CN105694894A - Preparation method and application of hexavalent chromium contaminated soil conditioner - Google Patents
Preparation method and application of hexavalent chromium contaminated soil conditioner Download PDFInfo
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- CN105694894A CN105694894A CN201610154106.6A CN201610154106A CN105694894A CN 105694894 A CN105694894 A CN 105694894A CN 201610154106 A CN201610154106 A CN 201610154106A CN 105694894 A CN105694894 A CN 105694894A
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- soil
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/06—Calcium compounds, e.g. lime
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the field of soil restoration and provides a preparation method and application of a hexavalent chromium contaminated soil conditioner. The conditioner is composed of a first chemical agent and a second chemical agent. By means of the conditioner, hexavalent chromium in soil can be efficiently reduced into trivalent chromium low in toxicity, the soil structure is improved, the acid-base property of improved soil is effectively stabilized within a certain range, long-time stability of trivalent chromium in soil is guaranteed, and environmental risk is greatly lowered. The preparation method of the conditioner is simple, hexavalent chromium in improved soil is low in leaching toxicity, appropriate in acid-base range and long in stable cycle, environmental benefits are obvious, and it is beneficial to further development and utilization of soil. The conditioner has great application significance on chemical restoration of hexavalent chromium contaminated soil, and market application prospect is wide.
Description
Technical field
The invention belongs to contaminated soil remediation technical field, be specifically related to preparation method and the application of a kind of hexavalent chromium polluted soil conditioner。
Background technology
All poisonous containing chromium compound, containing in chromium compound, chromic toxicity is maximum all, and it has been listed in one of eight kinds of chemical substances that harm is maximum, is also one of 129 kinds of priority pollutants generally acknowledging of Environmental Protection in America tissue。
The method of existing hexavalent chromium polluted soil remediation has a lot, mainly has chemical leaching method, biological restoration, electricity repairing method, curing/stabilizing method, chemical reduction method etc.。Wherein chemical leaching method can being limited in scope of practical application, require that chemical leaching can be fully contacted with the Cr VI in soil and by its eluting, this method is only applicable to the soil that the infiltration coefficients such as sandy loam are big, and after its drip washing, eluent must be dealt carefully with, it is to avoid secondary pollution。Biological restoration includes microorganism remediation and phytoremediation two kinds, microorganism remediation refers to the biochemical action utilizing microorganism in soil, it is trivalent chromium by hexavalent chrome reduction in soil, and by stable for trivalent chromium in soil, current microorganism remediation technology remains a need for research work basic in a large number；Phytoremediation technology includes plant extract technology, plant-securing technique and phytovolatilization technology, relative to other technologies, phytoremediation cost is low, environmental friendliness, but its repairing efficiency is long, for the engineering that construction period is short, it is difficult to quick reparation in a short time, and the soil that pollution level is big is existed the problem being difficult to repair。Curing/stabilizing method is the method that current restoration of soil polluted by heavy metal is conventional, due to chromic high toxicity and reducibility, before it is carried out curing/stabilizing, to be first generally trivalent chromium by hexavalent chrome reduction。Therefore, chemical reduction method is a kind of method of hexavalent chromium polluted soil of effective improvement。This method is generally with chemical reducing agents such as ferrous salt for basic medicament, and the repairing efficiency of soil is short, effect is obvious, it is possible to large-scale application。
The soil conditioner invented, while reduction of hexavalent chromium, the aluminosilicate such as flyash contained can improve the structure of soil。Additionally, trivalent chromium in alkalescence soil with Cr (OH)3The form of precipitation exists, and the soda acid of soil after reduction can be maintained within a certain range by modifying agent, is conducive to chromium compound existence steady in a long-term in soil after improvement。
Summary of the invention
The preparation method that an object of the present invention is to provide a kind of hexavalent chromium polluted soil conditioner。
The two of the purpose of the present invention are the improvement that the modifying agent of preparation is used for hexavalent chromium polluted soil property, and after improvement, the chromic Leaching of soil significantly reduces, Soil structure improves, the animal migration of chromium compound and can reducing by bioavailability。
The three of the purpose of the present invention are that after improvement, soil ph is suitable for, and trivalent chromium compound is with the form stable existence in soil for a long time of precipitation state, and stable period is long。
The present invention implements by the following technical solutions, specifically implements according to following steps:
1. the preparation method of a hexavalent chromium polluted soil conditioner
1) modifying agent of hexavalent chromium polluted soil is made up of 1# medicament and 2# medicament, and 1# medicament is formed than mixing and stirring with certain mass by hexavalent chrome reduction agent, flyash, gangue, slag, quick lime, and sealing is kept in Dark Place；Described hexavalent chrome reduction agent, is by the mixture of one or more chemical reducing agents in ferrous sulfate, ferrous chloride, sodium sulfite, sodium sulfide, calcium polysulfide；
Described flyash, gangue, slag, quick lime, particle diameter is respectively less than 1mm；
Described 1# medicament, refers to that according to mass ratio be hexavalent chrome reduction agent: flyash: gangue: slag: quick lime=(40 ~ 70): (30 ~ 60): (6 ~ 10): (2 ~ 10): the mixture that (1 ~ 5) is mixed to get；
2) 2# medicament refers to soil acid-base buffering medicament, the mixture that 2# medicament is made up of four kind of two acid phosphate, its composition and mass ratio are diammonium phosphate: ammonium dihydrogen phosphate: sodium dihydrogen phosphate: disodium hydrogen phosphate=(5 ~ 10): (10 ~ 20): (30 ~ 50): (30 ~ 50)。
2. modifying agent application in hexavalent chromium polluted soil improvement
1) mensuration of contaminated soil Cr VI leaching content and pH
The preparation of lixiviating solution: the mixed liquor of concentrated sulphuric acid that mass ratio is 2:1 with concentrated nitric acid is added in deionized water, regulates pH to 3.20 ± 0.05；
Soil sample crushes, crosses the sieve in 9.5mm aperture, it it is soil according to mass ratio: the ratio of lixiviating solution=1:10, upset vibration 18 hours, then adopts " solid waste Determination of Hexavalent Chromium diphenyl carbazide spectrophotometry (GBT15555.4-1995) " to measure chromic content in soil extract；
Soil pH value is measured according to the requirement of national standard " mensuration (NY/T1377-2007) of soil pH "；
2) improvement of chromium-polluted soil
By soil breaking, the sieve crossing 2mm aperture, regulate the moisture content of soil to 40% ~ 80%, according to Cr VI leaching content and pH value in soil, add the 1# medicament of 8% ~ 20%, stir, after maintenance 7 ~ 30 days, measure the pH value of soil, further according to the 2# medicament needing addition 5% ~ 30%, continue maintenance 30 ~ 60 days, after improvement, soil Cr VI Leaching meets " hazardous waste judging standard leaching characteristic identification (GB5085.3-2007) " Cr VI Leaching requirement, and soil pH is in 6 ~ 9 scopes。
The invention have the advantages that:
(1) Cr VI in contaminated soil is converted into trivalent chromium by the modifying agent invented, and makes Cr VI Leaching reduce, and effectively reduces toxicity and the bioavailability of chromium compound；
(2) aluminosilicate such as flyash, gangue is the modifying agent of raw material, thus it is possible to vary the physical arrangement of soil, and after being conducive to improvement, the further of soil develops；
(3) introducing of soil acid-base buffer agent can increase the soil buffer capacity to soda acid, by soil acidity or alkalinity long-term stability within the specific limits, trivalent chromium exists with precipitation state for a long time, and the animal migration of chromium compound is low, is conducive to the long term maintenance of soil hypotoxicity environment after improveing。
Detailed description of the invention
The preparation of the hexavalent chromium polluted soil conditioner of embodiment 1
According to quality than hexavalent chrome reduction agent: flyash: gangue: slag: quick lime=60:30:6:3:1 mix homogeneously, prepare 1# medicament, seal preserve, wherein, flyash, gangue, slag, quick lime particle diameter be respectively less than 1mm；
It is diammonium phosphate according to mass ratio: ammonium dihydrogen phosphate: sodium dihydrogen phosphate: disodium hydrogen phosphate=8:15:40:37 mix homogeneously, prepares 2# medicament。
The preparation of the hexavalent chromium polluted soil conditioner of embodiment 2
According to quality than hexavalent chrome reduction agent: flyash: gangue: slag: quick lime=40:40:8:8:4 mix homogeneously, prepare 1# medicament, seal preserve, wherein, flyash, gangue, slag, quick lime particle diameter be respectively less than 1mm；
It is diammonium phosphate according to mass ratio: ammonium dihydrogen phosphate: sodium dihydrogen phosphate: disodium hydrogen phosphate=10:10:50:30 mix homogeneously, prepares 2# medicament。
The application in hexavalent chromium polluted soil conditioner of embodiment 3 modifying agent
1) mensuration of contaminated soil Cr VI leaching content and pH
The preparation of lixiviating solution: the mixed liquor of concentrated sulphuric acid that mass ratio is 2:1 with concentrated nitric acid is added in deionized water, regulates pH to 3.20 ± 0.05；
Soil sample crushes, crosses the sieve in 9.5mm aperture, it it is soil according to mass ratio: the ratio of lixiviating solution=1:10, upset vibration 18 hours, then adopts " solid waste Determination of Hexavalent Chromium diphenyl carbazide spectrophotometry (GBT15555.4-1995) " to measure chromic content in soil extract；
Soil pH value is measured according to the requirement of national standard " mensuration (NY/T1377-2007) of soil pH "；
2) improvement of chromium-polluted soil
By soil breaking, the sieve crossing 2mm aperture, regulate the moisture content of soil to 60%, according to Cr VI leaching content and pH value in soil, add the 1# medicament of 10%, stir, after maintenance 30 days, measure the pH value of soil, further according to needing to add the 2# medicament of 10%, continuing maintenance 40 days, after detection improvement, soil Cr VI Leaching and pH meet requirement；
Described 1# medicament, for the 1# medicament prepared by embodiment 1 or embodiment 2；
Described 2# medicament, for the 2# medicament prepared by embodiment 1 or embodiment 2。
The application in hexavalent chromium polluted soil conditioner of embodiment 4 modifying agent
1) mensuration of contaminated soil Cr VI leaching content and pH
The preparation of lixiviating solution: the mixed liquor of concentrated sulphuric acid that mass ratio is 2:1 with concentrated nitric acid is added in deionized water, regulates pH to 3.20 ± 0.05；
Soil sample crushes, crosses the sieve in 9.5mm aperture, it it is soil according to mass ratio: the ratio of lixiviating solution=1:10, upset vibration 18 hours, then adopts " solid waste Determination of Hexavalent Chromium diphenyl carbazide spectrophotometry (GBT15555.4-1995) " to measure chromic content in soil extract；
Soil pH value is measured according to the requirement of national standard " mensuration (NY/T1377-2007) of soil pH "；
2) improvement of chromium-polluted soil
By soil breaking, the sieve crossing 2mm aperture, regulate the moisture content of soil to 50%, according to Cr VI leaching content and pH value in soil, add the 1# medicament of 20%, stir, after maintenance 30 days, measure the pH value of soil, further according to needing to add the 2# medicament of 5%, continuing maintenance 60 days, after detection improvement, soil Cr VI Leaching and pH meet requirement；
Described 1# medicament, for the 1# medicament prepared by embodiment 1 or embodiment 2；
Described 2# medicament, for the 2# medicament prepared by embodiment 1 or embodiment 2。
Claims (2)
1. the preparation method of a hexavalent chromium polluted soil conditioner, it is characterised in that comprise the steps:
1) modifying agent of hexavalent chromium polluted soil is made up of 1# medicament and 2# medicament, and 1# medicament is formed than mixing and stirring with certain mass by hexavalent chrome reduction agent, flyash, gangue, slag, quick lime, and sealing is kept in Dark Place；Described hexavalent chrome reduction agent, is by the mixture of one or more chemical reducing agents in ferrous sulfate, ferrous chloride, sodium sulfite, sodium sulfide, calcium polysulfide；
Described flyash, gangue, slag, quick lime, particle diameter is respectively less than 1mm；
Described 1# medicament, refers to that according to mass ratio be hexavalent chrome reduction agent: flyash: gangue: slag: quick lime=(40 ~ 70): (30 ~ 60): (6 ~ 10): (2 ~ 10): the mixture that (1 ~ 5) is mixed to get；
2) 2# medicament refers to soil acid-base buffering medicament, the mixture that 2# medicament is made up of four kind of two acid phosphate, its composition and mass ratio are diammonium phosphate: ammonium dihydrogen phosphate: sodium dihydrogen phosphate: disodium hydrogen phosphate=(5 ~ 10): (10 ~ 20): (30 ~ 50): (30 ~ 50)。
2. the preparation method of a kind of hexavalent chromium polluted soil conditioner as claimed in claim 1, it is characterised in that comprise the following steps:
1) mensuration of contaminated soil Cr VI leaching content and pH
The preparation of lixiviating solution: the mixed liquor of concentrated sulphuric acid that mass ratio is 2:1 with concentrated nitric acid is added in deionized water, regulates pH to 3.20 ± 0.05；
Soil sample crushes, crosses the sieve in 9.5mm aperture, it it is soil according to mass ratio: the ratio of lixiviating solution=1:10, upset vibration 18 hours, then adopts " solid waste Determination of Hexavalent Chromium diphenyl carbazide spectrophotometry (GBT15555.4-1995) " to measure chromic content in soil extract；
Soil pH value is measured according to the requirement of national standard " mensuration (NY/T1377-2007) of soil pH "；
2) improvement of chromium-polluted soil
By soil breaking, the sieve crossing 2mm aperture, regulate the moisture content of soil to 40% ~ 80%, according to Cr VI leaching content and pH value in soil, add the 1# medicament of 8% ~ 20%, stir, after maintenance 7 ~ 30 days, measure the pH value of soil, further according to the 2# medicament needing addition 5% ~ 30%, continue maintenance 30 ~ 60 days, after improvement, soil Cr VI Leaching meets " hazardous waste judging standard leaching characteristic identification (GB5085.3-2007) " Cr VI Leaching requirement, and soil pH is in 6 ~ 9 scopes。
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| CN201610154106.6A CN105694894A (en) | 2016-03-18 | 2016-03-18 | Preparation method and application of hexavalent chromium contaminated soil conditioner |
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| CN201610154106.6A CN105694894A (en) | 2016-03-18 | 2016-03-18 | Preparation method and application of hexavalent chromium contaminated soil conditioner |
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Cited By (10)
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| CN106583436A (en) * | 2016-12-16 | 2017-04-26 | 亿利首建生态科技有限公司 | Leaching method for remediating hexavalent chromium contaminated soil |
| CN106734169A (en) * | 2016-12-28 | 2017-05-31 | 广西博世科环保科技股份有限公司 | The processing method and processing equipment of repairing hexavalent chromium polluted soil |
| CN106984644A (en) * | 2017-05-10 | 2017-07-28 | 青岛科技大学 | The preparation of calcium polysulfide renovation agent and its application in pollution law |
| CN107486468A (en) * | 2017-08-15 | 2017-12-19 | 北京高能时代环境技术股份有限公司 | One kind is used for hexavalent chromium polluted soil heterotopic repairing method of microorganism |
| CN108276228A (en) * | 2018-01-16 | 2018-07-13 | 航天凯天环保科技股份有限公司 | One kind being used for the fertilizer and preparation method thereof of Cr (VI) contaminated soil remediations and improvement |
| CN108356069A (en) * | 2018-01-30 | 2018-08-03 | 上海岩土工程勘察设计研究院有限公司 | Polluted Soil stir in situ uniformity computational discrimination method |
| CN108726823A (en) * | 2017-12-19 | 2018-11-02 | 上海傲江生态环境科技有限公司 | The method that greasy filth stabilizes solidification medicament and repairs Heavy Metal Pollution in Sediments soil |
| CN109226239A (en) * | 2018-10-14 | 2019-01-18 | 中国计量大学 | A method of chromium-polluted soil is repaired using alkaline coal ash |
| CN111185474A (en) * | 2020-01-16 | 2020-05-22 | 招商局生态环保科技有限公司 | Chromium-contaminated soil in-situ remediation composite reagent and use method thereof |
| CN116174464A (en) * | 2023-03-06 | 2023-05-30 | 核工业北京化工冶金研究院 | Secondary restoration stable solidification method for 'yellowing' chromium-polluted soil |
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| CN106583436A (en) * | 2016-12-16 | 2017-04-26 | 亿利首建生态科技有限公司 | Leaching method for remediating hexavalent chromium contaminated soil |
| CN106734169A (en) * | 2016-12-28 | 2017-05-31 | 广西博世科环保科技股份有限公司 | The processing method and processing equipment of repairing hexavalent chromium polluted soil |
| CN106984644A (en) * | 2017-05-10 | 2017-07-28 | 青岛科技大学 | The preparation of calcium polysulfide renovation agent and its application in pollution law |
| CN107486468A (en) * | 2017-08-15 | 2017-12-19 | 北京高能时代环境技术股份有限公司 | One kind is used for hexavalent chromium polluted soil heterotopic repairing method of microorganism |
| CN108726823A (en) * | 2017-12-19 | 2018-11-02 | 上海傲江生态环境科技有限公司 | The method that greasy filth stabilizes solidification medicament and repairs Heavy Metal Pollution in Sediments soil |
| CN108276228A (en) * | 2018-01-16 | 2018-07-13 | 航天凯天环保科技股份有限公司 | One kind being used for the fertilizer and preparation method thereof of Cr (VI) contaminated soil remediations and improvement |
| CN108356069A (en) * | 2018-01-30 | 2018-08-03 | 上海岩土工程勘察设计研究院有限公司 | Polluted Soil stir in situ uniformity computational discrimination method |
| CN109226239A (en) * | 2018-10-14 | 2019-01-18 | 中国计量大学 | A method of chromium-polluted soil is repaired using alkaline coal ash |
| CN111185474A (en) * | 2020-01-16 | 2020-05-22 | 招商局生态环保科技有限公司 | Chromium-contaminated soil in-situ remediation composite reagent and use method thereof |
| CN116174464A (en) * | 2023-03-06 | 2023-05-30 | 核工业北京化工冶金研究院 | Secondary restoration stable solidification method for 'yellowing' chromium-polluted soil |
| CN116174464B (en) * | 2023-03-06 | 2024-05-14 | 核工业北京化工冶金研究院 | Secondary restoration stable solidification method for 'yellowing' chromium-polluted soil |
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Application publication date: 20160622 |