CN111036668A - Method for treating and repairing Cr (VI) slag and polluted soil thereof - Google Patents
Method for treating and repairing Cr (VI) slag and polluted soil thereof Download PDFInfo
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- CN111036668A CN111036668A CN201911163409.4A CN201911163409A CN111036668A CN 111036668 A CN111036668 A CN 111036668A CN 201911163409 A CN201911163409 A CN 201911163409A CN 111036668 A CN111036668 A CN 111036668A
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- 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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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
- A01B79/00—Methods for working soil
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
Abstract
The invention provides a method for treating and repairing Cr (VI) slag and polluted soil thereof, which comprises the following steps: applying rice straw powder, corn straw powder or alfalfa powder to soil, irrigating and coating to form a submerged soil system under a film; the Cr (VI) in the soil is reduced to Cr (III), so that the Cr (VI) polluted soil is strongly reduced and repaired. On one hand, the strong reduction treatment influences the valence state of iron in the soil, thereby not only generating a synergistic remediation effect on the remediation of Cr (VI) pollution in the soil, but also avoiding the color reversion phenomenon; on the other hand, the method has influence on the form of iron in the soil, and can effectively improve the utilization of the iron in the soil. The soil humification degree is increased, and the newly increased humus has a synergistic restoration effect on the Cr (VI) polluted soil. The method reduces the phosphorus in the occluded state, which is difficult to utilize in the soil, by 29-37 percent, and increases the phosphorus in the available state by 81-103 percent, which shows that the strong reduction treatment can effectively improve the utilization of the phosphorus in the soil.
Description
Technical Field
The invention relates to a soil remediation method, in particular to a method for treating and remedying Cr (VI) slag and polluted soil thereof.
Background
Chromium salt is one of the main series products in inorganic chemical industry in China, and is widely applied to industries such as metallurgy, electroplating, tanning, metal processing and the like, and the industries cannot avoid generating a large amount of Chromium slag, Chromium-containing waste water and waste gas in the production process (FendorfS, Wielinga B W, Hansel C M. Chromium transformation in natural environment: the roll of biological and biological processes in Chromium (VI) reduction [ J ]. International geographic Review,2000,42 (6918): 701.). The national soil pollution condition survey bulletin issued by the ministry of environmental protection and the ministry of homeland in 2014 indicates that the exceeding rate of the soil point location in China is 16.1%, wherein the exceeding rate of 8 heavy metals such as chromium, cadmium and the like accounts for 82.8% of all the exceeding rate points, and the exceeding rate points account for 35.9% of 775 soil point locations in 81 industrial abandoned areas, wherein chromium is one of the main pollutants (environmental protection ministry, ministry of homeland resources, national soil pollution soil survey bulletin [ R ]. 2014.). Chromium is a major hazard to humans and has been listed by the U.S. environmental protection agency as a heavy metal priority control by U.S. super funds, and soil chromium contamination presents a significant ecological and health risk (Chrysochou M, Johnston CP, Dahal G.A compatible evaluation of soil contaminated with chromium by calcium polysufide and green-tea nanoscale zero-value ion [ J ]. Journal of Hazardous Materials,2012,201: 33-42.). Chromium in soil exists mainly in two valence states of Cr (III) and Cr (VI). The toxicity of Cr (VI) is over 100 times that of Cr (III). In general, in uncontaminated soil, Cr (III) is the main existing form of chromium, Cr (VI) exists only in a small amount, the toxicity of Cr (III) is low, and Cr (III) is easy to adsorb with soil colloid or form precipitates and has low toxic action on organisms; but Cr (VI) has a weak adsorption effect with soil colloid, and is easy to pollute surrounding surface water by surface runoff or pollute underground water and deep soil by infiltration (Elangovan R, Philipl. Performance evaluation of variable biologicals for the removal of Cr (VI) and organic material from industrial effluence [ J ]. Biochemical Engineering Journal,2009,44(2-3): 174) 186.). Therefore, in terms of soil Cr (VI) pollution treatment and remediation, the soil Cr (VI) pollution is mainly reduced to Cr (iii), and then is solidified/stabilized by using other solidifying agents, wherein the reduction of the soil Cr (VI) to Cr (iii) is a key step (agusti ibarolaza, coptotelli B M, maria t.del Panno, et al, dynamics of microbial community and biological biochemical of phenanthrene and chromium [ J ] Biodegradation,2009,20(1): 95-107.).
Aiming at Cr (VI) pollution in soil, the chemical reduction technology is considered to be an in-situ remediation technology with mature remediation technology, strong operability and low cost. The principle is that the zero-valent iron Fe0 and Fe containing nano-iron are utilized2+Reducing Cr (VI) into Cr (III) by sulfide, hydrazine hydrate or other readily available reducing agents, and then forming hydroxide precipitate, thereby reducing the mobility of chromium in a soil system and lightening the harm of chromium pollution (Zhang J, Xu Y F, Li W T, et al].Journalof hazardous materials,2012,239:128-134.)。
The invention patent CN108410472A discloses a composite reagent ferrous sulfate for repairing low-concentration chromium-polluted soil, a natural material rich in humic acid and organic small molecular acid and a using method thereof; the invention patent CN106391695A makes chromium contaminated soil fully react with a reducer methanol, then adds a stabilizer magnesium salt or iron salt into the treated soil, uniformly mixes the materials, and keeps the soil humidity for film covering reaction for 3-45 days; the invention patent CN106623402A discloses a method for treating chromium-contaminated soil by using inorganic hydrazine; the invention patent CN109796984A discloses a reduction and stabilization medicament ferrous sulfate and a microbial medicament for chromium-contaminated soil; the invention patent CN109097060A discloses a hexavalent chromium repairing medicament and an application and a using method thereof, wherein the hexavalent chromium repairing medicament is a chemical reducing agent calcium polysulfide or sodium sulfide, a biological reducing agent vitamin C which is more than 0.1 percent of a plant material and a biomass stabilizer peat soil; in the invention patent CN110125164A, after the hexavalent chromium-containing waste residue or hexavalent chromium-polluted soil is pretreated, reduction reaction is carried out in a reducing agent ferrous sulfate and sodium metabisulfite solution, so that hexavalent chromium in slurry is converted into trivalent chromium; the invention patent CN108405602A discloses a medicament composition and a method for restoring chromium-contaminated soil, wherein the medicament composition comprises 10-70 parts by weight of ferrous sulfate, 2-10 parts by weight of iron powder, 2-10 parts by weight of alkaline medicament and 1-8 parts by weight of organic fertilizer; the invention patent CN106955888A adjusts the pH value of Cr-containing waste residue or Cr-polluted soil to 6-9, and then reacts with reducing agents ferrous sulfide, sodium metabisulfite or sodium hydrosulfite, adsorbent clay mineral, crystallization activator silicon dioxide, precipitator sodium sulfide or calcium polysulfide; the invention patent CN110076188A discloses a long-acting repairing agent and a repairing method for severe chromium-contaminated soil; wherein the rapid reducing agent is ferrous sulfate, the strong reducing agent is sodium sulfide and/or calcium polysulfide, and the long-acting stabilizing agent is ethyl lactate and vegetable oil.
When the chemical reduction technology is used for repairing Cr (VI) pollution in soil, not only a large amount of reducing agent is consumed, but also Cr (III) in the reduced soil can be oxidized into Cr (VI) again under the action of water, oxygen and manganese oxide (Elangovanr, Philip L.performance evaluation of vacuum biological reagents for the removal of Cr (VI) and organic material free flow [ J]Biochemical engineering journal,2009,44(2-3): 174-. Meanwhile, Fe (II) and N in the subsequent soil2O and other reducing substances react with Cr (VI) to generate Fe (III) and NO3 -These substances may cause soil reversion and secondary salinization (wittbody P. reduction of Cr (VI) in the presence of an exposed soil chemical contaminated [ J ]]Environmental Science and Technology,1995,29(1): 255-. Therefore, although the repair cost of the chemical reduction technology is low, the stability of Cr (VI) reduction is difficult to guarantee, and secondary pollution such as color reversion, secondary salinization and the like exist in soil by the chemical reduction technology.
The strong reduction, namely the reduction soil inactivation, RSD treatment technology is a broad-spectrum sterilization method for soil-borne pathogens. The application research of strong reduction soil sterilization, prevention and control of crop soil-borne diseases [ J ] soil science, 2015,52(3): 469-. The RSD treatment technology not only has better killing effect on continuous cropping obstacle soil-borne pathogenic bacteria, but also has better repairing effect on secondary salinization and soil acidification (Zhu Tong Bin, Phyllostachys bambusoides, Zhang jin wave, and the like. the strong reduction method is used for repairing degraded facility vegetable soil [ J ]. the application of ecology news, 2013,24(3):2619 one-shot 2624.). The RSD treatment technology reduces Cr (VI) in soil through a strong reduction environment on one hand, and reduces Cr (VI) in soil through Fe (II) and humus generated after RSD treatment on the other hand, and plays a synergistic role in repair. The RSD treatment technology has proved to have extremely good effect in the field of continuous cropping obstacle repair, but the effect of the RSD treatment in the field of soil Cr (VI) pollution repair is rarely reported.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a method for treating and repairing Cr (VI) slag and polluted soil thereof.
The technical scheme is as follows: a method for treating and repairing Cr (VI) slag and polluted soil thereof comprises the following steps: applying rice straw powder, corn straw powder or alfalfa powder to soil, irrigating and coating to form a submerged soil system under a film; the Cr (VI) in the soil is reduced to Cr (III), so that the Cr (VI) polluted soil is strongly reduced and repaired.
Preferably, the repair pond is a repair pond for laying anti-seepage measures.
Preferably, the weight of the rice straw powder, the corn straw powder or the alfalfa powder accounts for 0.2 to 1.5 percent of the total weight of the polluted soil.
Further, the weight of the rice straw powder, the corn straw powder or the alfalfa powder accounts for 0.6 to 1.0 percent of the total weight of the polluted soil.
Preferably, the subatmospheric flooded soil system is formed by applying alfalfa powder with the ratio of the C element to the N element of 1 (10-35) to soil, irrigating and coating.
Preferably, the subatmospheric flooded soil system temperature is 30 ℃ or above, so as to create a strongly reducing environment.
Preferably, 86.60% of the acetic acid extracted Cr (VI) in the soil can be reduced into Cr (III) by strong reduction treatment at a specific time period and temperature in a soil system at 30 ℃. The content of Fe (II) in the soil is increased by 2.9679mmol/kg, and the organic matter and sulfide combined iron and residue iron in the soil are converted into exchangeable iron and carbonate combined iron and iron-manganese oxide combined iron. On one hand, the strong reduction treatment influences the valence state of iron in the soil, thereby not only generating a synergistic remediation effect on the remediation of Cr (VI) pollution in the soil, but also avoiding the color reversion phenomenon; on the other hand, the method has influence on the form of iron in the soil, and can effectively improve the utilization of the iron in the soil. The soil humification degree is increased, and the newly increased humus has a synergistic restoration effect on the Cr (VI) polluted soil. The method reduces the close-storage phosphorus (O-P) which is difficult to utilize in the soil by 29-37 percent, increases the available phosphorus (A-P) by 81-103 percent, and shows that the strong reduction treatment can effectively improve the utilization of the phosphorus in the soil.
Further, the strong reduction treatment and restoration of the Cr (VI) polluted soil is realized by maintaining a submerged soil system under the film for 4-16 days; the film covering state is maintained in the curing process, and other operations are not needed in the curing process.
Preferably, the strong reduction treatment for restoring the Cr (VI) polluted soil is implemented by maintaining a submerged soil system under the film for 12-16 days.
Has the advantages that: (1) the soil is repaired by using waste organic materials such as rice straws, the waste is treated by the waste, the pollution is treated by the waste, the cost is low, and the soil salinization caused by conventional reducing agents such as ferrous sulfate and the like is avoided.
(2) Adding a certain amount of rice straw powder, corn straw powder or alfalfa powder, and carrying out strong reduction treatment at a specific time period and temperature to reduce 86.60% of acetic acid extracted Cr (VI) in soil into Cr (III).
(3) Adding a certain amount of rice straw powder, corn straw powder or alfalfa powder, and strongly reducing at a specific time and temperature to increase the content of Fe (II) in soil by 2.9679mmol/kg, so that the soil organic matter, sulfide combined iron and residue iron are converted into exchangeable, carbonate combined iron and iron-manganese oxide combined iron. On one hand, the strong reduction treatment influences the valence state of iron in the soil, thereby not only generating a synergistic remediation effect on the remediation of Cr (VI) pollution in the soil, but also avoiding the color reversion phenomenon; on the other hand, the method has influence on the form of iron in the soil, and can effectively improve the utilization of the iron in the soil.
(4) Adding a certain amount of rice straw powder, corn straw powder or alfalfa powder, and carrying out strong reduction treatment at a specific time period and temperature to increase the humification degree of the soil, wherein the newly added humus has a synergistic restoration effect on the Cr (VI) polluted soil.
(5) Adding a certain amount of rice straw powder, corn straw powder or alfalfa powder, and carrying out strong reduction treatment at a specific time period and temperature to reduce the closed phosphorus (O-P) which is difficult to utilize by 29-37% and increase the available phosphorus (A-P) by 81-103%, which indicates that the strong reduction treatment can effectively improve the utilization of phosphorus in soil.
Drawings
FIG. 1 is a process flow chart of a method for treating and repairing Cr (VI) slag and polluted soil thereof.
Detailed Description
In the following, embodiments of the present invention will be described in detail with reference to the accompanying drawings, and unless otherwise specified, the reagents used in the present invention are commercially available.
Example 1
Transferring the Cr (VI) slag polluted soil to a restoration pool paved with anti-seepage measures, adding 0.6 percent (w/w) of alfalfa powder into the Cr (VI) slag polluted soil at a concentration of 2mmol/kg, irrigating river water, covering an agricultural film, and after strong reduction is carried out for 8 days at 50 ℃, reducing the content of Cr (VI) in an acetic acid extraction state by 96.78 percent; after strong reduction for 12 days at 40 ℃, the content of Cr (VI) in an acetic acid extraction state is reduced by 95.90 percent; after strong reduction for 16 days at 30 ℃, the content of Cr (VI) in an acetic acid extraction state is reduced by 86.60 percent; after strong reduction at 20 ℃ for 20 days, the content of Cr (VI) in the acetic acid extraction state is reduced by 46.77 percent.
Example 2
The other steps and the raw materials are the same as those in example 1. 1.0 percent (w/w) of rice straw powder is added, and the content of Cr (VI) in an acetic acid extraction state is reduced by 84.7 percent after strong reduction is carried out for 12 days at 50 ℃; after strong reduction for 7 days at 50 ℃, the content of Cr (VI) in an acetic acid extraction state is reduced by 71.3 percent; after strong reduction for 4 days at 50 ℃, the content of Cr (VI) in the acetic acid extraction state is reduced by 49.7 percent.
Example 3
The other steps and the raw materials are the same as those in example 1. The adding amount of the corn straw powder is 1.5 percent (w/w), and the content of Cr (VI) in an acetic acid extraction state is reduced by 98.87 percent after strong reduction is carried out for 16 days at the temperature of 30 ℃; after strong reduction for 12 days at 40 ℃, the content of Cr (VI) in an acetic acid extraction state is reduced by 90.65 percent; after strong reduction for 5 days at 50 ℃, the content of Cr (VI) in the acetic acid extraction state is reduced by 52.8 percent.
Example 4
The other steps and the raw materials are the same as those in example 1. Transferring the Cr (VI) slag polluted soil to a restoration pool paved with anti-seepage measures, and reducing the content of Cr (VI) in an acetic acid extraction state by 63.48% after 2.6mmol/kg of Cr (VI) slag polluted soil is subjected to strong reduction without adding alfalfa powder for 16 days at the temperature of 40 ℃; the content of Cr (VI) in the acetic acid extraction state is reduced by 67.13 percent under the condition of 0.2 percent (w/w) of the added amount of the alfalfa powder; the content of Cr (VI) in the acetic acid extraction state is reduced by 78.52 percent under the condition of 0.6 percent (w/w) of the added amount of the alfalfa powder; under the condition of 1.0% (w/w) of the added amount of the alfalfa powder, the content of Cr (VI) in an acetic acid extraction state is reduced by 86.60%; 1.2% (w/w) of the alfalfa powder, the content of Cr (VI) in the acetic acid extraction state is reduced by 92.72%; under the condition of 1.5% (w/w) of the added amount of the alfalfa powder, the content of Cr (VI) in an acetic acid extraction state is reduced by 93.04 percent; under the condition of 1.8% (w/w) of the added alfalfa powder, the content of Cr (VI) in the acetic acid extraction state is reduced by 93.16%. The addition of the alfalfa powder is 0.6-1.0% (w/w) compared with 0.2-1.5% (w/w), and the reduction removal performance of the acetic acid extraction state Cr (VI) can be obviously improved.
Example 5
The other steps and the raw materials are the same as those in example 1. Under the condition of 0.6% (w/w) of added alfalfa powder, after strong reduction is carried out for 16 days at 50 ℃, the content of Fe (II) in soil is increased by 3.6195 mmol/kg; after strong reduction is carried out for 16 days at 40 ℃, the content of Fe (II) in the soil is increased by 3.3010 mmol/kg; after strong reduction is carried out for 16 days at the temperature of 30 ℃, the content of Fe (II) in the soil is increased by 2.9578 mmol/kg; after strong reduction for 16 days at 20 ℃, the Fe (II) content of the soil is increased by 2.3266 mmol/kg. On one hand, the strong reduction treatment can effectively avoid the color reversion phenomenon, and on the other hand, the reduction product Fe (II) of the strong reduction treatment can generate a synergistic effect on the restoration of Cr (VI) pollution in soil. When the temperature is higher than 30 ℃, the reduction performance of the Fe (II) in the soil is enhanced.
Example 6
The other steps and the raw materials are the same as those in example 1. Under the condition of 30 ℃, after the alfalfa powder is not added and strongly reduced for 16 days, the content of Fe (II) in the soil is increased by 2.7586 mmol/kg; under the condition of 0.6% (w/w) of the added amount of the alfalfa powder, the content of the Fe (II) in the soil is increased by 2.9578 mmol/kg; under the condition of 1.2% (w/w) of the added amount of the alfalfa powder, the content of the Fe (II) in the soil is increased by 3.1900 mmol/kg. The method shows that when the Cr (VI) is repaired by strong reduction treatment, the content of Fe (II) in the soil can be synchronously increased, and the Cr (III) in the reduced soil is effectively prevented from being oxidized into Cr (VI) again.
Example 7
The other steps and the raw materials are the same as those in example 1. After 0.6% (w/w) of the added amount of the alfalfa powder and a soil system at the temperature of 30 ℃ and after strong reduction for 16 days, the occupation ratios of the residual iron, the organic matters and the sulfide combined iron are respectively reduced by 13.85 percent and 1.75 percent, and the occupation ratios of the exchangeable carbonate combined iron and the iron-manganese oxide combined iron are respectively increased by 2.66 percent and 12.94 percent. This indicates that the iron in the soil is converted from a stable state to an unstable state under the action of the strong reduction treatment, and the strong reduction treatment can effectively improve the utilization of the iron in the soil.
Example 8
The other steps and raw materials are the same as those in example 1, the soil humification index (Humic index, HIX) is increased from the initial 1.2 to 6.2 after 16 days of strong reduction under the condition of 0.6% (w/w) alfalfa powder adding amount and a soil system at 30 ℃. This shows that the soil humus degree is increased after strong reduction treatment, and the newly increased humus can generate a synergistic remediation effect on the Cr (VI) pollution in the remediation soil.
Example 9
The other steps and raw materials are the same as those in the example 1, the adding amount of 0.6% (w/w) alfalfa powder and the strong reduction treatment is carried out for 16 days, the soil aluminum phosphate salt and the soil ferric phosphate salt are respectively increased by 29-46% and 14-21%, and the closed state phosphate is reduced by 29-37%, so that the effective phosphorus in the soil is increased by 81-103%. This indicates that the strong reduction treatment can increase the available phosphorus content and further improve the utilization of phosphorus in the soil.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; the essence of the corresponding technical solutions does not depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A method for treating and repairing Cr (VI) slag and polluted soil thereof is characterized by comprising the following steps: applying rice straw powder, corn straw powder or alfalfa powder to soil, irrigating and coating to form a submerged soil system under a film; the Cr (VI) in the soil is reduced to Cr (III), so that the Cr (VI) polluted soil is strongly reduced and repaired.
2. The method for treating and repairing Cr (VI) slag and the soil polluted by the Cr (VI) slag as claimed in claim 1, wherein the method comprises the following steps: the weight of the rice straw powder, the corn straw powder or the alfalfa powder accounts for 0.2 to 1.5 percent of the total weight of the polluted soil.
3. The method for treating and repairing Cr (VI) slag and the soil polluted by the Cr (VI) slag as claimed in claim 1, wherein the method comprises the following steps: the weight of the rice straw powder, the corn straw powder or the alfalfa powder accounts for 0.6 to 1.0 percent of the total weight of the polluted soil.
4. The method for treating and repairing Cr (VI) slag and polluted soil thereof as claimed in claim 1, wherein: the under-membrane waterlogged soil system is formed by applying alfalfa powder with the ratio of the C element to the N element of 1 (10-35) to soil, irrigating and coating a membrane.
5. The method for treating and repairing Cr (VI) slag and polluted soil thereof as claimed in claim 1, wherein: the temperature of the subatmospheric flooded soil system is 30 ℃ or above.
6. The method for treating and repairing Cr (VI) slag and polluted soil thereof as claimed in claim 1, wherein: the strong reduction treatment and restoration of the Cr (VI) polluted soil are realized by maintaining a submerged soil system under the film for 4-16 days.
7. The method for treating and repairing Cr (VI) slag and polluted soil thereof as claimed in claim 6, wherein: the strong reduction treatment and restoration of the Cr (VI) polluted soil are realized by maintaining a submerged soil system under the film for 12-16 days.
8. The method for treating and repairing Cr (VI) slag and polluted soil thereof as claimed in claim 1, wherein: the soil is transferred to a restoration pond.
9. The method for treating and repairing Cr (VI) slag and polluted soil thereof as claimed in claim 8, wherein: the restoration pool is a restoration pool paved with anti-seepage measures.
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| CN115500107A (en) * | 2022-10-25 | 2022-12-23 | 中国科学院生态环境研究中心 | Soil improvement method for crop continuous cropping land |
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