CN103736723B - Heavy-metal contaminated soil restorative procedure integrated with underground water - Google Patents
Heavy-metal contaminated soil restorative procedure integrated with underground water Download PDFInfo
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- CN103736723B CN103736723B CN201310278001.8A CN201310278001A CN103736723B CN 103736723 B CN103736723 B CN 103736723B CN 201310278001 A CN201310278001 A CN 201310278001A CN 103736723 B CN103736723 B CN 103736723B
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Abstract
The present invention relates to a kind of heavy-metal contaminated soil restorative procedure integrated with underground water.Be specially: heavy metal stabilization agent is applied in contaminated soil in proportion, polluted underground water is extracted out simultaneously, even sprinkling or to water in the pollution that is filled in and applies stabilization agent in earth, heavy metal in underground water retained by soil and adsorb with stabilization agent together with heavy metal original in soil, precipitate, the effect such as ion-exchange, heavy metal is stablized, underground water after being repaired returns and permeates the ground, thus reaches the effect that contaminated soil and underground water repairs simultaneously.Separate restorative procedure with traditional upper earth with underground water to compare, method of the present invention can repair the heavy metal in polluted underground water and soil in a better simply system simultaneously, reaches the object that integration is repaired.This method has the features such as treatment process is simple, cost is low.
Description
Technical field
The invention belongs to field of environment engineering technology, be specifically related to a kind of heavy-metal contaminated soil restorative procedure integrated with underground water.
Background technology
In recent years, due to the pollution of industrial and agricultural production and the continuous increase of strength of human activities, using of a large amount of chemical fertilizer, agricultural chemicals, the leakage of petroleum chemicals and fault discharge, the hazardous material situations that poisonous, hazardous solid waste reclamation causes, all causes soil pollution enlarged areas, and pollution level is deepened.And soil and groundwater also exists and contacts closely, contaminated soil easily causes down and covers underground water and also produce pollution, need to process contaminated soil and underground water, but, current soil and groundwater pollution amelioration is all individually repair substantially, processes if contaminated soil and underground water are integrated in a technique, can simplify processes technique, save disposal cost, save land resource.Therefore, repair integrated with underground water for soil the concern more and more causing people.At present, domestic also not about the patent of soil underground water integration recovery technique.
Summary of the invention
The object of the invention is to provide a kind of heavy-metal contaminated soil restorative procedure integrated with underground water for soil and groundwater heavy metal pollution problem.Be specially and soil chemistry stabilization method is combined with underground water pump-and-treat system method, heavy metal stabilization agent is added in contaminated soil, polluted underground water is extracted out by pump, leaching is in the contaminated soil adding heavy metal stabilization agent, make the effects such as the heavy metal in stabilization agent and contaminated soil and underground water precipitates, absorption, thus change the form of heavy metal, heavy metal is stablized, and polluted underground water is through adding the process such as adsorption by soil, precipitation of stabilization agent, ooze under freedom, again recharge groundwater.
The object of the invention is to be achieved through the following technical solutions:
The present invention relates to a kind of heavy-metal contaminated soil restorative procedure integrated with underground water, comprise the steps:
A, heavy metal stabilization agent is applied in contaminated soil;
B, by polluted underground water extract out, spray or water be filled in described in apply in the contaminated soil of heavy metal stabilization agent; Heavy metal in described polluted underground water is retained by soil and has an effect with heavy metal stabilization agent together with heavy metal original in soil, and heavy metal is stablized;
C, described heavy metal are trapped and underground water after stablizing returns and permeates the ground, and complete that described heavy metal soil is integrated with underground water to be repaired.
Preferably, in steps A, the selection of described heavy metal stabilization agent is specially: to the contaminated soil in contaminated site and polluted underground water investigation, sampling, research and application, determine the kind of heavy metal contaminants in contaminated soil and polluted underground water, pollute the volume of distribution, pollution level and polluted underground water; According to the kind of described heavy metal contaminants, the selecting of character determination heavy metal stabilization agent material of polluting distribution, pollution level and contaminated soil.
Preferably, in steps A, the determination of described heavy metal stabilization agent consumption is specially: according to the addition of the concentration of heavy metal in contaminated soil and polluted underground water and the volume determination heavy metal stabilization agent of polluted underground water.
Preferably, in steps A, described heavy metal stabilization agent is phosphorated material.
Preferably, described phosphorated material comprises apatite, double superhosphate.
Preferably, described phosphorated material be containing P ratio be the apatite of 1: 1 and the mixture of double superhosphate.
Preferably, in described heavy metal stabilization agent, the mol ratio of P element and heavy metal is (2 ~ 4): 1.
Preferably, in step B, described extraction out by polluted underground water is specially: in the place at described contaminated soil place, beat groundwater sampling well; Polluted underground water is extracted out from sampled well.
Preferably, in step B, acting as that described heavy metal and heavy metal stabilization agent occur is adsorbed, precipitate, one or more in ion-exchange.
Heavy-metal contaminated soil of the present invention restorative procedure integrated with underground water is that chemically stable method is combined with underground water pump-and-treat system method the integrated restorative procedure formed.The principle that this integrated restorative procedure fixes heavy metal is: the heavy metal in soil and underground water all by adsorbing with the heavy metal stabilization agent added in soil, precipitating, the effect such as ion-exchange, heavy metal in underground water is removed, and heavy metal in soil is stablized.Concrete fixed mechanism is as follows:
In apatite and double superhosphate stable soil and underground water, the mechanism of heavy metal is mainly based on the absorption of phosphonate functional group, precipitation or co-precipitation, adsorption or complexing mechanism, and reaction equation is summarized as follows:
5M
2++ 3H
2pO
4 -+ Cl
-=M
5(PO
4)
3cl+6H
+(M represents heavy metal as Pb, Cd etc.) (1.1)
≡ POH+M
2+=≡ POM
++ H
+(≡ POH represents apatite surface) (1.2)
≡ S-HPO
4 2-+ M
2+=≡ S-HPO
4 2--M
2+(≡ S represents Soil oxidation thing surface) (1.3)
Compared with prior art, the present invention has following beneficial effect:
1, heavy-metal contaminated soil and underground water repair is simultaneously achieved;
2, simplify the difference treatment process of heavy-metal contaminated soil and polluted underground water, reduce disposal cost, save soil resource.
Accompanying drawing explanation
By reading the detailed description done non-limiting example with reference to the following drawings, other features, objects and advantages of the present invention will become more obvious:
Fig. 1 is the flow chart of heavy-metal contaminated soil of the present invention restorative procedure integrated with underground water.
Detailed description of the invention
Below in conjunction with drawings and the specific embodiments, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
The flow chart of heavy-metal contaminated soil of the present invention restorative procedure integrated with underground water as shown in Figure 1, first to contaminated site carry out contaminated soil, polluted underground water investigation, sampling plan is set, carry out the sampling of contaminated soil and underground water, result according to research and application, determine the kind of place heavy metal contaminants, pollute distribution, the volume of pollution level and polluted underground water; Then according to the kind of heavy metal contaminants, pollution level, the agent of soil property determination heavy metal stabilization, as pollutions such as Pb, Cu, Zn, apatite, double superhosphate etc. can be selected; According to concentration and the area (volume) of heavy metal in soil and groundwater, setting repair materials addition.General phosphorated material addition (P content) is (2 ~ 4) with the molar concentration ratio of heavy metal pollution amount: 1, by heavy metal stabilization agent and pollution soil layer Homogeneous phase mixing; Then, with pump, polluted underground water is extracted out from extraction well, evenly be sprayed at contaminated site, make to ooze under freedom in polluted underground water soil after repair, utilize the mechanism such as the absorption of stabilized metal agent in soil, filtration, precipitation, remove heavy metal in underground water, simultaneously by the heavy metal in underground water together with heavy metal original in soil stabilized dose be fixed in soil, the underground water after being repaired returns and permeates the ground.Embody rule is shown in following embodiment:
embodiment 1
Certain irrigating region Cd contaminated soil (containing 60mg/kgCd), polluted underground water concentration is 10mg/LPb, 0.3mg/LCd, 10mg/LZn, heavy metal-polluted soil stabilisation repair materials is contain apatite and the double superhosphate mixture that P ratio is 1: 1, addition is the mol ratio of phosphorus and heavy metal is 2: 1, and groundwater abstraction evenly waters in the contaminated soil being filled in and applying phosphorated material.Through the reparation of 40 days, integrated processing system coprocessing polluted underground water amount was 673L/Kg.After leaching terminates, soil retains the amount of Pb in polluted underground water up to being 9915mg/Kg, and in underground water, Pb clearance reaches 91%; The amount that soil retains Cd in polluted underground water is 143mg/Kg, Cd clearance is 40.2%; The amount that soil retains Zn in polluted underground water is 3477mg/Kg, Zn clearance is 45.2%.Terminate to leaching, the adsorption capacity of integrated processing system to Pb reaches capacity not yet, still has and continues to retain the ability removing Pb in underground water, but reach capacity to the adsorbance of Cd and Zn.CaCl in soil
2extract state Pb compared with the control with TCLP, have dropped 60.5% and 62.8% respectively; CaCl
2state Cd is extracted compared with the control, soil CaCl with TCLP
2extract state Cd and have dropped 12.3%, but TCLP extracts, and state Cd is substantially constant to be worked as; CaCl
2extract state Zn compared with the control with TCLP, have dropped 7.5% and 10.2% respectively.To sum up, the soil of phosphorated material induction, in underground water heavy metal integration repair the fixing of the removal that simultaneously can realize heavy metal in polluted underground water and Heavy Metals in Contaminated Soils, especially to the successful of Pb and fixed capacity is larger.
embodiment 2
Contaminated soil (2850mg/kgPb, 31mg/kgCd, 975mg/kgZn) near certain smeltery, polluted underground water concentration is 10mg/LPb, 0.3mg/LCd, 10mg/LZn, heavy metal-polluted soil stabilisation repair materials is contain phosphorus ore tailing and the double superhosphate mixture that P ratio is 1: 1, addition is that the mol ratio of phosphorus and heavy metal is about 4: 1, and groundwater abstraction evenly waters to be filled in and is applied with in the contaminated soil of phosphorated material.Through the integration reparation of 120 days, coprocessing polluted underground water amount was 605.5L/Kg.After leaching terminates, soil retains the amount of Pb in polluted underground water up to being 14504mg/Kg, and in underground water, Pb clearance reaches 87.6%; The amount that soil retains Cd in polluted underground water is 64.6mg/Kg, Cd clearance is 30.0%; Substantially effect is not removed to Zn in underground water.Terminate to leaching, the adsorption capacity of integrated processing system to Pb reaches capacity not yet, still has and continues to be detained the ability removing Pb in underground water, but reach capacity to the adsorbance of Cd and Zn.CaCl in soil
2extract state Pb concentration lower than Flame Atomic Absorption Spectrometry detectability, TCLP extracts state Pb compared with the control, declines 51.0%; CaCl
2extract state Cd compared with the control with TCLP, have dropped 41.7% and 31.9% respectively; CaCl
2extract state Zn compared with the control with TCLP, decline 3.2% and 19% respectively.To sum up, the soil of phosphorated material induction, in underground water heavy metal integration repair the fixing of the removal that simultaneously can realize heavy metal in polluted underground water and Heavy Metals in Contaminated Soils, especially to the successful of Pb and fixed capacity is comparatively large, but less to Zn effect.
embodiment 3
Certain irrigating region soil is containing 86.6mg/kgCu, 175.8mg/kgZn, 3.48mg/kgCd, 94.2mg/kgCr, 22.9mg/kgPb, and underground water is containing 5.66 μ g/LCu, 559.2 μ g/LZn, 0.48 μ g/LCd, 9.18 μ g/LCr, Pb5.17 μ g/L.Heavy metal-polluted soil stabilisation repair materials is contain apatite and the double superhosphate mixture that P ratio is 1: 1, addition is that the mol ratio of phosphorus and heavy metal is about 3: 1, groundwater abstraction evenly waters to be filled in and is applied with in the contaminated soil of phosphorated material, and plants Chinese cabbage on contaminated soil.Through the integration reparation of 90 days, Chinese cabbage content of beary metal obviously declined, and Cu decline 10.2%, Cr decline 29.4%, Cd decline 21.6%, Pb declines 50.9%; Underground water heavy metal Cu decline 34.7%, Cd decline 80%, Pb declines 20%.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (4)
1. a heavy-metal contaminated soil restorative procedure integrated with underground water, is characterized in that, comprise the steps:
A, heavy metal stabilization agent is applied in contaminated soil;
B, by polluted underground water extract out, spray or water be filled in described in apply in the contaminated soil of heavy metal stabilization agent; Heavy metal in described polluted underground water is retained by soil and has an effect with heavy metal stabilization agent together with heavy metal original in soil, and heavy metal is stablized;
C, described heavy metal are trapped and underground water after stablizing returns and permeates the ground, and complete that described heavy-metal contaminated soil is integrated with underground water to be repaired;
In steps A, the selection of described heavy metal stabilization agent is specially: to the contaminated soil in contaminated site and polluted underground water investigation, sampling, research and application, determine the kind of heavy metal contaminants in contaminated soil and polluted underground water, pollute the volume of distribution, pollution level and polluted underground water; According to the kind of described heavy metal contaminants, the selecting of character determination heavy metal stabilization agent material of polluting distribution, pollution level and contaminated soil;
In steps A, the determination of described heavy metal stabilization agent consumption is specially: according to the addition of the concentration of heavy metal in contaminated soil and polluted underground water and the volume determination heavy metal stabilization agent of polluted underground water;
In steps A, described heavy metal stabilization agent is phosphorated material;
In step B, described extraction out by polluted underground water is specially: in the place at described contaminated soil place, beat groundwater sampling well; Polluted underground water is extracted out from sampled well;
In step B, acting as that described heavy metal and heavy metal stabilization agent occur is adsorbed, precipitate, one or more in ion-exchange.
2. heavy-metal contaminated soil according to claim 1 restorative procedure integrated with underground water, it is characterized in that, described phosphorated material comprises apatite, double superhosphate.
3. heavy-metal contaminated soil according to claim 2 restorative procedure integrated with underground water, is characterized in that, described phosphorated material is than being the apatite of 1:1 and the mixture of double superhosphate containing P.
4. the restorative procedure integrated with underground water of the heavy-metal contaminated soil according to claim 1,2 or 3, is characterized in that, in described heavy metal stabilization agent, the mol ratio of P element and heavy metal is (2 ~ 4): 1.
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| CN104043646A (en) * | 2014-06-24 | 2014-09-17 | 齐绍武 | Method for separating harmful heavy metals in paddy field |
| CN106126694A (en) * | 2016-06-30 | 2016-11-16 | 中国科学院烟台海岸带研究所 | The support of a kind of impurely Rehabilitation decision and the construction method of online evaluation platform |
| CN108393345A (en) * | 2018-03-09 | 2018-08-14 | 江苏索尔雷米环保科技有限公司 | A kind of integrated restorative procedure being used for contaminated soil and underground water |
| CN111451258A (en) * | 2020-04-27 | 2020-07-28 | 浙江省环境工程有限公司 | Pollute soil-groundwater integration repair system |
Citations (4)
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|---|---|---|---|---|
| CN101664757A (en) * | 2009-09-29 | 2010-03-10 | 农业部环境保护科研监测所 | Method for restoring heavy metal pollution of vegetable field soil with in-situ passivation method |
| CN101698521A (en) * | 2009-11-17 | 2010-04-28 | 重庆大学 | Method for electrically restoring soil and underground water |
| CN101829673A (en) * | 2009-03-09 | 2010-09-15 | 江西金达莱环保研发中心有限公司 | Soil remediation method |
| CN102335674A (en) * | 2010-07-27 | 2012-02-01 | 周静 | Method for restoring soil polluted by heavy metals Cu and Cd in apatite field |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101829673A (en) * | 2009-03-09 | 2010-09-15 | 江西金达莱环保研发中心有限公司 | Soil remediation method |
| CN101664757A (en) * | 2009-09-29 | 2010-03-10 | 农业部环境保护科研监测所 | Method for restoring heavy metal pollution of vegetable field soil with in-situ passivation method |
| CN101698521A (en) * | 2009-11-17 | 2010-04-28 | 重庆大学 | Method for electrically restoring soil and underground water |
| CN102335674A (en) * | 2010-07-27 | 2012-02-01 | 周静 | Method for restoring soil polluted by heavy metals Cu and Cd in apatite field |
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Effective date of registration: 20190426 Address after: Room 803, Building 1, 100 Qinzhou Road, Xuhui District, Shanghai, 200235 Patentee after: Shanghai Shenglong Environment Remediation Technologies Co., Ltd. Address before: Room 602, No. 69, 811 Lane, Dongchuan Road, Minhang District, Shanghai, 200240 Co-patentee before: Shanghai Shenglong Environment Remediation Technologies Co., Ltd. Patentee before: Cao Xinde |
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Address after: Room 803, Building 1, 100 Qinzhou Road, Xuhui District, Shanghai, 200235 Patentee after: Sinochem environmental remediation (Shanghai) Co.,Ltd. Address before: Room 803, Building 1, 100 Qinzhou Road, Xuhui District, Shanghai, 200235 Patentee before: SHANGHAI SHENGLONG ENVIRONMENT REMEDIATION TECHNOLOGIES Co.,Ltd. |