CN101585045B - Method for repairing heavy metal pollution soil by using chemical leaching and deep layer fixing combining technology - Google Patents
Method for repairing heavy metal pollution soil by using chemical leaching and deep layer fixing combining technology Download PDFInfo
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- CN101585045B CN101585045B CN2009100404038A CN200910040403A CN101585045B CN 101585045 B CN101585045 B CN 101585045B CN 2009100404038 A CN2009100404038 A CN 2009100404038A CN 200910040403 A CN200910040403 A CN 200910040403A CN 101585045 B CN101585045 B CN 101585045B
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Abstract
A method for repairing a heavy metal pollution soil by using a chemical leaching and deep layer fixed combining technology is characterized in that leaching the heavy metal pollution skin layer soil by a leaching agent, and the leached heavy metal is refastened by the soil processed by a fixation agent on the deep layer. By means of leaching the heavy metal pollution skin layer soil by the leaching agent with certain concentration, it is capable of reducing the skin layer soil heavy metal and the absorption of crops root system; the leached heavy metal is fixed on the deep layer, and the fixedheavy metal is not be leached again by a rain rarely, which avoids to pollute the groundwater, so as to repair and use safely the heavy metal pollution soil. The method for repairing the polluted soi l has a high efficiency, is capable of controlling an environment risk of the groundwater nicely, and is a new and low cost repairing route for the heavy metal pollution soil.
Description
Technical field
The present invention relates to a kind of United Technologies of restoration of soil polluted by heavy metal, specifically utilize to mix organic formulations drip washing heavy-metal contaminated soil, apply the heavy metal of passivator under fixedly drenching at deep soil.
Background technology
Along with the development of industrial and agricultural production, heavy metal pollution problem is on the rise in soil-plant-water system.The chief of State Environmental Protection Administration Zhou Shengxian is gone up expression at national soil pollution status investigation and prevention and cure of pollution special work video conferences (on July 18th, 2006), according to incomplete investigation, Chinese contaminated arable land has 1.5 hundred million mu approximately at present, the annual contaminated by heavy metals grain in the whole nation reaches 1,200 ten thousand tons, and the direct economic loss that causes is above 20,000,000,000 yuan.The annual contaminated by heavy metals grain of China is 1,200 ten thousand t nearly, and the economic loss that is caused by the heavy metal pollution of agricultural product reached 32,000,000,000 yuans in 2000 increasing year by year; And can worsen hydrological environment, and may pass through approach such as contact, food chain harm humans directly or indirectly by the leaching polluted underground water of rainwater.In many key areas, soil and underground water pollution have caused the M ﹠ M of diseases such as cancer apparently higher than many times of the check plot several times to 10 that do not have to pollute.Heavy metal pollution of soil has become one of major obstacles of restriction China's Agricultural international trade and social economy's sustainable development, and contaminated soil presses for repairing and treating.
The many clocks of improvement method of heavy-metal contaminated soil are various, and wherein chemical leaching is one of effective technology means of restoration of soil polluted by heavy metal.Under the situation, the original position reparation can demonstrate the superiority on its remediation efficiency and the cost mostly, but the processing of the pouring fluid that the problem that in-situ chemical drip washing faces is soil drip washing to be produced, and the pouring fluid is dealt with improperly, will cause underground water pollution.Drench normal employing of fluid at present in the world and pump processing (P﹠amp; T) technology, but cost height.Therefore be necessary to develop and effectively control the soil remediation method that drenches heavy metal in the fluid.
Summary of the invention
The present invention is directed to the deficiency in the prior art, purpose be to provide a kind of cheap, simple to operate, the method for the restoration of soil polluted by heavy metal that heavy metal can not got off by the precipitation drip washing in later stage.
The present invention is achieved through the following technical solutions the foregoing invention purpose:
A kind of method of utilizing chemical leaching and deep layer fixing combining technology restoration of soil polluted by heavy metal, be earlier fixative to be injected deep soil, utilize the topsoil of eluent drip washing heavy metal pollution again, it is fixing once more by the soil of handling through fixative in deep layer to drench the heavy metal that.
Method provided by the invention focuses on drip washing and fixing United Technologies rehabilitating soil, and used eluent is generally the mixing organic formulations, needs to adapt with the heavy metal that will remove, and fixative also adapts with wanting fixed heavy metal.
The eluent that the present invention selects for use is a kind of mixing organic formulations, for: the mixed aqueous solution of citric acid, b diammonium disodium edta salt and KCl, the ratio of the molar concentration of described citric acid, b diammonium disodium edta salt and KCl is 9-11: 1-3: 2-4.
The total mol concentration of described mixing organic formulations is preferably 5-50mmol/L.
The fixative that the present invention selects for use is the passivation fixative, is selected from iron chloride (FeCl
3, pH3-8), any one or the two or more aqueous solution of press the arbitrary proportion mixing in the polymerization iron (water treatment commonly used flocculant), CaO, the molar concentration that it is independent or the total mol concentration of mixing are 0.02-1mol/L.
The present invention selects the FeCl of pH3-8 for use
3The aqueous solution is a preferable range, but not implements whole scheme of the present invention.
CaO of the present invention also can use lime to replace, and does not influence enforcement of the present invention.
The described fixative that injects in soil adopts punching to inject the mode of solution; The degree of depth of punching is 50-100cm.This degree of depth is a preferred version, and the depth of soil that utilizes with present people adapts.
The method of the restoration of soil polluted by heavy metal that provides of the present invention, drip washing be from topsoil, and the deep soil that agent handles that can be fixed of the heavy metal in the pouring fluid that chemical leaching produces is fixed up, and then carries out the drip washing second time; So repeated multiple times can make the top layer polluted soil reach safety standard, the deep soil that deep layer is handled by fixative, root system of plant seldom, the plant growth can not absorb heavy metal substantially; The deep soil fixed heavy metal that fixative is handled is difficult for being got off by the precipitation drip washing in later stage, can control phreatic possibility risk.
Compared with prior art, the present invention has following beneficial effect:
(1) compare with commonly used eluent EDTA, EDDS, the selected mixing organic formulations of the present invention can effectively clean heavy metal in the soil as eluent, and cost is obviously lower;
(2) fixed heavy metal was difficult for being got off by the precipitation drip washing in later stage after the selected passivator of the present invention mixed with deep soil, had controlled effectively phreatic possibility risk;
(3) with drench fluid commonly used pump processing (P﹠amp; T) technology is compared, and the present invention uses the deep layer technique for fixing, and cost is obviously lower.
(4) with conventional topsoil fixedly heavy metal, reduce crop and absorb and compare, the present invention is fixed on root system deep soil seldom with heavy metal, safety coefficient is higher.
The specific embodiment
Below further specify technical scheme of the present invention by specific embodiment.
Embodiment of the invention test Agricultural University Of South China Environmental Science and Engineering are that the solarium carries out, and contaminated soil is taken from the rice terrace of certain plumbous zinc ore contaminated wastewater, and wherein heavy metal Zn, Cd and Pb surpass national soil environment quality standard (GB15618-1995).With mixing organic formulations soil is carried out drip washing.
Embodiment 1
The mix reagent that with 3L concentration is 10mmol/L carries out slow drip washing to the 5kg contaminated soil, collect and drench fluid and recording volume, the pouring fluid of collecting is mixed, be designated as to pollute and drench fluid I, drench the deep soil of the consumption of fluid I with every basin soil 1500ml then, and collect water sample through the fixative processing.After 40 days, contaminated soil is carried out drip washing, collect and drench fluid and recording volume with clear water, the pouring fluid of collecting is mixed, be designated as to pollute and drench fluid II, drench the deep soil of the consumption of fluid II with every basin soil 1500ml then, and collect water sample through the fixative processing.
The soil that fixative is handled: form with different fixatives by the 5kg lower soil.Soil is taken from the following soil of 20cm in the Agricultural University Of South China campus, is acid red earth, pollutes the rice field subsoil with the Lechang and has similarity, and soil places plastic tub, the porose outflow of supplying water in bottom.Fixedly have 4 processing: 1. contrast does not add fixative; 2. the CaO aqueous solution: add 7.5g CaO in the 1L water; 3. FeCl
3: the iron chloride of the 0.5mol/L of the pH=8 of adding 1L; 4. FeCl
3The ferric chloride solution that+CaO:7.5g CaO joins the 0.5mol/L of 1L pH=8 forms mixed solution, and each is handled 3 times and repeats.
Utilize to mix organic formulations and soil is carried out a drip washing just can remove heavy metal in the soil very effectively, the results are shown in Table 1:
Table 1 mixes the removal amount (mg/ basin) of a drip washing of organic formulations (MC) to heavy metal-polluted soil
Annotate: in the mixing organic formulations of the present invention, the ratio of the molar concentration of citric acid, b diammonium disodium edta salt and KCl all is controlled between this scope of 9-11: 1-3: 2-4, require very inaccurately owing to handle the required machine-processed agent concentration that is mixed with of soil, so embodiments of the invention also need not accurate weighing and preparation; The scope of the mixing organic formulations that the present invention selects for use is a preferable range; be not to have only the mixing organic formulations of this concentration proportioning could implement the present invention; simultaneously, other concentration ranges that those skilled in the art will envision that also are the claimed contents of the present invention.
The concentration of COD (COD), Zn, Cd and the Pb of the pouring fluid I that mixing organic formulations washed off soil of the present invention produces is respectively 2093mg/L, 10.02mg/L, and 0.0147mg/L, 25.20mg/L, as shown in table 2:
The agent of table 2 different fixing is handled deep soil to drenching the fixed effect (mg/L) of fluid I
As can be seen from Table 2, behind the deep soil through different fixing agent processing, COD and content of beary metal all obviously reduce.Drench fluid I through FeCl
3After handling deep soil, it is minimum drenching the fluid pollutant levels, and COD, Zn, Cd, Pb concentration are respectively 37.7%, 15.5%, 44.6%, 69.0% of CK processing, and wherein Zn, Cd concentration all are lower than groundwater quality standard I II class; Drench fluid I through CaO and FeCl
3Behind the deep soil that+CaO handles, pouring fluid COD, Zn, Cd, Pb concentration are all handled apparently higher than CK.
Different fixing agent processing deep soil sees Table 3 to the clearance of pollutant among the pouring fluid I of chemical leaching generation
The agent of table 3 different fixing is handled soil to polluting the fixed rate of drenching pollutant among the fluid I
Annotate: clearance %=(heavy metal concentration before fixing-fixing back heavy metal concentration)/fixing preceding heavy metal concentration * 100
Show FeCl in the table 3
3The deep soil of handling reaches 89.28%, 96.99%, 82.99%, 78.09% respectively to the clearance that drenches COD, Zn, Cd, Pb in the fluid, and removal effect is best.CaO and FeCl
3The clearance that+CaO handles is suitable, all is starkly lower than CK and FeCl
3Handle.
Interplant contaminated soil with water wash, can be regarded as with the simulated rainfall behind the mixing organic formulations washed off soil, following the oozing of water can exert an influence to the heavy metal of lower floor's fixative processing soil fixing.The pollution that the water washed off soil produces is drenched fluid II and is seen Table 4 through the heavy metal concentration before and after the deep soil of fixative processing:
The agent of table 4 different fixing is handled deep soil to drenching the fixed effect (mg/L) of fluid II
Can find out in the table 4, drench the deep soil that fluid II handles through different fixatives after, drench fluid Zn, Cd concentration all be lower than fixing before, all be lower than groundwater quality standard I II class.But for the Pb that drenches in the fluid, through CK, CaO and FeCl
3+ CaO fixative handle concentration behind the soil be higher than fixing before, surpassed groundwater quality standard I II class, with the Pb that is fixed early stage again desorb get off; Have only through FeCl
3Fixative handle pouring fluid Pb concentration behind the soil be lower than fixing before, also be lower than groundwater quality standard I II class (0.05mg/kg).Heavy metal in the pouring fluid that the effective fixing soil drip washing of alkaline iron chloride and subsoil mixing energy produces is described, and can not be leached out by later stage water (as rainfall).
Claims (9)
1. method of utilizing chemical leaching and deep layer fixing combining technology restoration of soil polluted by heavy metal, it is characterized in that earlier fixative being injected deep soil, utilize the topsoil of eluent drip washing heavy metal pollution again, it is fixing once more by the soil of handling through fixative in deep layer to drench the heavy metal that; The wherein said fixative metal passivation fixative of attaching most importance to, composition is: any one in the ferric chloride in aqueous solution of pH3-8, polymerization molten iron solution or the lime or two or more mixed aqueous solutions; Described eluent is the mixed aqueous solution of citric acid, b diammonium disodium edta salt and KCl.
2. the method for claim 1 is characterized in that described fixative adopts the mode of punching injection to inject deep soil.
3. method as claimed in claim 2, the degree of depth that it is characterized in that described punching is 50-100cm.
4. the method for claim 1 is characterized in that the fixative that is injected distributes by spreading naturally at deep soil.
5. the method for claim 1 is characterized in that the ratio of the molar concentration of citric acid in the described eluent, b diammonium disodium edta salt and KCl is preferably 9-11: 1-3: 2-4.
6. the method for claim 1, the total mol concentration that it is characterized in that described eluent is 5-50mmol/L.
7. the method for claim 1 is characterized in that described fixative is any one or the two or more aqueous solution that mixes by arbitrary proportion among ferric chloride in aqueous solution, polymerization molten iron solution or the CaO of pH3-8.
8. the method for claim 1, the concentration that it is characterized in that the aqueous solution of described fixative is 0.02-1mol/L.
9. as described any method of claim 1～8, it is characterized in that the step repeated several times of described washed off soil.
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| CN103357655B (en) * | 2013-07-15 | 2016-01-20 | 南京农业大学 | A kind of composite chemical ELUTION METHOD for restoration of soil polluted by heavy metal |
| CN103909091B (en) * | 2014-03-31 | 2015-09-23 | 中国有色桂林矿产地质研究院有限公司 | A kind of restorative procedure of heavy-metal contaminated soil |
| CN104070059B (en) * | 2014-06-06 | 2016-05-11 | 浙江省环境保护科学设计研究院 | A kind of drip washing stabilisation restorative procedure of processing lead-contaminated soil |
| CN105855283A (en) * | 2016-06-15 | 2016-08-17 | 中科院广州化灌工程有限公司 | Treatment method for heavy metal contaminated soil |
| CN106216379B (en) * | 2016-09-05 | 2022-02-15 | 华中科技大学 | Comprehensive leaching remediation method and system for heavy metal contaminated soil |
| CN106433653A (en) * | 2016-09-22 | 2017-02-22 | 北京新源环境有限公司 | Composite eluting agent for restoring Cd and Pb contaminated soil and application method thereof |
| 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 |
| 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 |
| CN108213069A (en) * | 2018-01-04 | 2018-06-29 | 中冶华天工程技术有限公司 | Acid heavy metal contaminated soil remediation method |
| CN108856282B (en) * | 2018-06-01 | 2020-12-08 | 湖南泰谷生态工程有限公司 | Composite remediation method for heavy metal contaminated farmland soil |
| CN110000206B (en) * | 2019-04-30 | 2024-02-27 | 北京贵清科技有限公司 | Rapid layered repair process and repair device for heavy metal contaminated site |
| CN110508608A (en) * | 2019-08-09 | 2019-11-29 | 广东东升实业集团有限公司 | A method of utilizing the leaching and repairing cadmium polluted soil of potash fertilizer |
| CN112574751A (en) * | 2019-09-29 | 2021-03-30 | 中国石油化工股份有限公司 | Ferric-iron-containing heavy metal leaching composition, application thereof and method for repairing heavy metal soil |
| 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 |
| CN113319110B (en) * | 2021-05-18 | 2023-01-24 | 昆明理工大学 | Method for restoring heavy metal contaminated soil and increasing fertilizer by spraying waste mash of alcohol |
| CN115055510B (en) * | 2022-06-14 | 2023-09-22 | 西北大学 | Restoration method and application of heavy metal contaminated soil |
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