CN106040736B - Heavy pollution site Sb in-situ and ex-situ coupling detoxification method based on biogas residues - Google Patents

Heavy pollution site Sb in-situ and ex-situ coupling detoxification method based on biogas residues Download PDF

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CN106040736B
CN106040736B CN201610370417.6A CN201610370417A CN106040736B CN 106040736 B CN106040736 B CN 106040736B CN 201610370417 A CN201610370417 A CN 201610370417A CN 106040736 B CN106040736 B CN 106040736B
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situ
soil
biogas residues
site
solution
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CN106040736A (en
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张大磊
李瑞栋
王欣玉
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Qingdao University of Technology
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Qingdao University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/08Reclamation of contaminated soil chemically
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/10Reclamation of contaminated soil microbiologically, biologically or by using enzymes

Abstract

The invention adopts a heavy pollution site Sb in-situ and ex-situ coupling detoxification method based on biogas residues, wherein the biogas residues, a carbon source and sulfate are prepared into a medicament to be applied to Sb-containing soil, and then a special construction and maintenance mode is adopted to enable a reduction ecological microbial inoculum to gradually permeate into the ground to reduce the Sb in the deep polluted soil. The method can be used for repairing the Sb-containing site with higher pollution depth at low cost and high efficiency, simultaneously treats waste by waste and treats biogas residues.

Description

Heavy pollution site Sb in-situ and ex-situ coupling detoxification method based on biogas residues
Technical Field
The invention provides a novel method for treating Sb-polluted soil, which is characterized in that biogas residues, a carbon source and sulfate are prepared into a medicament to be applied to the Sb-polluted soil, and then a special maintenance mode is adopted, so that Sb can be efficiently reduced, and secondary pollution of sulfate is avoided, and the method belongs to the field of environmental protection.
Background
Due to the random discharge of mine exploitation and metallurgical wastewater, a large amount of soil is polluted by Sb. Current methods of treating antimony-containing soils have drawbacks. The high-temperature melting method has high cost and large energy consumption. The biological method has long reaction period and is easy to cause secondary pollution of external biological agents. The curing method has unstable effect, and the curing agent is easy to cause secondary pollution to soil. Patent No. 201510056406.6 describes a method for solidifying soil containing heavy metals, but this method uses a large amount of materials and is relatively expensive, and on the other hand, the solidification effect is unstable, for example, calcium oxide added is liable to carbonation under natural conditions, so that the alkaline solidification effect is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention adopts a biogas residue-based Sb in-situ and ex-situ coupling detoxification method for a heavily polluted site, prepares biogas residues, a carbon source and sulfate into a medicament to be applied to Sb-containing soil, and then adopts a special construction and maintenance mode to enable a reduction ecological microbial inoculum to gradually permeate underground to reduce Sb in deep polluted soil. The method can be used for repairing the Sb-containing site with higher pollution depth at low cost and high efficiency, simultaneously treats waste by waste and treats biogas residues. Which comprises the following steps:
(1) mixing sodium sulfate, biogas residues or a carbon source solution according to a certain proportion, enabling the content of dry biogas residues of the mixed solution to be 0.1-20%, the solid content to be 0.5-25%, the content of organic carbon to be 0.5-25%, and the mass ratio of SO 4/organic carbon to be (0-1): 1, and reacting the mixed solution for 0-5 days to obtain an Sb soil remediation agent;
(2) excavating soil with the surface layer of 1-10m of the Sb-containing field, then paving a geomembrane with meshes at the bottom of the excavated field, and paving impermeable materials at the periphery of the excavated field to build a semi-closed storage yard;
(3) crushing the soil in the step (2) to be less than 10mm, paving the crushed soil on a semi-closed storage yard, and then spraying and mixing the medicament in the step (1), wherein the mixing ratio is that the mass ratio of the Sb-containing soil to the medicament is 1 (0.1-0.8);
(4) during the stockpiling period, the water content of the soil is kept within the range of 5-60% within 5-100 days in the initial stage, so that biochemical reaction can be carried out, and sulfate reducing bacteria are propagated in a large amount in the field; spraying the soil remediation agent or the carbon source solution in the step (1) to the site every 1-200 days, wherein the ratio of accumulated organic carbon in the agent or the carbon source solution sprayed for several times to the total Sb content of the whole site is not lower than 0.5: 1; the average rainfall of the field per year is required to be more than 200mm, and if the average rainfall is not enough, the ground is supplemented by adopting a surface water spraying mode, so that the medicine can continuously seep to the lower layer.
In the above steps, the biogas residue is solid residue in the dry, semi-dry and wet anaerobic fermentation process of organic waste in agriculture and food industry; the carbon source solution can be a solution containing alcohol, sugar, protein or starch, can also be a solution containing industrial organic waste or kitchen waste, can also be industrial and municipal organic wastewater, and the sodium sulfate can be replaced by other sulfates; the water sprayed on the surface can be replaced by organic solution, and the organic carbon content of the organic solution is 10-1000 mg/L; the material of the geomembrane paved with meshes in the step (2) can be a material which is difficult to biodegrade or a biodegradable material; the equivalent diameter of small holes in the mesh geomembrane is 1-100mm, and the distance between the holes is 0.01-10 m.
The method promotes the site to form a flora mainly comprising sulfate reducing bacteria in a large range by adding special ecological agents and maintaining the site, the flora can firstly effectively reduce Sb by utilizing a carbon source, simultaneously fully utilizes sulfate to convert the Sb into sulfide, and effectively reduces Sb and simultaneously converts Sb into more stable sulfide Sb precipitates.
Compared with the traditional Sb-containing soil treatment method, the method has the following advantages:
1. sulfate reducing bacteria in the biogas residue microbial inoculum reduce sulfate to generate sulfide, so that Sb can be more effectively fixed;
2. the cultured sulfate reducing flora is indigenous flora, has strong natural tolerance, is easy to propagate on site in a large scale, can permanently and effectively fix Sb, and does not cause ecological problems;
3. the reduced Sb and sulfide of a metabolite of the sulfate reducing bacteria form a Sb sulfide precipitate, so that the Sb in the soil is more stable and is obviously superior to other biochemical processes;
4. the method uses biogas residues and organic wastes as main raw materials, so that the cost is greatly reduced;
5. the method adopts in-situ remediation for the deep soil, avoids excavation of the deep soil and greatly reduces the cost.
The specific implementation example is as follows:
example 1:
(1) mixing sodium sulfate, biogas residues or a carbon source solution according to a certain proportion, enabling the content of dry biogas residues of the mixed solution to be 0.1-5%, the solid content to be 0.5-5%, the content of organic carbon to be 0.5-5% and the mass ratio of SO 4/organic carbon to be 0.7: 1, and reacting the mixed solution for 2 days to obtain an Sb soil remediation agent;
(2) excavating 10m soil on the surface layer of the Sb-containing field, then paving a geomembrane with meshes at the bottom of the excavated field, and paving impermeable materials at the periphery of the excavated field to build a semi-closed storage yard;
(3) crushing the soil in the step (2) to be less than 5mm, then mixing the soil with the medicament in the step (1) in a mass ratio of the Sb-containing soil to the medicament of 1:0.5, and then placing the mixture in a semi-closed storage yard in the step (2) for closed storage;
(4) during the stockpiling period, the water content of the soil is kept within the range of 5-60% within 20 days in the initial stage, so that biochemical reaction can be carried out, and a large amount of sulfate reducing bacteria are propagated in the field; sprinkling the soil remediation agent or the carbon source solution in the step (1) to the site every 2 days for the initial 100 days, wherein the number of days at intervals in the later period exceeds 20 days, and the ratio of accumulated organic carbon in the agent or the carbon source solution sprayed for a plurality of times to the total Sb content of the whole site is required to be not less than 0.5: 1; the average rainfall of the field is 500mm each year by natural rainfall and artificial spraying. After the engineering is carried out for 2 years, the Sb content of the soil with the depth of more than 20 meters is lower than 2mg/kg, and the Sb content of underground water is lower than 0.1 mg/L.
Example 2:
(1) mixing sodium sulfate, biogas residues or a carbon source solution according to a certain proportion, enabling the content of dry biogas residues of the mixed solution to be 5-15%, the solid content to be 5-15%, the content of organic carbon to be 5-15% and the mass ratio of SO 4/organic carbon to be 0.5:1, and reacting the mixed solution for 1 day to obtain an Sb soil remediation agent;
(2) excavating soil with the thickness of 5m on the surface layer of the Sb-containing field, then paving a geomembrane with meshes at the bottom of the excavated field, and paving impermeable materials around the excavated field to build a semi-closed storage yard;
(3) crushing the soil in the step (2) to be less than 5mm, then mixing the soil with the medicament in the step (1) in a mass ratio of the Sb-containing soil to the medicament of 1:0.5, and then placing the mixture in a semi-closed storage yard in the step (2) for closed storage;
(4) during the stockpiling period, the water content of the soil is kept within the range of 5-60% within 20 days in the initial stage, so that biochemical reaction can be carried out, and a large amount of sulfate reducing bacteria are propagated in the field; sprinkling the soil remediation agent or the carbon source solution in the step (1) to the site every 2 days for the initial 100 days, wherein the number of days at intervals in the later period exceeds 20 days, and the ratio of accumulated organic carbon in the agent or the carbon source solution sprayed for a plurality of times to the total Sb content of the whole site is required to be not less than 0.5: 1; the average rainfall of the field is 500mm each year by natural rainfall and artificial spraying. After the engineering is carried out for 1 year, the Sb content of the soil with the depth of more than 40 meters is lower than 2mg/kg, and the Sb content of underground water is lower than 0.1 mg/L.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.

Claims (5)

1. A heavy pollution site Sb in-situ and ex-situ coupling detoxification method based on biogas residues is characterized by comprising the following steps:
(1) mixing sodium sulfate, biogas residues and a carbon source solution according to a certain proportion, enabling the content of dry biogas residues of the mixed solution to be 0.1-20%, the solid content to be 0.5-25%, the content of organic carbon to be 0.5-25% and the mass ratio of SO 4/organic carbon to be 1: 1, and reacting the mixed solution for 0-5 days to obtain an Sb soil remediation agent;
(2) excavating soil with the surface layer of 1-10m of the Sb-containing field, then paving a geomembrane with meshes at the bottom of the excavated field, and paving impermeable materials at the periphery of the excavated field to build a semi-closed storage yard;
(3) crushing the soil in the step (2) to be less than 10mm, paving the crushed soil on a semi-closed storage yard, mixing the crushed soil and the medicament in the step (1) according to the mass ratio of the Sb-containing soil to the medicament of 1 (0.1-0.8), and then placing the mixture on the semi-closed storage yard in the step (2) for closed storage;
(4) during the stockpiling period, keeping the water content of the soil within the range of 5-60% within 5-100 days in the initial period, simultaneously sprinkling the soil remediation agent or the carbon source solution in the step (1) to the site every 1-200 days, and sprinkling the agent or the carbon source solution for a plurality of times, wherein the ratio of the accumulated organic carbon in the agent or the carbon source solution to the total Sb content of the whole site is not lower than 0.5: 1; the average rainfall of the field per year is required to be more than 200mm, and if the average rainfall is not enough, the ground is supplemented by adopting a surface water spraying mode, so that the medicine can continuously seep to the lower layer.
2. The in-situ and ex-situ coupling detoxification method for heavily polluted site Sb based on biogas residues as claimed in claim 1, wherein the biogas residues are solid residues in the dry, semi-dry and wet anaerobic fermentation processes of organic wastes in agriculture and food industry.
3. The in-situ and ex-situ coupling detoxification method for heavily polluted site Sb based on biogas residues as claimed in claim 1, wherein the carbon source solution can be a solution containing alcohol, sugar, protein or starch, a solution containing industrial organic waste or kitchen waste, industrial and municipal organic waste water, and the sodium sulfate can be replaced by other sulfate.
4. The in-situ and ex-situ coupling detoxification method for heavily polluted site Sb based on biogas residues as claimed in claim 1, wherein the water sprayed on the surface of the heavily polluted site Sb is replaced by an organic solution, and the organic carbon content of the organic solution is 10-1000 mg/L.
5. The in-situ and ex-situ coupling detoxification method for heavily polluted site Sb based on biogas residues as claimed in claim 1, wherein the geomembrane material laid with meshes in the step (2) can be a nonbiodegradable material or a biodegradable material; the equivalent diameter of the small holes in the mesh geomembrane is 1-100 mm.
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CN102598911A (en) * 2012-03-29 2012-07-25 常熟市佳盛农业科技发展有限公司 Method for remedying heavy metal polluted mining soil
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CN105032912A (en) * 2015-07-17 2015-11-11 中国科学院武汉岩土力学研究所 In-situ repair method for shallow-buried heavy metal pollution site

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CN102500612A (en) * 2011-10-28 2012-06-20 中南大学 Chemical leaching restoring method for soil polluted by heavy metals
CN102598911A (en) * 2012-03-29 2012-07-25 常熟市佳盛农业科技发展有限公司 Method for remedying heavy metal polluted mining soil
CN104759466A (en) * 2014-01-08 2015-07-08 湖北科技学院 Soil heavy metal ex-situ remediation method based on molecular combination
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