CN112122334A - Method for repairing organic-heavy metal combined contaminated soil by coupling chemical oxidation with biochar and strengthening microorganisms - Google Patents
Method for repairing organic-heavy metal combined contaminated soil by coupling chemical oxidation with biochar and strengthening microorganisms Download PDFInfo
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Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Soil Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
- Mycology (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for repairing organic-heavy metal composite polluted soil by coupling chemical oxidation with biochar to strengthen microorganisms. Crushing the soil to be repaired, screening the soil to be repaired to a particle size of less than 4mm by a wet method, adjusting the soil-water ratio of the soil to the water solution to be 1: 3-1: 5, adjusting the pH to be 5, adding a sodium persulfate solution activated by biochar for leaching treatment, oxidizing organic pollutants by sodium persulfate during leaching, and transferring heavy metal pollutants from the soil to the water solution. After the soil-water is separated by a dewatering device, the liquid is treated by an advanced oxidation device, organic pollutants are further oxidized, and heavy metals reach the standard after coagulating sedimentation by adjusting the pH value to 9-10; the treated water solution is recycled for the soil leaching in the previous step. The separated soil is added with the biochar, the biochar is stacked and kept ventilated after being uniformly mixed, organic matters remained in the soil are further oxidized, heavy metals are slowly released, and the microbial activity of the soil is increased until the polluted soil reaches the standard.
Description
Technical Field
The invention relates to the field of organic-heavy metal composite contaminated soil enhanced remediation, in particular to a method for enhancing the remediation of organic-heavy metal composite contaminated soil by microorganisms through chemical oxidation coupling with biochar.
Background
Soil is a system consisting of multiple media and interfaces. Along with the rapid development of industrial and agricultural production, the pollution substances entering the soil are increasingly intensified. The pollutants mainly comprise organic pesticides, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, heavy metals and the like. A plurality of pollutants are discharged into the soil simultaneously or sequentially, so that the phenomenon of soil combined pollution is quite common.
Currently, remediation technologies for single pollutants, such as organically contaminated sites/soils, are abundant, and mainly include physical, chemical, biological and combined remediation technologies. The chemical oxidation method is widely used because of its high repair efficiency and short repair cycle. The oxidation/reduction technique converts pollutants in soil into non-toxic or relatively less toxic substances by oxidation or reduction by adding an oxidizing agent (hydrogen peroxide, persulfate, permanganate, fenton's reagent, ozone, etc.) or a reducing agent (sodium bisulfite, sodium hydrosulfite, ferrous sulfate, ferrous iron, zero-valent iron, calcium polysulfide, etc.) to the contaminated soil. The method is suitable for organic pollutants which are easy to oxidize and reduce, the repair period is short, and the oxidant which is retained in the soil has certain ecological risks.
Thus, bioremediation in combination with various technologies has gradually developed great remediation potential due to low ecological risk. Bioremediation covers both phytoremediation and microbial remediation, but is central to microbial remediation. The microbial remediation can completely remove organic matters in the polluted soil through the degradation of microorganisms, and the technology is green and economic and gradually becomes one of the mainstream technologies in the field of soil remediation. Meanwhile, the soil inhabits the microbial resources with the highest diversity on the earth, and the development of the resources is only one corner of the iceberg, so that the oriented development of the functions of the resources has immeasurable significance on the development of the human society. The combined repairing method can combine the advantages of various repairing methods, and greatly improves the repairing effect: for example, chemical oxidation repair-biological repair coupling, chemical oxidation can greatly improve the efficiency of organic matter oxidation, and meanwhile, electron chains and free radicals generated by chemical oxidation reduction can promote the electron chain migration and transformation in the microbial degradation biochemical process, so that the process of microbial repair of industrial organic polluted sites/soil is enhanced. The contents disclosed in some granted or published patents (such as CN201310660839.3 and CN 201810348216.5) focus on chemical remediation or microbial remediation and simple combination coupling of the two, and do not effectively combine the advantages of the two, and CN201510635827.4 adopts a method of coupling biochar with animals and plants, but the remediation period is long, which is not beneficial to remediation of high-concentration organically-polluted soil.
Remediation of heavy metal contaminated soil is often carried out by leaching, chemical passivation or barrier treatment.
However, the treatment cases of the compound pollution of organic pollutants and heavy metals are few, and efficient treatment methods are rare.
Disclosure of Invention
The embodiment of the invention aims to provide a method for reinforcing microbial remediation of organic-heavy metal combined contaminated soil by coupling chemical oxidation with biochar, so as to solve the problems of combined contamination and ecological risks caused by oxidants which are difficult to completely remove pollutants and are retained in soil in the related art.
In order to achieve the above purpose, an embodiment of the present invention provides a method for restoring organic-heavy metal complex contaminated soil by coupling chemical oxidation with biochar to enhance microorganisms, which includes the following steps:
step S100, ex-situ leaching: crushing the soil to be repaired, removing stones and coarse sand larger than 4mM through wet screening until the particle size of the soil is smaller than 4mM, pouring the soil to be repaired into a leaching tank, adjusting the pH value to 5, and adding an activated sodium persulfate (PS, 0.5-0.8 mM) solution for leaching treatment, wherein the soil-water ratio is 1: 3-1: 5(v: v); the leaching process comprises the steps of stirring for 30 minutes at 200-300r/min under a strong stirrer, and then stirring for 15 minutes at a stirring speed of 100-150r/min and standing.
Step S101, separating soil from water: and (4) carrying out filter pressing on the soil-water mixed liquid obtained in the step (S100) by using an acid-resistant filter press to ensure that the dehydration efficiency reaches more than 80%. Collecting the leacheate, and allowing the mud cake after pressure filtration to enter the next step.
Step S102, adding carbon in soil pile: and (4) placing the mud cakes separated in the step (S101) in a soil stacking reaction tank, spraying charcoal powder into a soil reactor, adding 0.1-2.0 g/kg of soil, keeping the water content of the soil to be more than 60%, adjusting the pH value of the stacked soil to be 7, keeping the temperature of the stacked body to be 37 ℃, and stacking the soil for 14 days.
And S103, checking and accepting the soil, and returning the unqualified soil to the step S100 or the step S101 until the repair is qualified, thereby completing the repair.
Further, the biochar is prepared by washing canna for 4 times by water to remove surface adherents, then air-drying for 2 days, drying in an oven at 70-80 ℃ overnight, crushing, sieving with a 100-mesh sieve, and packaging in a brown bottle for later use. Then weighing 20g of the biomass powder in a crucible, and putting the crucible in a muffle furnace at 350 ℃ for carbonization for 6 hours; cooling to room temperature and taking out; the carbide was treated with 200mL of hydrochloric acid (1M) solution for 12 hours to remove ash; filtering, washing with distilled water to neutrality, and oven drying at 70-80 deg.C.
Further, in step S104, the rinse solution process: placing the leacheate separated in the step S101 in advanced oxidation equipment for advanced oxidation treatment of sodium persulfate, adjusting the pH to 9-10 after reacting for 20 minutes, adding polyaluminum chloride or polyferric chloride to enable the solution to be coagulated and precipitated, separating clear water and sludge through a plate-and-frame filter press, wherein the sludge is solid waste obtained after coagulation and precipitation of heavy metals, and delivering the solid waste to qualified unit treatment or resource utilization;
further, in step S105, the clean leacheate processed in step S104 is used as reuse water to prepare sodium persulfate solution for ectopic leaching of the soil in step S101, so as to realize recycling of water resources.
According to the technical scheme, the embodiment of the invention takes the biochar as a bridge, realizes the cooperative treatment of organic matters and heavy metals, strengthens the cooperative action between chemical oxidation and microbial remediation, ensures the remediation efficiency, promotes thorough removal of pollutants, and does not generate the problem of secondary pollution; solves the problem of ecological risk of the oxidant retained in the soil, and is beneficial to the restoration of the ecological function of the soil after chemical oxidation and the subsequent development and utilization of the soil after restoration.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a technical optimization combinatorial route diagram provided by an embodiment of the present invention;
FIG. 2 shows the total polycyclic aromatic hydrocarbon content of the raw soil, leached and oxidized and biochar enhanced according to the embodiment of the present invention;
FIG. 3 shows the PLFA content distribution in the raw soil to be treated according to the embodiment of the present invention;
FIG. 4 is the PLFA content distribution in the soil after leaching oxidation according to the embodiment of the present invention;
FIG. 5 is a PLFA content distribution in the soil after strengthening by biochar in the heap soil provided by embodiments of the present invention;
FIG. 6 is the Shannon index of biodiversity after ex-situ treatment provided by an embodiment of the invention;
FIG. 7 shows the effect of the bacterial community gene (enzyme) KO on the ectopic treatment (+ BC for biochar addition) provided in the examples of the present invention.
Fig. 8 shows the distribution of cadmium content in raw soil, leached and coagulated precipitated soil and biochar enhanced according to the embodiment of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which should be understood not to limit the scope of the invention.
Example 1:
as shown in fig. 1, the present embodiment provides a method for repairing organic-heavy metal complex contaminated soil by coupling chemical oxidation with biochar to enhance microorganisms, which adopts an ex-situ repair manner and includes the following steps:
step S100: leaching: crushing 100kg of soil by using a stirring cutting machine, conveying the crushed soil to a roller stone washer, removing stones and coarse sand larger than 4mM, conveying the crushed soil to a leaching tank (a large stainless steel and resin tank body is adopted), adding water with different proportions (1:3, 1:4 and 1:5 volume ratios), adjusting the pH value to be 5, adding sodium persulfate powder to ensure that the concentration of sodium persulfate in the reaction tank is 0.5-0.8 mM, adding ferrous sulfate and charcoal powder to activate potassium persulfate, adding the mixture according to the following table, or adopting an ultraviolet irradiation activation method, stirring the mixture for 30 minutes with strong force (300 r/min), and then stirring the mixture for 15 minutes at the stirring speed of 100 plus 150 r/min.
Activation mode and proportion of sodium persulfate
Activating mode and proportion of sodium persulfate
Preparing biochar in advance, washing harvested plants including canna, thalictrum, allium mongolicum regel and calamus with water for 4 times by adopting a program temperature control muffle furnace to remove surface adhesion substances, then air-drying for 2 days, drying in an oven at 70-80 ℃ overnight, crushing by a crusher, sieving by a 100-mesh standard sieve, weighing 20g of the biomass powder in a crucible, and carbonizing for 6 hours in the muffle furnace at 6 temperatures of 300 ℃, 350 ℃, 450 ℃, 600 ℃, 700 ℃, 900 ℃ and the like; cooling to room temperature, taking out and weighing, treating the prepared carbide with 200mL hydrochloric acid (1 mol/L) solution for 12h, and removing ash; and (4) washing the mixture to be neutral by using distilled water after filtration, drying and weighing the mixture, and calculating ash content according to the mass difference between the front mass and the rear mass. By comparing that the ash content of the canna plant charcoal fired at 350 ℃ is the lowest, the following implementation is conducted with the canna charcoal for reinforcement design.
Step S101: and (4) carrying out filter pressing on the soil-water mixed liquid obtained in the step (S100) by using an acid-resistant filter press, wherein the final dehydration efficiency reaches 80%. The water after filter pressing is led into the reaction tank through a conduit. And collecting the mud cakes, and piling the mud cakes into a soil piling reaction tank after the mass of the mud cakes reaches 100 kg.
Step S102, spraying charcoal powder into a soil reactor, keeping the water content of soil above 60%, adjusting the pH of the piled soil to 7, keeping the temperature of the piled soil at 37 ℃, and piling the soil for 14 days, wherein the adding amount is 0.1g/kg (charcoal/soil).
Collecting raw soil, leaching and filter-pressing soil and soil which completes a soil piling period, and sending the soil and the soil to a laboratory to respectively detect the contents of biomass, heavy metals, organochlorine pesticides and polycyclic aromatic hydrocarbons.
Step S103, soil stacking acceptance: and (5) returning the unqualified soil to the step S100 or the step S101 until the repair is qualified, and finishing the repair.
Further comprising the steps of:
and S104, placing the leacheate separated in the step S101 in advanced oxidation equipment for advanced oxidation treatment of sodium persulfate, wherein the reaction concentration is 0.1mM, adjusting the pH to 9 after reacting for 20 minutes, adding 0.05mM of polyaluminum chloride for coagulating sedimentation for 30 minutes, stirring at the speed of 100r/min, discharging supernatant through an overflow port, separating clear water and sludge from bottom sludge through a plate and frame filter press, wherein the sludge is solid waste obtained after coagulating sedimentation of heavy metal, and delivering the solid waste to qualified units for treatment or resource utilization.
And S105, taking the eluate processed in the step S104 as reuse water to prepare sodium persulfate solution for ectopic elution of the soil in the step S101, so as to realize recycling of water resources.
Example 2:
step S100 is the same as in embodiment 1, and is not described here again.
Step S101: and (4) carrying out filter pressing on the soil-water mixed liquid obtained in the step (S100) by using an acid-resistant filter press, wherein the final dehydration efficiency reaches 85%. The water after filter pressing is led into the reaction tank through a conduit. And collecting the mud cakes, and piling the mud cakes into a soil piling reaction tank after the mass of the mud cakes reaches 100 kg.
Step S102, spraying charcoal powder into a soil reactor, keeping the water content of soil above 60%, adjusting the pH of the piled soil to 7, keeping the temperature of the piled soil at 37 ℃, and piling the soil for 14 days, wherein the adding amount is 0.1g/kg (charcoal/soil).
Step S103, soil stacking acceptance: and (5) returning the unqualified soil to the step S100 or the step S101 until the repair is qualified, and finishing the repair.
Further comprising the steps of:
step S104, placing the leacheate obtained by separation in the step S101 into advanced oxidation equipment for advanced oxidation treatment of sodium persulfate, wherein the reaction concentration is 0.1mM, the pH value is adjusted to 10 after the reaction is carried out for 20 minutes, adding 0.05mM of polyaluminium chloride for coagulating sedimentation for 30 minutes, stirring at the speed of 100r/min, discharging supernatant through an overflow port, separating clear water and sludge from bottom sludge through a plate-and-frame filter press, wherein the sludge is solid waste obtained after heavy metal is subjected to coagulating sedimentation, and delivering the solid waste to qualified units for treatment or resource utilization;
and S105, taking the eluate processed in the step S104 as reuse water to prepare sodium persulfate solution for ectopic elution of the soil in the step S101, so as to realize recycling of water resources.
Example 3:
step S100 is the same as in embodiment 1, and is not described here again.
Step S101: and (4) carrying out filter pressing on the soil-water mixed liquid obtained in the step (S100) by using an acid-resistant filter press, wherein the final dehydration efficiency reaches 85%. The water after filter pressing is led into the reaction tank through a conduit. And collecting the mud cakes, and piling the mud cakes into a soil piling reaction tank after the mass of the mud cakes reaches 100 kg.
Step S102, spraying charcoal powder into a soil reactor, keeping the water content of soil above 60%, adjusting the pH of the piled soil to 7, keeping the temperature of the piled soil at 37 ℃, and piling the soil for 14 days, wherein the adding amount is 0.5g/kg (charcoal/soil).
Step S103, soil stacking acceptance: and (5) returning the unqualified soil to the step S100 or the step S101 until the repair is qualified, and finishing the repair.
Further comprising the steps of:
step S104, placing the leacheate obtained by separation in the step S101 into advanced oxidation equipment for advanced oxidation treatment of sodium persulfate, wherein the reaction concentration is 0.1mM, the pH value is adjusted to 10 after the reaction is carried out for 20 minutes, adding 0.05mM of polyaluminium chloride for coagulating sedimentation for 30 minutes, stirring at the speed of 100r/min, discharging supernatant through an overflow port, separating clear water and sludge from bottom sludge through a plate-and-frame filter press, wherein the sludge is solid waste obtained after heavy metal is subjected to coagulating sedimentation, and delivering the solid waste to qualified units for treatment or resource utilization;
and S105, taking the eluate processed in the step S104 as reuse water to prepare sodium persulfate solution for ectopic elution of the soil in the step S101, so as to realize recycling of water resources.
Example 4:
step S100 is the same as in embodiment 1, and is not described here again.
Step S101: and (4) carrying out filter pressing on the soil-water mixed liquid obtained in the step (S100) by using an acid-resistant filter press, wherein the final dehydration efficiency reaches 85%. The water after filter pressing is led into the reaction tank through a conduit. And collecting the mud cakes, and piling the mud cakes into a soil piling reaction tank after the mass of the mud cakes reaches 100 kg.
Step S102, spraying charcoal powder into a soil reactor, keeping the water content of soil above 60%, adjusting the pH of the piled soil to 7, keeping the temperature of the piled soil at 37 ℃, and piling the soil for 14 days, wherein the adding amount is 2.0g/kg (charcoal/soil).
Step S103, soil stacking acceptance: and (5) returning the unqualified soil to the step S100 or the step S101 until the repair is qualified, and finishing the repair.
Further comprising the steps of:
step S104, placing the leacheate obtained by separation in the step S101 into advanced oxidation equipment for advanced oxidation treatment of sodium persulfate, wherein the reaction concentration is 0.1mM, the pH value is adjusted to 10 after the reaction is carried out for 20 minutes, adding 0.05mM of polyaluminium chloride for coagulating sedimentation for 30 minutes, stirring at the speed of 100r/min, discharging supernatant through an overflow port, separating clear water and sludge from bottom sludge through a plate-and-frame filter press, wherein the sludge is solid waste obtained after heavy metal is subjected to coagulating sedimentation, and delivering the solid waste to qualified units for treatment or resource utilization;
and S105, taking the eluate processed in the step S104 as reuse water to prepare sodium persulfate solution for ectopic elution of the soil in the step S101, so as to realize recycling of water resources.
As shown in fig. 2, by taking polycyclic aromatic hydrocarbons as an example, the removal efficiency of pollutants of the raw soil after leaching treatment reaches 79-93%, and the removal efficiency of organic matters of sodium persulfate activated by activated carbon is highest. The soil treated by the sodium persulfate activated by the activated carbon is respectively added with 0.1g/kg, 0.5g/kg and 2g/kg to continuously promote the degradation of organic matters, and the adding amount of the biochar with the weight of more than 0.5g/kg can reduce the content of the organic matters to below 2 mg/kg.
Biomass was measured according to the phospholipid fatty acid (PLFA) method, and microbial community structure was determined using the 16S rDNA method.
As shown in fig. 3, 4, 5, the PLFA content after 3 days of reaction after activation by biochar showed a tendency to decrease first and then increase, indicating that the addition of biochar contributes to the alteration of the soil microbial community structure.
As shown in fig. 6, the eluted soil is beneficial to increase the total biomass number of the bacterial flora along with the addition of the biochar during the stacking process; as shown in FIG. 7, the relative abundance of genes (enzymes) such as 1-hydroxy-2-naphthoate dioxygenase and PAH dioxygenase large subustit is increased, and the function of the PAHs degrading bacteria is strengthened. The biochar has an improvement effect on the microbial habitat of the leached soil.
Collecting the soil leacheate after leaching, the supernatant after coagulating sedimentation and the treated soil to determine the content of heavy metals such as cadmium, copper, chromium, nickel, zinc, mercury, arsenic, lead and the like. In the embodiment, the cadmium content in the soil is high, taking cadmium as an example, as shown in FIG. 8, the cadmium content in the leacheate after leaching is higher than 10mg/L, and the cadmium content is reduced to below 0.1mg/L after coagulating sedimentation. The cadmium content in the stack is again reversed, and the original 48.2mg/kg is reduced to 2.48 mg/kg. And (4) transferring heavy metals from the soil to leacheate from the soil by leaching, and then carrying out coagulating sedimentation to realize reduction, wherein the content of the finally treated heavy metals is lower than 3 mg/kg.
The above examples are merely illustrative of the present invention and the scope of the present invention is not limited by the examples.
Claims (4)
1. A method for strengthening microorganism to repair organic-heavy metal composite polluted soil by coupling chemical oxidation with biochar is characterized by comprising the following steps:
step S100, ex-situ leaching: crushing soil to be repaired, removing stones and coarse sand larger than 4mM through wet screening until the particle size of the soil is smaller than 4mM, pouring the soil to be repaired into a leaching pond with a soil-water ratio of 1: 3-1: 5(v: v), adjusting the pH value to 5, adding an activated sodium persulfate (PS, 0.5-0.8 mM) solution for leaching treatment, and obtaining a soil-water mixed liquid;
step S101, separating soil from water: filter-pressing the soil-water mixed liquid obtained in the step S100 to enable the dehydration efficiency to reach more than 80%, collecting eluent, and enabling filter-pressed mud cakes to enter the next step;
step S102, adding carbon in soil pile: putting the mud cake obtained in the step S101 into a soil stacking reaction tank, spraying charcoal powder into a soil reactor, adding the charcoal powder into the soil reactor, keeping the water content of the soil to be more than 60%, adjusting the pH value of the stacked soil to be 7, keeping the temperature of a stacked body to be 37 ℃, and stacking the soil for 14 days;
step S103, soil stacking acceptance: and (5) returning the unqualified soil to the step S100 or the step S101 until the repair is qualified, and finishing the repair.
2. The method according to claim 1, wherein the leaching treatment is carried out by stirring for 30 minutes at 200-300r/min with a stirrer, and then stirring for 15 minutes at a stirring speed of 100-150r/min and standing.
3. The method according to claim 1, characterized in that the biochar is prepared by washing canna for multiple times by water to remove surface adherents, then air-drying for 2 days, drying in an oven at 70-80 ℃ overnight, crushing, sieving by a 100-mesh sieve, and filling in a brown bottle for later use; then weighing 20g of the biomass powder in a crucible, and putting the crucible in a muffle furnace at 350 ℃ for carbonization for 6 hours; cooling to room temperature and taking out; the carbide was treated with 200mL of hydrochloric acid (1M) solution for 12 hours to remove ash; filtering, washing with distilled water to neutrality, and oven drying at 70-80 deg.C.
4. The method of claim 1, further comprising the steps of:
step S104, leacheate treatment: placing the leacheate separated in the step S101 in advanced oxidation equipment for advanced oxidation treatment of sodium persulfate, adjusting the pH to 9-10 after reacting for 20 minutes, adding polyaluminum chloride or polyferric chloride to coagulate and precipitate the solution, and separating clear water and sludge through a plate-and-frame filter press, wherein the sludge is solid waste obtained after coagulating and precipitating heavy metals;
step S105, leaching liquor recycling: and (4) taking the eluate treated in the step (S104) as reuse water to prepare a sodium persulfate solution for ectopic elution of the soil in the step (S101), so as to realize recycling of water resources.
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