CN113025339B - Chemical biological reduction and fixation synergistic remediation agent for chromium-contaminated soil - Google Patents
Chemical biological reduction and fixation synergistic remediation agent for chromium-contaminated soil Download PDFInfo
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- CN113025339B CN113025339B CN202110176747.2A CN202110176747A CN113025339B CN 113025339 B CN113025339 B CN 113025339B CN 202110176747 A CN202110176747 A CN 202110176747A CN 113025339 B CN113025339 B CN 113025339B
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- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
Abstract
The invention relates to the technical field of environmental protection, in particular to a chemical biological reduction fixation synergistic remediation agent for chromium-contaminated soil. The repairing medicament consists of the following components: quicklime, sulfur, a biosurfactant, potassium salt and water; the biosurfactant consists of at least one of glycolipid and alkyl glycoside; the content of calcium in the repairing medicament is 39-57g/L, the content of sulfur in the repairing medicament is 205-310g/L, the content of the biosurfactant is 0.05-2g/L, and the content of potassium salt in the repairing medicament is 5-8 g/L.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a chemical biological reduction fixation synergistic remediation agent for chromium-contaminated soil.
Background
Soil is an important material base for human production and life. The industries of electroplating, tanning, metallurgy, petrochemical industry, pesticide production and the like can generate a large amount of heavy metals such as copper, chromium, nickel, lead and the like, and the heavy metals enter soil through irrigation, precipitation, atmospheric sedimentation and the like.
Among them, chromium and its compounds are widely used in various fields as industrial raw materials. Chromium pollution is mainly formed by industrial application and discharge of mining, electroplating, leather tanning, stainless steel, welding, coating and pigment application, wood corrosion prevention and the like of chromium ores, a plurality of chromium-polluted plots are located in urban development areas, and the environmental risk of the plots is large.
The chromium in the soil mainly exists in two forms of hexavalent chromium Cr (VI) and trivalent chromium Cr (III), wherein the hexavalent chromium Cr (VI) has triple toxicity, is classified as a preferential pollutant, is more easily absorbed by a human body, can invade the human body through digestion, respiratory tracts, skin and mucous membranes, causes skin and intestinal ulcer, and even induces canceration.
Hexavalent chromium cr (vi) accumulates in soil for a long period of time due to its inability to be degraded by microorganisms and can be bio-enriched, ultimately causing it to pass through the food chain and be a serious health hazard. Because hexavalent chromium Cr (VI) has higher chemical activity, the hexavalent chromium Cr (VI) is easier to migrate in soil and pores thereof, and the toxicity is far stronger than that of trivalent chromium Cr (III).
The existing common chromium-contaminated soil remediation technologies include a physical remediation technology, a chemical remediation technology and a biological remediation technology.
Common physical remediation methods include soil replacement, vitrification, and thermal desorption. Among them, the soil replacement method is frequently used in engineering, including soil dressing, soil replacement, and soil turning. The soil dressing method is that a large amount of uncontaminated soil is covered on the surface of the contaminated soil and is fully mixed with the contaminated soil, so that the chromium concentration of the contaminated soil is reduced, and the harm brought by chromium pollution of the soil is reduced; the soil replacement method is to dig away part or all of the polluted soil and take the uncontaminated soil to fill the soil replacement area; the soil-turning method is to turn the polluted soil into the deep layer of the soil to reduce the chromium concentration on the surface layer of the soil. The soil replacement method has the advantages of high repair speed and high cost and is difficult to popularize and apply in a large range; the polluted soil is directly discarded, and the chromium cannot be further treated, so that secondary pollution is easily caused.
The chemical remediation technology is characterized in that a remediation agent is added into polluted soil, so that the properties of the soil are changed, the form and the biological effectiveness of the soil are further changed, and the purpose of remedying the soil pollution is finally achieved. Common chemical repair methods include leaching, electrokinetic repair, curing/stabilization, and the like. Wherein the leaching method is to introduce the leacheate into the polluted soil, desorb heavy metals in the soil from the surface of the soil under the action of gravity and water pressure, and then treat the leacheate containing the heavy metals. The leaching solution commonly used at present comprises water, a chelating agent, a surfactant and the like. The method has the advantages of low cost; people and pollutants can not be in direct contact, and the disadvantage is that the leacheate is easy to cause secondary pollution; has poor repairing effect on clay soil and other soils with poor permeability.
The bioremediation technology is that organisms enrich Cr (VI) in soil into organisms through a food chain or convert the Cr (VI) into Cr (III) with low toxicity, and the Cr (III) comprises animal remediation, plant remediation and microbial remediation, and is most widely researched and applied in the aspects of microbial remediation and plant remediation. But the bioremediation technology has a long repair period and can only effectively repair the characteristic pollutants.
Chinese patent application CN108746191A discloses a method for removing heavy metals in soil by in-situ remediation, which comprises a, diluting a composite material with water, spraying the diluted composite material on heavy metal contaminated soil according to 200L/mu of water, applying the diluted composite material once every 1 week for 1 month continuously; b. mixing the modified traditional Chinese medicine residues with an organic fertilizer, and sowing the mixture into heavy metal contaminated soil by a mechanical tillage method; c. watering by a weighing method to keep the water content of the soil to be 50-60% of the water capacity of the treated soil for 7-10 days; the soil conditioner can restore the soil polluted by various heavy metals (such As Pb, Cd, Cu, Zn, Cr and As) and toxic organic matters (such As chlorinated organic matters, brominated organic matters, antibiotics and the like), reduce the forms of strong activity and strong bioavailability of the heavy metals in the soil, prevent the heavy metals from migrating and converting from the soil to plants, prevent the biological enrichment and amplification of the heavy metals, can efficiently remove the heavy metals such As chromium, mercury and the like in the soil, and restore the original functions of the soil. However, the repairing method of the patent application adopts more composite materials, the preparation process of the modified traditional Chinese medicine residues is complex, the chromium content in the repaired soil is still higher, and the soil treatment requirement of high hexavalent chromium content caused by production is more difficult to meet.
At present, the site soil treatment with high hexavalent chromium content caused by production often has a yellowing phenomenon.
Therefore, it is necessary to develop a chemical biological reduction and fixation synergistic remediation agent for chromium-contaminated soil, which can solve the above technical problems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a chemical biological reduction fixation synergic remediation agent for chromium-contaminated soil and a preparation process thereof, wherein the chemical biological reduction fixation synergic remediation agent has the advantages of high hexavalent chromium reduction rate, stable effect and simple process.
The invention is realized by the following technical scheme:
a chemical biological reduction and fixation synergistic remediation agent for chromium-contaminated soil comprises the following components: quicklime, sulfur, a biosurfactant, potassium salt and water; the biosurfactant consists of at least one of glycolipid and alkyl glycoside; the content of calcium in the repairing medicament is 39-57g/L, the content of sulfur is 205-310g/L, the content of biosurfactant is 0.05-2g/L, and the content of potassium salt is 5-8 g/L.
Preferably, the mass ratio of the raw materials of quicklime, sulfur and water is quicklime: and (3-5) mixing sulfur and water: (10-15): 50.
preferably, the biosurfactant consists of a glycolipid and an alkyl glycoside.
More preferably, the glycolipid is one of a sophorolipid and a rhamnolipid.
More preferably, the glycolipid and alkylglycoside are present in a mass ratio of 1: 1-3.
Preferably, the potassium salt is KH and one of glycine, oxalic acid and acetic acid2PO4A mixture of (a).
More preferably, the KH is one of glycine, oxalic acid and acetic acid2PO4Is 1: 1.
Preferably, the pH of the restorative agent is 8-11.
The invention also relates to a preparation process of the repairing medicament, which comprises the following steps:
(1) mixing quicklime with part of water to obtain a substance A;
(2) mixing sulfur with part of water to obtain a substance B;
(3) adding the substance B into the substance A, and adding the rest water to obtain a substance C;
(4) adding potassium salt and biosurfactant into the substance C to obtain the product.
Preferably, the temperature of the water in the steps (1) to (3) is 80 ℃ or higher.
Preferably, the portion of water in step (1) is 35-45% water.
Preferably, the portion of water in step (2) is 25-35% water.
Preferably, the step (2) comprises the steps of: adding sulfur into part of water while stirring, and stirring to obtain paste to obtain material B.
More preferably, the step (2) comprises the steps of: adding sulfur into 25-35% water (above 80 deg.C), stirring, and stirring to obtain paste to obtain material B.
Preferably, the water level line is marked after the rest water is added in the step (3), the mixture is heated to be boiled and then decocted for 25 to 55 minutes, and the water is supplemented to the marked water level line by hot water with the temperature of more than 80 ℃ in the decocting process to obtain a substance C.
The substance C is a transparent dark reddish brown liquid, and the decoction dregs are yellow green after the decoction is finished.
Preferably, in the step (4), the substance C is cooled to 25-50 ℃, then the dregs of a decoction are removed, and potassium salt and biosurfactant are added.
More preferably, the preparation process comprises the following steps:
(1) mixing quicklime with 35-45% water (above 80 deg.C) to obtain substance A;
(2) adding sulfur into 25-35% water (above 80 deg.C), stirring, and stirring to obtain paste to obtain substance B;
(3) adding the substance B into the substance A, adding the rest water, marking the water level line, heating to boil, decocting for 25-55 minutes, and supplementing water to the marked water level line with hot water of more than 80 ℃ in the decocting process to obtain a substance C;
(4) cooling the substance C to 25-50 deg.C, removing residue, and adding potassium salt and biosurfactant.
Applying a repairing agent according to the amount of hexavalent chromium in the soil, wherein the repairing agent is 6-11 times of the amount of the hexavalent chromium in the soil according to a certain formula amount.
According to the soil moisture content and the water conservancy condition, the remediation agent can be properly diluted by 1-5 times and then applied to the polluted soil.
According to specific conditions, processes such as spraying and strong stirring, pressure injection, high-pressure rotary spraying and the like are selected to ensure that the remediation agent is fully contacted with the polluted soil.
The invention has the beneficial effects that:
the invention optimizes the composition of the repairing medicament and the dosage proportion of each component, and the stabilizing effect of the chromium is obviously improved.
The invention optimizes the mixing sequence of the components and the specific preparation process in the preparation process of the repair medicament, and the prepared repair medicament has further improved chromium stabilization effect.
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
The sophorolipid is purchased from Beijing Miruida science and technology Limited, with the product number of M016138-10 g. Rhamnolipids are available from mitsunsen biotechnology limited, tetrachio, under the name R5L. The alkyl glycosides were purchased from Shanghai Michelin Biochemical technology Ltd, cat # A864768-100g, 50% solution.
Example 1
A chemical biological reduction and fixation synergistic remediation agent for chromium-contaminated soil comprises the following components: calcium lime, sulfur, sophorolipid, potassium salt and water, wherein the content of calcium in the repairing medicament is 39g/L, the content of sulfur is 215g/L, the content of sophorolipid is 0.05g/L, the content of potassium salt is 5g/L, and the pH value of the repairing medicament is 8. The potassium salt isAminoacetic acid and KH2PO4In a molar ratio of 1: 1.
the preparation process of the repairing medicament comprises the following steps:
(1) adding quicklime into water (80 ℃) accounting for 35% of the total water consumption, and stirring while adding to obtain a substance A;
(2) adding sulfur into water (80 ℃) accounting for 25% of the total water consumption, stirring while adding, and stirring into paste to obtain a substance B;
(3) adding the substance B into the substance A, stirring while adding, adding the rest water (80 ℃), marking the water level line, heating to boil, decocting for 25 minutes, and supplementing water to the marked water level line with hot water at 80 ℃ at any time in the decocting process to obtain a substance C;
(4) cooling the substance C to 25 deg.C, removing residue, adding potassium salt and sophorolipid, stirring, and dissolving and dispersing completely.
Example 2
A chemical biological reduction and fixation synergistic remediation agent for chromium-contaminated soil comprises the following components: calcium oxide, sulfur, alkyl glycoside, potassium salt and water, wherein the content of calcium in the repairing medicament is 57g/L, the content of sulfur is 205g/L, the content of alkyl glycoside is 2g/L, the content of potassium salt is 8g/L, and the pH value of the repairing medicament is 10. The potassium salt is oxalic acid and KH2PO4In a molar ratio of 1: 1.
the preparation process of the repairing medicament comprises the following steps:
(1) adding quicklime into water (81 ℃) accounting for 45% of the total water consumption, and stirring while adding to obtain a substance A;
(2) adding sulfur into water (81 ℃) accounting for 35% of the total water consumption, stirring while adding, and stirring into paste to obtain a substance B;
(3) adding the substance B into the substance A, stirring while adding, adding the rest water (81 ℃), marking the water level line, heating to boil, decocting for 55 minutes, and supplementing water to the marked water level line with 81 ℃ hot water at any time in the decocting process to obtain a substance C;
(4) cooling the substance C to 50 deg.C, removing residue, adding potassium salt and alkyl glycoside while stirring, and completely dissolving and dispersing.
Example 3
The difference from example 1 is only that the dosage of the biosurfactant is unchanged, the sophorolipid is replaced by a mixture of sophorolipid and alkyl glycoside, the mass ratio of the sophorolipid to the alkyl glycoside is 1:2, and the rest conditions are the same.
Example 4
The difference from example 3 is only that the mass ratio of sophorolipid to alkyl glycoside is 2:1, and the other conditions are the same.
Example 5
The difference from example 3 is only that the amount of potassium salt is unchanged and only KH is contained2PO4The same applies to the other conditions, except that acetic acid is not contained.
Example 6
The difference from example 3 is only that the amount of potassium salt is unchanged and only acetic acid, no KH is present2PO4The other conditions were the same.
Field test 1
The hexavalent chromium content in the soil of a chromium-polluted area of a certain polluted site far exceeds the national corresponding environmental quality standard, wherein the hexavalent chromium content of a land polluted area reaches 800-1100 mg/kg, the average content is 1000mg/kg, and the specific gravity of the soil in the area is 1.8t/m3。
Spraying 11L of the remediation agent into 1 cubic meter of polluted soil, and stirring. Sampling and detecting after 2 hours, and displaying that the content of hexavalent chromium in the soil is lower than a type of land use screening value (3.0mg/kg) of soil pollution risk control standard (trial) for soil environment quality construction land (GB 36600-2018). And sampling and detecting after 15 days, wherein the content of hexavalent chromium in the soil is lower than 3.0 mg/kg. And the yellowing phenomenon does not occur after long-term observation in the later period.
Field test 2
883m hexavalent chromium polluted soil in certain field3The content of hexavalent chromium is between 3mg/kg and 6500mg/kg, and the volume weight of the soil is 1.6t/m3. The repairing agent is added according to 2 percent of the weight of the experimental soil, and 28.3 tons in total are applied.
Sampling and detecting after 2 hours and 15 days respectively, and the result shows that the content of hexavalent chromium in the soil is lower than a land use screening value (3.0mg/kg) of soil pollution risk control standard (trial) for soil environment quality construction land (GB 36600-2018). And the yellowing phenomenon does not occur after long-term observation in the later period.
Laboratory experiments
Taking the polluted soil with the hexavalent chromium content of 1000mg/kg in the field test 1 to perform a laboratory experiment. Weighing 250g of experimental soil in a 1000mL beaker, taking 2mL of remediation agent, diluting by 5 times, sprinkling on the polluted soil, stirring for 3 minutes while sprinkling, standing for 2 hours, and then sampling; sampling 15 days after the experiment, spraying water to wet the experimental soil for 24 hours and sampling; and (6) detecting.
The hexavalent chromium content of the field and laboratory experiments is specifically shown in table 1.
TABLE 1 soil hexavalent chromium content after remediation
| 2 hours (mg/kg) | 15 days (mg/kg) | 15 days wetting for 24h (mg/kg) | |
| Example 1 (field test 1) | 2.38 | 2.35 | -- |
| Example 2 (field test 2) | 0.38～2.38 | 0.35～2.81 | -- |
| Example 1 (laboratory experiment) | 1.85 | 1.61 | 1.60 |
| Example 2 (laboratory experiment) | 1.50 | 1.35 | 1.35 |
| Example 3 (laboratory experiment) | 1.48 | 1.32 | 1.32 |
| Example 4 (laboratory experiment) | 1.87 | 3.10 | 3.52 |
| Example 5 (laboratory experiment) | 1.85 | 3.51 | 4.10 |
| Example 6 (laboratory experiment) | 1.82 | 2.68 | 3.50 |
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (8)
1. The chemical biological reduction and fixation synergistic remediation agent for chromium-contaminated soil is characterized by comprising the following components: quicklime, sulfur, a biosurfactant, potassium salt and water; the content of calcium in the repairing medicament is 39-57g/L, the content of sulfur is 205-310g/L, the content of biosurfactant is 0.05-2g/L, and the content of potassium salt is 5-8 g/L; the biosurfactant consists of glycolipids and alkyl glycosides; the mass ratio of the glycolipid to the alkyl glycoside is 1: 1-3; the glycolipid is one of sophorolipid and rhamnolipid; the potassium salt is KH and one of glycine, oxalic acid and acetic acid2PO4The mixture of KH and one of glycine, oxalic acid and acetic acid2PO4Is 1: 1.
2. The restorative agent of claim 1, having a pH of 8-11.
3. A process for the preparation of a restorative agent according to any of claims 1-2, comprising the steps of:
(1) mixing quicklime with part of water to obtain a substance A;
(2) mixing sulfur with part of water to obtain a substance B;
(3) adding the substance B into the substance A, and adding the rest water to obtain a substance C;
(4) adding potassium salt and biosurfactant into the substance C to obtain the product.
4. The process according to claim 3, wherein the temperature of water in the steps (1) to (3) is 80 ℃ or higher.
5. The process according to claim 3, wherein the portion of water in step (1) is 35 to 45% water; in the step (2), the part of water is 25-35% of water.
6. The production process according to claim 3, wherein the step (2) comprises the steps of: adding sulfur into part of water while stirring, and stirring to obtain paste to obtain material B.
7. The preparation process according to claim 3, wherein the residual water is added in the step (3) and then the water level line is marked, the mixture is heated to boiling and then decocted for 25-55 minutes, and the water level is supplemented to the marked water level line by hot water with the temperature of more than 80 ℃ in the decocting process to obtain the substance C.
8. The process according to claim 3, wherein the potassium salt and the biosurfactant are added after cooling the substance C to 25-50 ℃ in the step (4).
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