司 | A kind of restorative procedure of lower valency heavy-metal contaminated soil |
| CN107674679A (en) * | 2017-08-21 | 2018-02-09 | 武汉和尔环保科技有限公司 | A kind of cadmium pollution soil renovation agent |
| CN107674679B (en) * | 2017-08-21 | 2020-12-04 | 武汉和尔环保科技有限公司 | Cadmium-polluted soil remediation agent |
| CN108579669A (en) * | 2018-04-24 | 2018-09-28 | 太原科技大学 | For the regenerated regenerative agent of heavy-metal contaminated soil ring waste and preparation method and application |
| 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 |
| CN111073654A (en) * | 2018-10-19 | 2020-04-28 | 南京化学工业园环保产业协同创新有限公司 | Heavy metal contaminated soil composite eluting agent |
| CN109807165A (en) * | 2019-02-12 | 2019-05-28 | 四川省地质矿产勘查开发局成都综合岩矿测试中心（国土资源部成都矿产资源监督检测中心） | Heavy metal leaching and reducing method for cadmium-polluted 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 |
| CN110976497A (en) * | 2019-12-17 | 2020-04-10 | 河南省地质环境规划设计院有限公司 | Method for treating polluted soil of waste industrial and mining sites |
| CN111662724A (en) * | 2020-06-12 | 2020-09-15 | 广州润方环保科技有限公司 | Heavy metal contaminated soil eluting agent and preparation method and application thereof |
| CN111957734A (en) * | 2020-07-03 | 2020-11-20 | 广东省生态环境技术研究所 | Method for in-situ remediation of soil heavy metal pollution |
| CN111957734B (en) * | 2020-07-03 | 2022-04-15 | 广东省生态环境技术研究所 | Method for in-situ remediation of soil heavy metal pollution |
| CN113736469A (en) * | 2021-08-06 | 2021-12-03 | 华东理工大学 | Leaching agent suitable for high-concentration arsenic-antimony composite polluted soil and preparation and application thereof |
| CN113736469B (en) * | 2021-08-06 | 2022-08-12 | 华东理工大学 | Leaching agent suitable for high-concentration arsenic-antimony composite polluted soil and preparation and application thereof |
| CN114479875A (en) * | 2022-02-23 | 2022-05-13 | 生态环境部南京环境科学研究所 | Eluting agent for restoring pesticide chemical polluted soil and preparation process thereof |
| CN115747522A (en) * | 2022-10-21 | 2023-03-07 | 广西博世科环保科技股份有限公司 | Method for recycling and cyclically utilizing soil heavy metal oxalic acid leaching waste liquid |
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