CN103170501A - Preparation method of in-situ repair material for soil polluted by heavy metal chromium and application of material - Google Patents
Preparation method of in-situ repair material for soil polluted by heavy metal chromium and application of material Download PDFInfo
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Abstract
The invention discloses a preparation method of an in-situ repair material for soil polluted by heavy metal chromium and an application of the material. According to the invention, the in-situ repair material, which is modified nano metal particles, for the soil polluted by chromium is prepared by taking steel pickling waste liquor as a raw material and carboxymethylcellulose as a dispersing agent; the material has the advantages of good mobility, great specific surface area and strong stability and has good reaction activity in the in-situ repair of the soil polluted by the chromium and better repair effect than common nano zero-valent iron; as the preparation method is simple, the in-situ repair material can be prepared in the site and used for implementing the in-situ repair of the soil polluted by the chromium; and meanwhile, the steel pickling waste liquor is used for preparing the zero-valent iron, so that the treatment cost can be reduced and the purpose of treating waste by using waste is achieved.
Description
Technical field
The invention belongs to nano material preparation and environmental pollution improvement and recovery technique field, particularly a kind of heavy metal chromium contaminated soil original position repair materials---preparation method and the application thereof of modification type nano-metal particle.
Background technology
Chromium compound is one of main series of products of inorganic chemical industry, is widely used in the industries such as chemical industry, light industry, metallurgy, weaving, machinery.According to statistics, in Chinese national economy, approximately 15% product is relevant with chromium compound.May cause soil Cr to pollute by the sedimentation that contains the chromium particle, chromium-bearing sludge and the abandoning of refuse of industry in the production process of chromium.The regional agriculture ecological deterioration of current China and agricultural product are subjected to the heavy metal pollution phenomenon also very serious, and according to incompletely statistics, the arable land of China is subject to nearly 2,000 ten thousand hm in arable land of the heavy metal pollutions such as cadmium, arsenic, lead, chromium, mercury
2, account for 1/5 of total area under cultivation, annual because of approximately 1,000 ten thousand tons, heavy metal pollution of soil underproduction grain.2011, country released " heavy metal pollution integrated control " 12 " planning ", required by 2015, and the discharging of the heavy metal contaminants such as key area lead, mercury, chromium, cadmium and metalloid arsenic cut down 15% than 2007.
At present, the recovery technique of heavy-metal contaminated soil mainly is divided into two classes: original position reparation and showering.Wherein showering is only applicable to small size, sudden serious pollution soil due to expensive with characteristics such as quantities are large.The original position reparation mainly comprises: physics reparation, biological restoration, chemistry reparation etc.Wherein, the physics reparation mainly contains elution method etc., be that the 201210117234.5(publication number is CN102652956A as application number) a kind of by name " a kind of chromium-polluted soil original position drip washing processing method " disclosed, by the drip washing contaminated soil, make chromyl washing water enter underground water, more chromyl underground water is extracted into the earth's surface processes, although the method treatment effect is obvious, but rehabilitation cost is high, quantities is large, is not suitable for large tracts of land and uses.Biological restoration often utilizes plant or animal that heavy metal in soil is absorbed, be that the 200910214428.5(publication No. is CN101797579A as application number) application documents a kind of by name " a kind of method of administering soil heavy metal combined pollution " disclosed, the method utilizes ramie to carry out the absorption transfering type reparation to the heavy metal in contaminated soil, introduce simultaneously earthworm to increase the organic matter of soil, although implement simpler, cost is low, but the improvement cycle is long, effect is not remarkable, can not administer heavily contaminated soil.Chemistry is repaired by selecting suitable chemical renovation agent to add soil, to the biological effectiveness that heavy metal adsorbs, redox, precipitation etc. reduce heavy metal, due to easy to operate and administer fast, makes it become the study hotspot that contaminated soil is in recent years repaired.In disclosed patent application document in recent years, be that the 201010288476.1(publication number is CN101962551A as application number) application documents disclose a kind of name and be called " be used for administering heavy-metal contaminated soil contain sepiolite curing agent ", this curing agent adopts sepiolite replacing partial cement, quick lime to fix the heavy metal in soil, although can reduce the destruction to the soil body, but adopt the method thoroughly not solve the problem of destroying the soil body, the soil after reparation no longer is fit to carry out agricultural operation.
The seriousness of polluting in view of China soil Cr and the severity of national policy rules are needed a kind of economy of exploitation, efficient, practical improvement technology badly.Use at present Zero-valent Iron technical finesse heavy metal chromium and pollute and mostly concentrate in aqueous medium, and be used for repairing the practicality of chromium-polluted soil, reliable and ripe method and technology is few.Contain the characteristics such as organic matter, inanimate matter and impurity, density is large in soil, compare the removal of Cr in water body (VI), system is complicated, so intractability is larger, this point can be found out from reaction time and the dosage about in the article of " removing Cr (VI) water body with nano zero valence iron " delivered.Also should investigate the optimum process condition of practical application in the practice of repairing, and overcome rehabilitation cost and these two bottlenecks of remediation efficiency, consider simultaneously the risk of secondary pollution environment, make it bring into play larger effect in the removal process of heavy metal.
Summary of the invention
The object of the invention is to the deficiency for the prior art existence, a kind of preparation method who modifies the type nano-metal particle is provided, easily reunite to overcome traditional nano-metal particle, poor fluidity, high in cost of production defective.
Another object of the present invention is to provide the application of above-mentioned modification type nano-metal particle in the chromium-polluted soil original position is repaired, to solve the problems such as the traditional treatment method treatment effeciency is low, the cycle is long, engineering is complicated.
The technical solution used in the present invention is:
A kind of preparation method who modifies type nano-metal particle suspension comprises the steps:
1) carboxymethyl cellulose is water-soluble, and carry out deoxygenation and process, then add iron and steel pickling waste liquid, stir 5～30min, obtain solution A;
2) reducing agent is dissolved in 15～50% ethanolic solution (mass ratio of ethanol and water), obtains solution B;
3) under stirring, solution B is added dropwise in solution A, continues to be stirred to the solution blackening, after ultrasonic wave is processed 5～30min, obtain solution C, namely contain the modification type nano-metal particle suspension of Zero-valent Iron.
Preferably, above-mentioned iron and steel pickling waste liquid contains the H of 0.05～5g/L
+Fe element with 60～250g/L.
Preferably, in step 3), the volume ratio of solution A and solution B is (1～10): 1.
Preferably, in solution C, the mass percent of carboxymethyl cellulose is 0.1～4%.
Preferably, in reducing agent and iron and steel pickling waste liquid, the mol ratio of Fe element is (1～8): 1.
Preferably, Fe in solution C
0Concentration be 0.01～10g/L.
Preferably, in step 1), mixing speed is 20～50rpm.
Preferably, ultrasonic frequency is 30～50Hz.
A kind of original position is repaired the method for chromium-polluted soil, it is characterized in that: modification type nano-metal particle suspension is added in soil, mix, carry out the original position reparation;
Modification type nano-metal particle suspension used is prepared by said method.
Preferably, when carrying out the original position reparation, cover the film of perforation on soil.
The invention has the beneficial effects as follows:
(1) modification type nano zero-valence good fluidity of the present invention, stability strong, be difficult for reuniting, can rapid osmotic arrive the depth of soils, go back rapidly in native soil chromium and with insoluble hydroxide (Cr (OH)
3And/or Fe
xCr
1-x(OH)
3) be fixed on soil particle, separate out without noxious material, do not produce secondary pollution; Compare with common nano zero valence iron, degradation efficiency improves approximately 39%.
(2) this recovery technique is suitable for the original position reparation, compares with the method such as other reparations, and this material preparation method is simple, can in situ preparation is on-the-spot uses, and is convenient to implement.
(3) modification type nano-metal particle of the present invention utilizes iron and steel pickling waste liquid to be prepared from, and compares with common nano-metal particle, and this material preparation cost is low, is conducive to the recycling of resource, turns waste into wealth, and has great economic results in society.
(4) modification type nano-metal particle of the present invention can be used for processing the soil of DIFFERENT Cr pollution level, rehabilitating soil at short notice.
Description of drawings
Fig. 1 is TEM image and the SEM image of the CMC-nZVI suspension 2 of embodiment 1 preparation.
Fig. 2 is the exterior appearance of the CMC-nZVI suspension of embodiment 1 preparation;
Fig. 3 is that the different CMC-nZVI dosages of embodiment 3 are to the repairing effect of chromium-polluted soil;
Fig. 4 is that embodiment 5 uses CMC-nZVI to the repairing effect of the chromium-polluted soil of different initial concentrations;
Fig. 5 is that the different repair materials of embodiment 6 are to the repairing effect of chromium-polluted soil;
Fig. 6 is that embodiment 10 uses the CMC-nZVI original position to repair the effect of chromium-polluted soil.
The specific embodiment
A kind of preparation method who modifies type nano-metal particle suspension comprises the steps:
1) carboxymethyl cellulose is water-soluble, and carry out deoxygenation and process, then add iron and steel pickling waste liquid, stir 5～30min, obtain solution A;
2) reducing agent is dissolved in 15～50% ethanolic solution (mass ratio of ethanol and water), obtains solution B;
3) under stirring, solution B is added dropwise in solution A, continues to be stirred to the solution blackening, after ultrasonic wave is processed 5～30min, obtain solution C, namely contain the modification type nano-metal particle suspension of Zero-valent Iron.
As preferably, above-mentioned iron and steel pickling waste liquid contains the H of 0.05～5g/L
+Fe element with 60～250g/L.Due to its serious corrosivity, be put into " national Hazardous Waste List ", the direct discharging of such waste liquid is serious environment pollution not only, and cause great waste, the present invention utilizes iron and steel pickling waste liquid to prepare the water pollution and processes the recycling that material is conducive to resource, turn waste into wealth, have great economic results in society.In following examples, iron and steel pickling waste liquid used comes from Guangzhou cold-strip steel company, contains the H of 0.9g/L
+Fe element with 121.8g/L.
Preferably, in step 1), carboxymethyl cellulose is water-soluble after, with nitrogen blowing 10～20min, carry out deoxygenation and process.
Preferably, in step 3), the volume ratio of solution A and solution B is (1～10): 1.
As preferably, the dosage of carboxymethyl cellulose is 0.1～4% of solution C quality, carboxymethyl cellulose is controlled in this concentration range, can make the nano-metal particle suspension that makes just be suspension, and can layering in standing 10 minutes, be difficult for being precipitated by magnet adsorption, both guaranteed that the material after the preparation keeps high activity, reach the purpose that directly adds use, strictly controlled again production cost.
Preferably, reducing agent used is NaBH
4, KBH
4, N
2H
2In at least a, consider the stability of degradation effect, the present invention preferably adopts NaBH
4In reducing agent and iron and steel pickling waste liquid, the mol ratio of Fe element is (1～8): 1.
Preferably, Fe in solution C
0Concentration be 0.01～10g/L.
Preferably, in step 1), mixing speed is 20～50rpm.
Preferably, ultrasonic frequency is 30～50Hz; Solution after ultrasonic wave is processed, standing 15～20min.
A kind of original position is repaired the method for chromium-polluted soil, it is characterized in that: modification type nano-metal particle suspension is added in soil, mix, carry out the original position reparation; Modification type nano-metal particle suspension used is prepared by said method.
Preferably, when carrying out the original position reparation, cover the film of perforation on soil.
The nano zero-valence iron surface has very high activity due to the atom that lacks contiguous coordination, thereby has each other the trend of reunion, and nano zero valence iron has magnetic simultaneously, and it is more easily reunited.201010182687.7 in application documents, by adding dispersant kollidon (PVP), the surface charge that changes particle distributes, and produces the effect that the static space steric effect reaches dispersion.After product drying due to the method preparation, therefore nano zero valence iron need grind before coming into operation because magnetic still can be reunited; And carboxymethyl cellulose (CMC) is thick after water-soluble, complex compound with Fe formation CMC-Fe, both can separate zero-valent iron particle, can make again it present suspended state, can again not reunite because of magnetic, the nano-metal particle Fibre Suspensions of preparation is good, stability is strong, can rapid osmotic arrive the depth of soils, should directly add the original position reparation of carrying out soil.
Because original position repair materials of the present invention exists with liquid form, so should suitably become flexible soil before repairing, make it have certain gap; And after adding material on soil cover film, enter soil oxidation Zero-valent Iron to reduce airborne oxygen, simultaneously, for the eliminating that produces gas in the metabolism breathing of Soil Microorganism and course of reaction leaves suitable hole.
The present invention is further illustrated below in conjunction with embodiment, but be not limited to this.
Embodiment 1
The preparation method of the CMC-nZVI of different stabilitys comprises the steps:
1) get 1.2g carboxymethyl cellulose (CMC) and be dissolved in the 900mL deionized water, be stirred to dissolving fully, use nitrogen blowing 15min, to remove the dissolved oxygen in solution, add the 20mL iron and steel pickling waste liquid, stir 5min with 30rpm, obtain solution A;
2) the 13g sodium borohydride is dissolved in 280mL 30%(w/w) in ethanolic solution, obtain solution B;
3) stirring is lower slowly drips solution B in solution A, continue to be stirred to the solution blackening, processes 15min through the ultrasonic wave that frequency is 30Hz, and standing 20min obtains solution C, namely contains Zero-valent Iron (Fe
0) concentration is the 0.1%CMC(w/w of 0.2g/L) the modification type nano-metal particle suspension (suspension 1) modified, represent with CMC-nZVI.
4) prepare respectively again Fe
0Concentration be 0.2g/L 0.2, the CMC-nZVI(suspension 2,3 modified of 0.3%CMC), wherein the dosage of CMC be 2.4,3.6g, other conditions such as above-mentioned.
Fig. 1 (a) is the TEM image of suspension 2, and Fig. 1 (b) is the SEM image of suspension 2, and Fig. 2 is suspension 1,2,3 exterior appearance.
Different Fe
0The preparation method of the CMC-nZVI of concentration comprises the steps:
1) get the 0.2g carboxymethyl cellulose and be dissolved in the 80ml deionized water, be stirred to dissolving fully, use nitrogen blowing 10min, add the iron and steel pickling waste liquid of 10 times of 0.1mL dilutions, stir 20min with 25rpm, obtain solution A;
2) the 3mg sodium borohydride is dissolved in 39.9mL 30%(w/w) in ethanolic solution, obtain solution B;
3) stirring is lower slowly drips solution B in solution A, continue to be stirred to the solution blackening, processes 5min through the ultrasonic wave that frequency is 45Hz, and standing 15min obtains Fe
0Concentration is the CMC-nZVI(suspension 4 that the 0.17%CMC of 0.01g/L modifies), its exterior appearance is similar to embodiment 1 products therefrom.
According to the method described above, prepare respectively Fe
0Concentration is the CMC-nZVI(suspension 5～8 that the 0.17%CMC of 0.01～0.21g/L modifies), the consumption of required iron and steel pickling waste liquid, sodium borohydride is as shown in the table, and other parameters are the same.
Embodiment 3
Utilize the sample treatment chromium-polluted soil of embodiment 2 preparations:
This example adopts laboratory test, is the not comtaminated soil that picks up from Guangzhou university city for examination soil, and is air-dry after gathering, and crosses 60 mesh sieves, and sealed storage is standby in drier, and measuring its PH is 6.22.
With analyzing pure potassium bichromate artificial pollution, making Cr in soil (VI) concentration is 102mg/kg with above-mentioned soil; Get the polyethylene centrifuge tube of 10mL, add respectively 1g chromium-polluted soil and the addition of C MC-nZVI(suspension 4～8), make Fe in soil
0Content be 0～12mgFe
0/ mgCr (VI); Tighten lid after purging with the nitrogen head space, be placed in 360 ° of impellers with 35rpm concussion 24 hours; With CMC solution sample in contrast, measure total chromium in supernatant and Cr (VI) concentration after reaction with the checking degradation effect.The soil that adds CMC-nZVI after reaction in supernatant Cr (VI) and always the concentration of chromium significantly reduce.When the dosage of CMC-nZVI is 4.4mgFe
0During/mgCr (VI), Cr (VI), total chromium have reduced respectively 98.21%, 88%, as shown in Figure 3.
Embodiment 4
Fe
0Concentration is the preparation method of the CMC-nZVI that modifies of the 0.1%CMC of 0.09g/L, comprises the steps:
1) get the 0.24g carboxymethyl cellulose and be dissolved in the 200mL deionized water, mix to dissolving fully, use nitrogen blowing 15min, add the iron and steel pickling waste liquid of 10 times of 1.8mL dilutions, stir 5min with 50rpm, obtain solution A;
2) the 45mg sodium borohydride is dissolved in 38.2mL 15%(w/w) in ethanolic solution, obtain solution B;
3) stirring is lower slowly drips solution B in solution A, continue to be stirred to the solution blackening, processes 5min through the ultrasonic wave that frequency is 50Hz, and standing 15min obtains Fe
0Concentration is the 0.1%CMC(w/w of 0.09g/L) CMC-nZVI(suspension 9).
Embodiment 5
Utilize the CMC-nZVI suspension 9 of embodiment 4 to process the contaminated soil that contains DIFFERENT Cr concentration:
Soil used such as embodiment 3, consider that Cr in the most domestic chromium-polluted soil (VI) concentration is tens mg/kg soil (Zhao Guanghui etc., typical case's chromium slag muck is deposited place chromium (VI) migration path analysis and the research of anti-chromium plant Preliminary screening, " 2011 China Environmental Science association's Annual Conference collection of thesis (volume Two) "), the present embodiment adds the pure potassium bichromate of the analysis of variable concentrations in soil, make that the concentration of Cr in soil (VI) is respectively 50,102,223,360,424,520mg/kg; Adopt 10ml polyethylene centrifuge tube, add respectively the above-mentioned soil sample of 1g and 5mL suspension 9, tighten lid after purging with the nitrogen head space, put as for 360 ° of impellers with 50rpm concussion 24 hours; With deionized water sample in contrast, measure total chromium in supernatant and Cr (VI) concentration after reaction with the checking degradation effect.The soil that adds the CMC-nZVI total chromium in supernatant and Cr (VI) after reaction have reduction in various degree, along with initial Cr (VI) concentration rises to 520mg/kg from 50mg/kg, the clearance of total chromium drops to 45% from 100%, the clearance of Cr (VI) drops to 29% from 98%, as shown in Figure 4.
Embodiment 6
Utilize the CMC-nZVI suspension 9 of reduced iron powder, nano zero valence iron and embodiment 4 to process chromium-polluted soil:
Soil used such as embodiment 3 adopt 10ml polyethylene centrifuge tube, add respectively the above-mentioned soil sample of 1g and 5mL water+0.45mg reduced iron powder, 5mL water+0.45mg nano zero valence iron, 5mL suspension 9, and the content that makes Iron in Soil is 4.4mgFe/mgCr (VI).Tighten lid after purging with the nitrogen head space, put as for 360 ° of impellers and shake with 50rpm; With deionized water sample in contrast, Cr (VI) concentration is with the contrast degradation effect in setting-up time sampling and measuring supernatant.Add CMC-nZVI soil reaction after 24h the Cr in supernatant (VI) reduced by 98.2%, and the degradation rate that has added nano zero valence iron and reduced iron powder only has respectively 60.1% and 2.3%, as shown in Figure 5.
Fe
0Concentration is the preparation method of the CMC-nZVI suspension modified of the 1%CMC of 2g/L, comprises the steps:
1) get 5g CMC and be dissolved in the 446mL deionized water, be stirred to dissolving fully, use nitrogen blowing 15min, add the 8.2mL iron and steel pickling waste liquid, stir 15min with 40rpm, obtain solution A;
2) the 675mg sodium borohydride is dissolved in 45.8mL 30%(w/w) in ethanolic solution, obtain solution B;
3) stirring is lower slowly drips solution B in solution A, continue to be stirred to the solution blackening, processes 20min through the ultrasonic wave that frequency is 30Hz, and standing 5min obtains solution C, namely contains Fe
0Concentration is the CMC-nZVI(suspension 10 that the 1%CMC of 2g/L modifies).
Embodiment 8
Fe
0Concentration is the preparation method of the CMC-nZVI that modifies of the 4%CMC of 10g/L, comprises the steps:
1) get 20g CMC and be dissolved in the 210mL deionized water, be stirred to dissolving fully, use nitrogen blowing 15min, add the 40mL iron and steel pickling waste liquid, stir 30min with 20rpm, obtain solution A;
2) the 17g sodium borohydride is dissolved in 250mL 40%(w/w) in ethanolic solution, obtain solution B;
3) stirring is lower slowly drips solution B in solution A, continue to be stirred to the solution blackening, processes 30min through the ultrasonic wave that frequency is 45Hz, and standing 15min obtains solution C, namely contains Fe
0Concentration is the CMC-nZVI(suspension 11 that the 4%CMC of 10g/L modifies).
Embodiment 9
Fe
0Concentration is the preparation method of the CMC-nZVI that modifies of the 2%CMC of 4.7g/L, comprises the steps:
1) get the 10g carboxymethyl cellulose and be dissolved in the 300mL deionized water, mix to dissolving fully, use nitrogen blowing 20min, to remove the dissolved oxygen in solution, add 19.6mL iron and steel pickling waste liquid (stoste), stir 30min with 50rpm, obtain solution A;
2) the 5g sodium borohydride is dissolved in 180.4mL 50%(w/w) in ethanolic solution, obtain solution B;
3) stirring is lower slowly drips solution B in solution A, continue to be stirred to the solution blackening, processes 15min through the ultrasonic wave that frequency is 49Hz, and standing 15min obtains Fe
0Concentration is the CMC-nZVI(suspension 12 that the 2%CMC of 4.7g/L modifies).
Utilize the place simulated experiment of the suspension 12 reparation chromium-polluted soils of embodiment 9 preparations.
(carry out in 15cm * 5cm * 10cm), fill up with 1kg chromium-polluted soil (Cr (VI)=102mg/kg is as embodiment 3), making its density is 1.7t/m at a square glass case in the place simulated experiment
3Suspension 12 is added in soil equably, and mix, then the preservative film with perforation covers.Get at regular intervals the concentration of the soil test Cr (VI) of 3cm depths, its repairing effect is seen Fig. 6, and experiment shows, after the reparation of 42 days, the Cr in soil (VI) concentration has reduced by 82%, and its concentration is 19.4mg/kg.
The present invention utilizes the modification type nano-metal particle of iron and steel pickling waste liquid preparation, has the advantages such as good fluidity, specific area is large, stability is strong, can rapid osmotic to the depth of soils, go back rapidly in native soil chromium and with insoluble hydroxide (Cr (OH)
3And/or Fe
xCr
1-x(OH)
3) be fixed on soil particle, separate out without noxious material, do not produce secondary pollution; And repairing effect is higher than common nano zero valence iron, and degradation efficiency has improved approximately 39%.Because modification type nano-metal particle of the present invention utilizes iron and steel pickling waste liquid to be prepared from, to compare with common nano-metal particle, this material preparation cost is low, is conducive to the recycling of resource, turns waste into wealth, and has great economic results in society.And compare with the method such as other reparations, because the preparation method is simple, can in situ preparation, be fit to original position and repair chromium-polluted soil.Simulated experiment proves through the place, and modification type nano-metal particle of the present invention can be used for processing the soil of DIFFERENT Cr pollution level, original position rehabilitating soil at short notice.
Claims (10)
1. a preparation method who modifies type nano-metal particle suspension, comprise the steps:
1) carboxymethyl cellulose is water-soluble, and carry out deoxygenation and process, then add iron and steel pickling waste liquid, stir 5～30min, obtain solution A;
2) reducing agent is dissolved in 15～50% ethanolic solution (mass ratio of ethanol and water), obtains solution B;
3) under stirring, solution B is added dropwise in solution A, continues to be stirred to the solution blackening, after ultrasonic wave is processed 5～30min, obtain solution C, namely contain the modification type nano-metal particle suspension of Zero-valent Iron.
2. preparation method according to claim 1, it is characterized in that: described iron and steel pickling waste liquid contains the H of 0.05～5g/L
+Fe element with 60～250g/L.
3. preparation method according to claim 1, it is characterized in that: in step 3), the volume ratio of solution A and solution B is (1～10): 1.
4. preparation method according to claim 3, it is characterized in that: in solution C, the mass percent of carboxymethyl cellulose is 0.1～4%.
5. according to claim 1～3 described preparation methods of any one is characterized in that: in reducing agent and iron and steel pickling waste liquid, the mol ratio of Fe element is (1～8): 1.
6. according to claim 1～4 described preparation methods of any one, is characterized in that: Fe in solution C
0Concentration be 0.01～10g/L.
7. preparation method according to claim 1, it is characterized in that: in step 1), mixing speed is 20～50rpm.
8. preparation method according to claim 1, it is characterized in that: ultrasonic frequency is 30～50Hz.
9. the method that original position is repaired chromium-polluted soil, is characterized in that: modification type nano-metal particle suspension is added in soil, mix, carry out the original position reparation;
Modification type nano-metal particle suspension used is by the described method preparation of claim 1～8 any one.
10. original position according to claim 9 is repaired the method for chromium-polluted soil, it is characterized in that: when carrying out the original position reparation, cover the film of perforation on soil.
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| CN103934264A (en) * | 2014-03-18 | 2014-07-23 | 北京国环建邦环保科技有限公司 | In-situ reduction restoration method for chromium contaminated soil |
| CN104043642A (en) * | 2014-06-25 | 2014-09-17 | 柏连阳 | Method for in-situ separation of harmful heavy metal in soil |
| CN105670643A (en) * | 2016-03-08 | 2016-06-15 | 华南师范大学 | Preparation method and application of repair material for heavy metal cadmium polluted soil |
| CN106391689A (en) * | 2016-05-26 | 2017-02-15 | 上海泽耀环保科技有限公司 | Soil pollution remediation method and device |
| CN107915420A (en) * | 2017-11-16 | 2018-04-17 | 广东弘朝科技有限公司 | A kind of hexavalent chrome reduction agent and preparation method thereof |
| CN109731888A (en) * | 2019-01-29 | 2019-05-10 | 郗丹 | A kind of chromium slag innocent treatment method |
| CN110280581A (en) * | 2019-07-09 | 2019-09-27 | 浙江大学 | The method of Zero-valent Iron reduction joint persulfate oxidation remedying soil polluted by organic chloride |
| CN114682617A (en) * | 2022-03-31 | 2022-07-01 | 四川农业大学 | Oil soil remediation device and method by coupling double-frequency ultrasonic waves with sodium persulfate |
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