CN103934264A - In-situ reduction restoration method for chromium contaminated soil - Google Patents
In-situ reduction restoration method for chromium contaminated soil Download PDFInfo
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- CN103934264A CN103934264A CN201410101586.0A CN201410101586A CN103934264A CN 103934264 A CN103934264 A CN 103934264A CN 201410101586 A CN201410101586 A CN 201410101586A CN 103934264 A CN103934264 A CN 103934264A
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- soil
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- reducing agent
- injection well
- ferrous sulfate
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Abstract
The invention relates to an in-situ reduction restoration method for chromium contaminated soil. The method includes: preparing a mixed solution of 0.1mol/L citric acid with pH of 2.1 and 0.5mol/L ferrous sulfate to serve as a Cr (VI) reducing agent, determining the dosage of the reducing agent according to the total amount of Cr (VI) in the to-be-restored soil, and controlling the mass ratio of Cr (VI) in the soil to ferrous sulfate at 8-9:1; contacting the reducing agent with the to-be-restored soil fully by a way combining surface spraying and a water injection well, injecting the reducing agent into the underground through the water injection well, and laying pumping wells around the water injection well, controlling the flow rate of injected water and pumped water, and controlling the contact time of the reducing agent and the soil at 10min. The in-situ reduction restoration method for chromium contaminated soil provided by the invention has high restoration efficiency on soil with a Cr (VI) content of 1000-5500mg/kg and a permeability coefficient of larger than 8*10<-3>cm/s. The removal rate of Cr (VI) in the soil reaches 96%-99%, and the pH value of the restored soil is 7.5.
Description
Technical field
The invention belongs to contaminated soil repairing and treating technical field, be specifically related to a kind of chromium-polluted soil in-situ reducing restorative procedure.
Background technology
Pollution of chromium place is a kind of typical industrial pollution place, is because unordered the storing up of chromium slag caused.According to investigations, the current chromium slag muck of China is deposited total amount over 6,000,000 tons, being scattered in more than 80 of 20Duo Ge provinces and cities locates, through rainwater leaching, infiltration all the year round, it is hexavalent chromium polluted serious that chromium slag muck is deposited place (and chromium salt production enterprise place), and contaminated soil is by the several times and even the decades of times that are chromium slag muck storage.Along with storing up the carrying out of the harmlessness disposing of chromium slag, chromium slag contaminated site problem becomes increasingly conspicuous.
In environment, the form of common chromium has trivalent chromium and Cr VI.Trivalent chromium normal form with indissoluble hydroxide in soil exists, the Cr in solution
3+concentration is very little, so toxicity is very little; Cr VI solubility is large, thereby toxicity is very strong.The chromium of trace is needed by human.For many years, as High risk population is generally classified pollution of chromium in countries in the world.The governance way of pollution of chromium mainly contains two kinds: the one, and change chromium and have a form in soil, by hexavalent chrome reduction, be trivalent chromium, reduce its transfer ability and bioavailability in environment; The 2nd, chromium is removed from contaminated soil.
In-situ chemical reducing process, its principle is that to utilize iron filings, ferrous sulfate or the facile chemical reducing agent of some other appearance be trivalent chromium by hexavalent chrome reduction, form the compound of indissoluble, thereby reduce animal migration and the bioavailability of chromium in environment, alleviate the harm of pollution of chromium.Reducing agent can directly join in soil, or adopts the form of " permeable oxidation reduction reaction wall (permeable-reactive redox wall) ".When Cr VI mainly concentrates on soil particle surface, directly in soil, add reducing agent to work quickly and effectively.But when Cr VI is present in soil particle inside, needs it from soil, to leach, then reduce it with reducing agent.In general, in-situ chemical reduction restorative procedure, cost is lower, can realize large-scale application.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of chromium-polluted soil in-situ reducing restorative procedure, Cr(VI in soil) percent reduction more than 96%.
For achieving the above object, the technical scheme that the present invention takes is:
A chromium-polluted soil in-situ reducing restorative procedure, comprises the following steps:
1) the ferrous sulfate mixed solution of the pH of the preparation 0.1mol/L citric acid that is 2.1 and 0.5mol/L is as Cr(VI) reducing agent, citric acid and ferrous sulfate volume ratio are 2～5:1;
2) according to Cr(VI in soil to be repaired) total amount, determine the consumption of reduction medicament, control Cr(VI in soil) with the mass ratio of ferrous sulfate be 8～9:1;
3) mode reducing agent being combined with water injection well with earth's surface sprinkle fully contacts with soil to be repaired, and reducing agent is injected into below earth's surface by water injection well, at water injection well, lays pumped well around, and the flow velocity of controlling water filling is 35～65m
3/ d, the flow velocity drawing water is 10～25m
3/ d, makes reducing agent and soil be controlled at 10min time of contact.
Chromium-polluted soil in-situ reducing restorative procedure is to Cr(VI) content is that 1000～5500mg/kg, infiltration coefficient are greater than 8*10
-3the soil of cm/s all has high remediation efficiency, Cr(VI in soil) percent reduction reach 96%～99%, after repairing, soil pH value is 7.5.
Chromium-polluted soil in-situ reducing restorative procedure to the repairing effect of differing texture chromium-polluted soil is: sand > loam > clay.
Tool of the present invention has the following advantages and high-lighting effect:
(1) the medicament economy that this method adopts is easy to get, and non-secondary pollution provides a kind of practicable soil in-situ reduction recovery technique.
(2) this method is to pollution of chromium site remediation successful, Cr(VI in soil after repairing) concentration is at 27～198mg/kg, can recover Soil Utilization function.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1
Take certain carryover contamination place, chromic salts chemical plant is example, and this contaminated site gross area reaches 75000m
2, from earth's surface to level of ground water (16 meters dark) soil, all polluted.Cr(VI in 0～3 meter of soil of its mesexine) content is 3200～11200mg/kg, Cr(VI in 3～16 meters of soil) content is 1450～3000mg/kg, average out to 2120mg/kg left and right, if adopt the scheme of showering, quantities is large, energy consumption is high.This place soil simple structure, 0～3 meter belongs to sand loam, and 3 meters take down to level of ground water is gravel layer, and infiltration coefficient is 4.5*10
-2cm/s, be applicable to adopt chromium-polluted soil in-situ reducing restorative procedure, and it is demonstration area that the implementation case be take wherein 8m*8m*15m.
A chromium-polluted soil in-situ reducing restorative procedure, comprises the following steps:
1) pH of preparation 0.1mol/L is that the ferrous sulfate mixed solution of 2.1 citric acids and 0.5mol/L is as Cr(VI) reducing agent, citric acid and ferrous sulfate volume ratio are 2.8:1;
2) according to Cr(VI in soil to be repaired) total amount, determine the consumption of reduction medicament, control Cr(VI in soil) with the mass ratio of ferrous sulfate be 8.7:1, reducing agent total amount used is 4.68*10
5l;
3) 30% reducing agent is mixed with soil in earth's surface sprinkle mode by 9 showers, 70% reduction medicament is injected into following 6 meters of earth's surface by 1 mouthful of water injection well, and at 4 mouthfuls of pumped wells of surrounding's laying of water injection well, rectangular, the flow velocity of controlling water filling is 45m
3/ d, the flow velocity drawing water is 10m
3/ d～15m
3/ d, reducing agent and soil are controlled at 10min time of contact.
The effect of the present embodiment: clearance Cr(VI in soil) reaches 97.6%, after repairing, soil pH value is 7.5.
Embodiment 2
Take certain chromium slag muck field contaminated site is example, and this contaminated site gross area reaches 21500m
2, from earth's surface to level of ground water (18 meters dark) soil, be subject to pollution in various degree.Cr(VI in 0～3 meter of soil of its mesexine) content is 4300～10400mg/kg, Cr(VI in 3～18 meters of soil) content is 1150～3460mg/kg, average out to 1940mg/kg left and right.This place soil simple structure, 0～3 meter belongs to sand, take down to level of ground water as loam and gravel layer for 3 meters, and infiltration coefficient is 6.2*10
-2cm/s, be applicable to adopt chromium-polluted soil in-situ reducing restorative procedure, and it is demonstration area that the implementation case be take wherein 6m*4m*16m.
A chromium-polluted soil in-situ reducing restorative procedure, comprises the following steps:
1) pH of preparation 0.1mol/L is that the ferrous sulfate mixed solution of 2.1 citric acids and 0.5mol/L is as Cr(VI) reducing agent, citric acid and ferrous sulfate volume ratio are 3.1:1;
2) according to Cr(VI in soil to be repaired) total amount, determine the consumption of reduction medicament, control Cr(VI in soil) with the mass ratio of ferrous sulfate be 8.8:1;
3) 26% reducing agent is mixed with soil in earth's surface sprinkle mode by 9 showers, 74% reduction medicament is injected into following 6 meters of earth's surface by 1 mouthful of water injection well, and at 4 mouthfuls of pumped wells of surrounding's laying of water injection well, rectangular, the flow velocity of controlling water filling is 42m
3/ d, the flow velocity drawing water is 10m
3/ d～13m
3/ d, reducing agent and soil are controlled at 10min time of contact.
The effect of the present embodiment: clearance Cr(VI in soil) reaches 98.8%, after repairing, soil pH value is 7.5.
Embodiment 3
In certain carryover contamination place, chromic salts chemical plant, marking plot 4m*3m*12m is demonstration area, from earth's surface to level of ground water (15 meters dark) soil, is all polluted.0～3 meter of genus loam of this Site Soil, take down to level of ground water as clay and loam for 3 meters, and infiltration coefficient is 8.4*10
-3cm/s, adopts chromium-polluted soil in-situ reducing restorative procedure.
A chromium-polluted soil in-situ reducing restorative procedure, comprises the following steps:
1) pH of preparation 0.1mol/L is that the ferrous sulfate mixed solution of 2.1 citric acids and 0.5mol/L is as Cr(VI) reducing agent, citric acid and ferrous sulfate volume ratio are 3:1;
2) according to Cr(VI in soil to be repaired) total amount, determine the consumption of reduction medicament, control Cr(VI in soil) with the mass ratio of ferrous sulfate be 8.7:1;
3) 30% reducing agent is mixed with soil in earth's surface sprinkle mode by 9 showers, 70% reduction medicament is injected into following 6 meters of earth's surface by 1 mouthful of water injection well, and at 4 mouthfuls of pumped wells of surrounding's laying of water injection well, rectangular, the flow velocity of controlling water filling is 45m
3/ d, the flow velocity drawing water is 10m
3/ d～12m
3/ d, more than reducing agent and soil are controlled at 10min time of contact.
The effect of the present embodiment: clearance Cr(VI in soil) reaches 96.42%, after repairing, soil pH value is 7.5.
Claims (3)
1. a chromium-polluted soil in-situ reducing restorative procedure, is characterized in that, comprises the following steps:
1) pH of preparation 0.1mol/L is that the ferrous sulfate mixed solution of 2.1 citric acids and 0.5mol/L is as Cr(VI) reducing agent, citric acid and ferrous sulfate volume ratio are 2～5:1;
2) according to Cr(VI in soil to be repaired) total amount, determine the consumption of reduction medicament, control Cr(VI in soil) with the mass ratio of ferrous sulfate be 8～9:1;
3) mode reducing agent being combined with water injection well with earth's surface sprinkle fully contacts with soil to be repaired, and reducing agent is injected into below earth's surface by water injection well, at water injection well, lays pumped well around, and the flow velocity of controlling water filling is 35～65m
3/ d, the flow velocity drawing water is 10～25m
3/ d, makes reducing agent and soil be controlled at 10min time of contact.
2. a kind of chromium-polluted soil in-situ reducing restorative procedure according to claim 1, is characterized in that: chromium-polluted soil in-situ reducing restorative procedure is to Cr(VI) content is that 1000～5500mg/kg, infiltration coefficient are greater than 8*10
-3the soil of cm/s all has high remediation efficiency, Cr(VI in soil) clearance reach 96%～99%, after repairing, soil pH value is 7.5.
3. a kind of chromium-polluted soil in-situ reducing restorative procedure according to claim 1, is characterized in that: chromium-polluted soil in-situ reducing restorative procedure to the repairing effect of differing texture chromium-polluted soil is: sand > loam > clay.
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| CN104475440A (en) * | 2014-12-04 | 2015-04-01 | 唐山柯林环保科技有限公司 | In-situ remediation method of chromium pollution site and special water treatment equipment |
| CN104611250A (en) * | 2014-11-24 | 2015-05-13 | 苏州嘉禧萝生物科技有限公司 | Chromium polluted soil composite microbial repairing agent, preparation method and application thereof |
| CN104815844A (en) * | 2015-04-03 | 2015-08-05 | 北京建工环境修复股份有限公司 | Chromium contamination in-situ remediation method |
| CN105295932A (en) * | 2015-11-24 | 2016-02-03 | 北京高能时代环境技术股份有限公司 | Eluting agent used for remediation of chromium-contaminated soil, remediation method and apparatus |
| CN105537260A (en) * | 2015-12-11 | 2016-05-04 | 上海交通大学 | Synchronous soil heavy-metal Zn and Cr stabilizing remediation method |
| CN105880271A (en) * | 2016-07-02 | 2016-08-24 | 李康 | Method for repairing mine chrome heavy metal pollution soil |
| WO2017219791A1 (en) * | 2016-06-23 | 2017-12-28 | 北京建工环境修复股份有限公司 | Method for determining diffusion radius of contaminated soil and groundwater in situ injection repairing |
| CN111228712A (en) * | 2020-02-13 | 2020-06-05 | 国家电投集团远达环保工程有限公司重庆科技分公司 | Heavy metal stabilizing chelating agent, aqueous solution thereof and preparation methods thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104611250A (en) * | 2014-11-24 | 2015-05-13 | 苏州嘉禧萝生物科技有限公司 | Chromium polluted soil composite microbial repairing agent, preparation method and application thereof |
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| CN105295932A (en) * | 2015-11-24 | 2016-02-03 | 北京高能时代环境技术股份有限公司 | Eluting agent used for remediation of chromium-contaminated soil, remediation method and apparatus |
| CN105537260A (en) * | 2015-12-11 | 2016-05-04 | 上海交通大学 | Synchronous soil heavy-metal Zn and Cr stabilizing remediation method |
| CN105537260B (en) * | 2015-12-11 | 2018-05-01 | 上海交通大学 | A kind of restorative procedure of synchronism stability heavy metal-polluted soil Zn and Cr |
| WO2017219791A1 (en) * | 2016-06-23 | 2017-12-28 | 北京建工环境修复股份有限公司 | Method for determining diffusion radius of contaminated soil and groundwater in situ injection repairing |
| US10788408B2 (en) | 2016-06-23 | 2020-09-29 | Bceg Environmental Remediation Co., Ltd | Method for determining diffusion radius of in-situ injection and remediation of contaminated soil and groundwater |
| CN105880271A (en) * | 2016-07-02 | 2016-08-24 | 李康 | Method for repairing mine chrome heavy metal pollution soil |
| CN111228712A (en) * | 2020-02-13 | 2020-06-05 | 国家电投集团远达环保工程有限公司重庆科技分公司 | Heavy metal stabilizing chelating agent, aqueous solution thereof and preparation methods thereof |
| CN111228712B (en) * | 2020-02-13 | 2021-07-16 | 国家电投集团远达环保工程有限公司重庆科技分公司 | Heavy metal stabilizing chelating agent, aqueous solution thereof and preparation methods thereof |
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