CN105542776A - Stabilizing agent for harmless treatment of arsenic-contaminated soil - Google Patents
Stabilizing agent for harmless treatment of arsenic-contaminated soil Download PDFInfo
- Publication number
- CN105542776A CN105542776A CN201510949628.0A CN201510949628A CN105542776A CN 105542776 A CN105542776 A CN 105542776A CN 201510949628 A CN201510949628 A CN 201510949628A CN 105542776 A CN105542776 A CN 105542776A
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- Prior art keywords
- hydrogen peroxide
- aqueous solution
- ferrous sulfate
- soil
- arsenic
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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
-
- 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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- 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 discloses a stabilizing agent for harmless treatment of arsenic-contaminated soil and application thereof. The stabilizing agent of the present invention is prepared by the following method: adding an aqueous solution of hydrogen peroxide into an aqueous solution of ferrous sulfate under stirring; and sealing after addition, and continuing stirring until the liquid polymerizes into a viscous red liquid hydroxyl polymeric ferric sulfate. The stabilizing agent of the present invention can fast and efficiently conduct harmless treatment on arsenic-contaminated soil, reduce arsenic leaching from soil; and compared with the soil treated by the commercially available curing agents, the soil treated by the stabilizing agent of the invention has enlargement ratio of no more than 1.2, structure intact, and pH remaining in the range of 6-9.
Description
Technical field
The invention belongs to contaminated soil remediation field, relate to the stabilization agent of process As polluted soil, waste residue, mud, make arsenic stabilization wherein, reduce the stripping of arsenic.
Background technology
In environmental chemical pollutants, arsenic is one of the most common, that harm residents ' health is the most serious pollutent.Particularly along with the development of modern industrial and agricultural production, the pollution of arsenic to environment is on the rise.The main source that arsenic pollutes mainly comprises: the exploitation of (1) arsenide and smelting.Particularly spread Indigenous Smelting Method arsenic widely in China, often cause arsenic to the chronic pollution of environment; (2) in the exploitation of some non-ferrous metal with in smelting, usually there is arsenide more or less to discharge, pollute surrounding environment; (3) the extensive utilization of arsenide, as contained production and the use of arsenic agricultural chemicals, and for example as the starting material of the industry such as glass, timber, process hides, weaving, chemical industry, pottery, pigment, chemical fertilizer, all adds the arsenic contamination level in environment; (4) burning of coal, the arsenic that can cause in various degree pollutes.
The residual serious harm environmental safety of arsenic pollutent in soil and HUMAN HEALTH, the improvement of As polluted soil causes the attention of domestic and international environmental worker, the improvement of As polluted soil and repair one of hot issue of having become environmental protection circle research.
As polluted soil recovery technique conventional at present has phytoremediation, soil moved in improve the original soil replacement method, soil washing out method, microorganism remediation method, solidification and stabilization repairing method etc.In the As polluted soil recovery project completed at home, more technology is adopted to be solidification and stabilization technology, engineering construction As polluted soil solidification and stabilization medicament used is generally made up of phosphoric acid salt, silicate cement, slag, gypsum, iron ore etc., there is the problems such as pH is higher, increase-volume compares comparatively greatly, Soil structure is destroyed in the soil used after this kind of chemicals treatment, and As polluted soil solidification and stabilization medicament price comparison commercially available is at present expensive.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides the stabilization agent for As polluted soil harmless treatment.
Stabilization agent for As polluted soil harmless treatment provided by the invention, it prepares by the following method:
Under stirring, in ferrous sulfate aqueous solution, add aqueous hydrogen peroxide solution, seal after interpolation, continue to be stirred to the hydroxyl polymeric ferric sulfate that liquid is polymerized to thick red liquid shape.
Wherein, the mass ratio of ferrous sulfate and hydrogen peroxide is 1.82:1.
Preferably, the mass concentration of ferrous sulfate aqueous solution is 20 ~ 40%; The mass concentration of aqueous hydrogen peroxide solution is 5-15%; The volume ratio of ferrous sulfate aqueous solution and aqueous hydrogen peroxide solution is 1:0.73 ~ 4.4.
The present invention also provides the another kind of stabilization agent for As polluted soil harmless treatment, and it prepares by the following method:
(1) get ferrous sulfate aqueous solution and aluminum sulfate aqueous solution mixing, obtain mixing solutions;
(2), under stirring, in the mixing solutions that step (1) obtains, add aqueous hydrogen peroxide solution, seal after interpolation, continue to be stirred to the hydroxyl polymeric aluminium iron sulfate that liquid is polymerized to thick red liquid shape.
Wherein, the mass ratio of ferrous sulfate, Tai-Ace S 150 and hydrogen peroxide is 1:1.5:0.55.
Preferably, the mass concentration of ferrous sulfate aqueous solution is 20 ~ 40%, the mass concentration of aluminum sulfate aqueous solution is 20 ~ 40%, and the mass concentration of aqueous hydrogen peroxide solution is 5-15%, and the volume ratio of ferrous sulfate aqueous solution, aluminum sulfate aqueous solution and aqueous hydrogen peroxide solution is 1:0.75 ~ 3:0.73 ~ 4.4.
The present invention also provides the application method of the above-mentioned stabilization agent for As polluted soil harmless treatment, adds in As polluted soil, stirs, maintenance by described stabilization agent.
The present invention has following beneficial effect:
1, the stabilization agent for As polluted soil harmless treatment of the present invention not only rapidly and efficiently can carry out harmless treatment to As polluted soil, reduce the leaching of Arsenic in Soil, and compared with existing commercially available solidification and stabilization medicament, after process, the increase-volume ratio of soil is not more than 1.2, Soil structure is not destroyed, and after process, the pH of soil still maintains within the scope of 6-9.
2, the stabilization agent for harmless treatment As polluted soil of the present invention, its main component is the polymerization iron carbonyl, the hydroxy aluminum iron that are formed by reactions two such as molysite, aluminium salt, oxygenants, this stabilization agent is a kind of semi-fluid condition of g., jelly-like, character is unstable, with joining during general onsite application.This kind of stablizer is built bridge by hydroxyl and arsenic forms multinuclear complex ion inorganic macromolecule compound, and form similar after inorganic macromolecule compound dehydration in the complicated magnetite co-precipitation of Z 250, permanent stability are better.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, can better understand the present invention and can be implemented, but illustrated embodiment is not as a limitation of the invention to make those skilled in the art.
Stabilization agent for As polluted soil harmless treatment of the present invention, prepares by the following method:
Under stirring, in ferrous sulfate aqueous solution, add aqueous hydrogen peroxide solution, seal after interpolation, continue to be stirred to the hydroxyl polymeric ferric sulfate that liquid is polymerized to thick red liquid shape.
Another kind of the present invention is used for the stabilization agent of As polluted soil harmless treatment, prepares by the following method:
(1) ferrous sulfate aqueous solution got and aluminum sulfate aqueous solution mixing, obtain mixing solutions;
(2), under stirring, in the mixing solutions that step (1) obtains, add aqueous hydrogen peroxide solution, seal after interpolation, continue to be stirred to the hydroxyl polymeric aluminium iron sulfate that liquid is polymerized to thick red liquid shape.
Hydroxyl polymeric aluminium iron sulfate, using ferrous sulfate, Tai-Ace S 150 as polymerization single polymerization monomer, by regulating polymerization single polymerization monomer Fe in oxydrolysis process
2+, Fe
3+, SO
4 2-between proportionlity, generate molecular formula be [FeAl (OH)
n(SO
4)
3-n/2]
msulfovinic acid ferro-aluminum superpolymer.Hydroxyl polymeric aluminium iron sulfate is built bridge by hydroxyl and metalloid arsenic forms multinuclear complex ion inorganic macromolecule compound, and rear inorganic macromolecule compound dehydration forms the complicated magnetite co-precipitation of similar Z 250, and permanent stability are better.
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1:
1) hydroxyl polymeric ferric sulfate preparation:
(1) to 2m
30.5m is added in medicament whipping device
3water, adds 150kg ferrous sulfate, uniform stirring;
(2) by 0.275m
330% hydrogen peroxide dilution is to 0.825m
3, pass into ferrous sulfate whipping device by peristaltic pump average rate, passing into speed should too fast (controlling at 10 ~ 20L/min), passes into continuously stirring in process, passes into ferrous sulfate whipping device in process and forbids sealing; The mass ratio of ferrous sulfate and hydrogen peroxide: 1.82:1.
(3) oxidising process terminates, and sealing ferrous sulfate whipping device Keep agitation, is only polymerized to thick red liquid to liquid.
2) hydroxyl polymeric ferric sulfate process As polluted soil.
As polluted soil is taken near the solfatara of Guangxi Hechi.Adopt " solid waste Leaching leaching method sulfonitric method " (HJ/T299-2007) to carry out leaching experiment to contaminated soil, the leaching content of Arsenic in Soil is 1.51mg/L.
The hydroxyl polymeric ferric sulfate prepared is joined 1m with 3% adding proportion
3(density of soil is 1.6t/m to arsenic Polluted Soil
3) in, need above-mentioned hydroxyl polymeric ferrum sulfuricum oxydatum solutum 0.42m
3.Small-sized cement stirrer is adopted contaminated soil and hydroxyl polymeric ferrum sulfuricum oxydatum solutum to be stirred, maintenance sampled after 3 days, " solid waste Leaching leaching method sulfonitric method " (HJ/T299-2007) is adopted to carry out leaching experiment to the soil after process, after process, the leaching content of Arsenic in Soil is 0.4mg/L, the increase-volume ratio of process soil is 1.11, and soil pH is 6.5.
Embodiment 2 ~ 5
Embodiment 2 ~ 5 is identical with the preparation method of embodiment 1, and difference is the different ferrous sulfate aqueous solution of compound concentration and aqueous hydrogen peroxide solution, and the volume ratio of the two is different.Process identical As polluted soil according to the method identical with embodiment 1, result is as follows:
| Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| The mass concentration of ferrous sulfate aqueous solution | 20% | 25% | 35% | 40% |
| The mass concentration of aqueous hydrogen peroxide solution | 15% | 10% | 10% | 5% |
| The volume ratio of ferrous sulfate aqueous solution and aqueous hydrogen peroxide solution | 1:0.73 | 1:1.375 | 1:1.92 | 1:4.4 |
| The mass ratio of ferrous sulfate and hydrogen peroxide | 1.82:1 | 1.82:1 | 1.82:1 | 1.82:1 |
| The leaching content (mg/L) of Arsenic in Soil after process | 0.3 | 0.33 | 0.36 | 0.29 |
| The increase-volume ratio of soil after process | 1.11 | 1.11 | 1.12 | 1.12 |
| The pH of soil after process | 7.3 | 7.3 | 7.0 | 6.5 |
Embodiment 6:
1) hydroxyl polymeric aluminium iron sulfate preparation:
(1) 2m
30.5m is added in medicament whipping device
3water, adds 60kg ferrous sulfate and 90kg Tai-Ace S 150, uniform stirring;
(2) by 0.11m
330% hydrogen peroxide dilution is to 0.33m
3, passed in ferrous sulfate, aluminum sulfate mixture solution whipping device by peristaltic pump average rate, passing into speed should too fast (controlling at 10-20L/min), passes into continuously stirring in process, passes into whipping device in process and forbids sealing; The mass ratio of ferrous sulfate, Tai-Ace S 150 and hydrogen peroxide is 1:1.5:0.55.
(3) oxidising process terminates, and sealing whipping device Keep agitation, is only polymerized to thick red liquid to liquid.
2) hydroxyl polymeric aluminium iron sulfate process As polluted soil
As polluted soil is taken near the solfatara of Guangxi Hechi.Adopt " solid waste Leaching leaching method sulfonitric method " (HJ/T299-2007) to carry out leaching experiment to contaminated soil, the leaching content of Arsenic in Soil is 1.51mg/L.
The polymerization sulfovinic acid ferro-aluminum prepared is joined 1m with 3% adding proportion
3pollute in dregs (dregs unit weight gets 1.6), need above-mentioned polymerization sulfovinic acid ferro-aluminum solution 0.27m
3.Adopt small-sized cement stirrer by contaminated soil with to be polymerized sulfovinic acid ferro-aluminum solution stirring even, maintenance sampled after 3 days, " solid waste Leaching leaching method sulfonitric method " (HJ/T299-2007) is adopted to carry out leaching experiment to the soil after process, after process, the leaching content of Arsenic in Soil is 0.41mg/L, and after process, soil pH is that after 6.8 process, soil increase-volume ratio is 1.08.
Embodiment 7 ~ 10
Embodiment 7 ~ 10 is identical with the preparation method of embodiment 1, and difference is the different ferrous sulfate aqueous solution of compound concentration and aqueous hydrogen peroxide solution, and the volume ratio of the two is different.Process identical As polluted soil according to the method identical with embodiment 1, result is as follows:
| Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | |
| The mass concentration of ferrous sulfate aqueous solution | 20% | 20% | 40% | 40% |
| The mass concentration of aluminum sulfate aqueous solution | 20% | 40% | 20% | 40% |
| The mass concentration of aqueous hydrogen peroxide solution | 15% | 5% | 15% | 5% |
| The volume ratio of ferrous sulfate aqueous solution, aluminum sulfate aqueous solution and aqueous hydrogen peroxide solution | 1:1.5:0.73 | 1:0.75:2.2 | 1:3:1.47 | 1:1.5:4.4 |
| The mass ratio of ferrous sulfate, Tai-Ace S 150 and hydrogen peroxide | 1:1.5:0.55. | 1:1.5:0.55. | 1:1.5:0.55. | 1:1.5:0.55. |
| The leaching content (mg/L) of Arsenic in Soil after process | 0.32 | 0.33 | 0.35 | 0.32 |
| The increase-volume ratio of soil after process | 1.05 | 1.08 | 1.1 | 1.1 |
| The pH of soil after process | 7.2 | 7.0 | 6.8 | 7.3 |
The above embodiment is only that protection scope of the present invention is not limited thereto in order to absolutely prove the preferred embodiment that the present invention lifts.The equivalent alternative or conversion that those skilled in the art do on basis of the present invention, all within protection scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (7)
1. for a stabilization agent for As polluted soil harmless treatment, it is characterized in that, it prepares by the following method:
Under stirring, in ferrous sulfate aqueous solution, add aqueous hydrogen peroxide solution, seal after interpolation, continue to be stirred to the hydroxyl polymeric ferric sulfate that liquid is polymerized to thick red liquid shape.
2. stabilization agent according to claim 1, is characterized in that, the mass ratio of ferrous sulfate and hydrogen peroxide is 1.82:1.
3. stabilization agent according to claim 2, is characterized in that, the mass concentration of ferrous sulfate aqueous solution is 20 ~ 40%; The mass concentration of aqueous hydrogen peroxide solution is 5-15%; The volume ratio of ferrous sulfate aqueous solution and aqueous hydrogen peroxide solution is 1:0.73 ~ 4.4.
4. for a stabilization agent for As polluted soil harmless treatment, it is characterized in that, it prepares by the following method:
(1) get ferrous sulfate aqueous solution and aluminum sulfate aqueous solution mixing, obtain mixing solutions;
(2), under stirring, in the mixing solutions that step (1) obtains, add aqueous hydrogen peroxide solution, seal after interpolation, continue to be stirred to the hydroxyl polymeric aluminium iron sulfate that liquid is polymerized to thick red liquid shape.
5. stabilization agent according to claim 4, is characterized in that, the mass ratio of ferrous sulfate, Tai-Ace S 150 and hydrogen peroxide is 1:1.5:0.55.
6. stabilization agent according to claim 5, it is characterized in that, the mass concentration of ferrous sulfate aqueous solution is 20 ~ 40%, the mass concentration of aluminum sulfate aqueous solution is 20 ~ 40%, the mass concentration of aqueous hydrogen peroxide solution is 5-15%, and the volume ratio of ferrous sulfate aqueous solution, aluminum sulfate aqueous solution and aqueous hydrogen peroxide solution is 1:0.75 ~ 3:0.73 ~ 4.4.
7. the application method of the stabilization agent for As polluted soil harmless treatment described in any one of claim 1 ~ 6, is characterized in that, adds in As polluted soil, stirs, maintenance by described stabilization agent.
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|---|---|---|---|
| CN201510949628.0A CN105542776A (en) | 2015-12-18 | 2015-12-18 | Stabilizing agent for harmless treatment of arsenic-contaminated soil |
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|---|---|---|---|
| CN201510949628.0A CN105542776A (en) | 2015-12-18 | 2015-12-18 | Stabilizing agent for harmless treatment of arsenic-contaminated soil |
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Cited By (5)
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| CN106621169A (en) * | 2016-12-30 | 2017-05-10 | 深圳市能源环保有限公司 | Waste incineration fly ash stabilization chemical and preparing method thereof |
| CN106699387A (en) * | 2016-12-28 | 2017-05-24 | 贵州省贵福生态肥业有限公司 | Multifunctional soil remediation fertilizer |
| CN106734175A (en) * | 2017-01-20 | 2017-05-31 | 湖南艾布鲁环保科技有限公司 | Solidification and stabilization medicament that a kind of As polluted soil is repaired and its preparation method and application |
| CN107254313A (en) * | 2017-06-29 | 2017-10-17 | 中南大学 | As polluted soil passivator and preparation method, the method for administering As polluted soil |
| CN114029337A (en) * | 2021-12-09 | 2022-02-11 | 中国建筑第四工程局有限公司 | In-situ preoxidation-stabilization combined remediation agent and remediation method for deep arsenic-polluted soil |
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| CN106621169A (en) * | 2016-12-30 | 2017-05-10 | 深圳市能源环保有限公司 | Waste incineration fly ash stabilization chemical and preparing method thereof |
| CN106734175A (en) * | 2017-01-20 | 2017-05-31 | 湖南艾布鲁环保科技有限公司 | Solidification and stabilization medicament that a kind of As polluted soil is repaired and its preparation method and application |
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| CN114029337A (en) * | 2021-12-09 | 2022-02-11 | 中国建筑第四工程局有限公司 | In-situ preoxidation-stabilization combined remediation agent and remediation method for deep arsenic-polluted soil |
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Application publication date: 20160504 |