CN105945054B - Heavily-polluted site Zn in-situ and ex-situ coupling detoxification method based on biogas residues - Google Patents
Heavily-polluted site Zn in-situ and ex-situ coupling detoxification method based on biogas residues Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 10
- 230000008878 coupling Effects 0.000 title claims abstract description 9
- 238000010168 coupling process Methods 0.000 title claims abstract description 9
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 9
- 238000001784 detoxification Methods 0.000 title claims abstract description 9
- 238000011066 ex-situ storage Methods 0.000 title claims abstract description 9
- 239000002689 soil Substances 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000003814 drug Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 18
- 238000003860 storage Methods 0.000 claims description 11
- 238000005067 remediation Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002344 surface layer Substances 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 2
- 239000010815 organic waste Substances 0.000 claims description 2
- 239000002352 surface water Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 229920002472 Starch Polymers 0.000 claims 1
- 238000000855 fermentation Methods 0.000 claims 1
- 230000004151 fermentation Effects 0.000 claims 1
- 235000013305 food Nutrition 0.000 claims 1
- 102000004169 proteins and genes Human genes 0.000 claims 1
- 108090000623 proteins and genes Proteins 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- 239000008107 starch Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000012423 maintenance Methods 0.000 abstract description 4
- 230000002829 reductive effect Effects 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 2
- 239000012466 permeate Substances 0.000 abstract description 2
- 230000000813 microbial effect Effects 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 34
- 241000894006 Bacteria Species 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 238000005842 biochemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000644 propagated effect Effects 0.000 description 3
- 238000001723 curing Methods 0.000 description 2
- 239000002068 microbial inoculum Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 239000003124 biologic agent Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
Landscapes
- 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 adopts a biogas residue-based Zn in-situ and ex-situ coupling detoxification method for a heavily polluted site, wherein biogas residues, a carbon source and sulfate are prepared into a medicament to be applied to Zn-containing soil, and then a special construction and maintenance mode is adopted to enable a reductive ecological microbial agent to gradually permeate into the ground to reduce Zn in deep polluted soil. The method can be used for repairing the Zn-containing site with higher pollution depth at low cost and high efficiency, simultaneously treats waste by waste and treats biogas residues.
Description
Technical Field
The invention provides a novel method for treating Zn-polluted soil, which is characterized in that biogas residues, a carbon source and sulfate are prepared into a medicament to be applied to Zn-containing soil, and then a special maintenance mode is adopted, so that Zn can be efficiently fixed, 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 waste water, a large amount of soil is polluted by Zn. Current methods of treating zinc-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 Zn in-situ and ex-situ coupling detoxification method for a heavily polluted site, wherein biogas residues, a carbon source and sulfate are prepared into a medicament to be applied to Zn-containing soil, and then a special construction and maintenance mode is adopted to enable a reduction ecological microbial inoculum to gradually permeate underground and reduce Zn in deep polluted soil. The method can be used for repairing the Zn-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 sulfate (recorded as SO 4)/organic carbon to be (0-1): 1, and reacting the mixed solution for 0-5 days to obtain a Zn soil remediation agent;
(2) excavating soil with the surface layer of 1-10m of the Zn-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 Zn-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 Zn 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.
According to the method, through special ecological agent addition and special field maintenance, a flora mainly comprising sulfate reducing bacteria is promoted to be formed in a large range in a field, the flora can effectively fix Zn by utilizing a carbon source, and meanwhile, sulfate is fully utilized and converted into sulfide, and Zn is converted into more stable Zn sulfide precipitate while being effectively fixed.
Compared with the traditional Zn-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 Zn 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 Zn, and does not cause ecological problems;
3. the reduced Zn and sulfide of a metabolic product of sulfate reducing bacteria form Zn sulfide precipitate, so that the Zn 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 sulfate (recorded as SO 4)/organic carbon to be 0.7: 1, and reacting the mixed solution for 2 days to obtain a Zn soil remediation agent;
(2) excavating 10m soil on the surface layer of the Zn-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, mixing the crushed soil with the medicament in the step (1) in a mass ratio of the Zn-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 several times to the total Zn content of the whole site is not lower than 0.5: 1; the average rainfall of the field is 500mm each year by natural rainfall and artificial spraying. After 2 years of engineering implementation, the Zn content of the soil with the depth of more than 20 meters is less than 2mg/kg, and the Zn content of underground water is less 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 sulfate (recorded as SO 4)/organic carbon to be 0.5:1, and reacting the mixed solution for 1 day to obtain a Zn soil remediation agent;
(2) excavating soil with the surface layer of 5m of a Zn-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, mixing the crushed soil with the medicament in the step (1) in a mass ratio of the Zn-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 several times to the total Zn content of the whole site is not lower 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 Zn content of the soil with the depth of more than 40 meters is less than 2mg/kg, and the Zn content of underground water is less 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 heavily polluted site Zn 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 (0.5-1) to 1, and reacting the mixed solution for 0-5 days to obtain a Zn soil remediation agent;
(2) excavating soil with the surface layer of 1-10m of the Zn-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, flatly paving the crushed soil on a semi-closed storage yard, spraying and mixing the medicament in the step (1) according to the mass ratio of the Zn-containing soil to the medicament of 1 (0.1-0.8), and then entering a storage period;
(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 injecting the soil remediation agent or the carbon source solution in the step (1) into the field every 1-200 days, and the ratio of accumulated organic carbon in the agent or the carbon source solution to the total Zn content of the whole field is required to be not less 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 of Zn in heavily polluted site 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 of Zn in heavily polluted site based on biogas residues as claimed in claim 1, wherein the carbon source solution can be a solution containing alcohol, sugar, protein, starch, industrial organic garbage, kitchen garbage, industrial and municipal organic wastewater, and the sodium sulfate can be replaced by other sulfate-containing substances.
4. The in-situ and ex-situ coupling detoxification method of Zn in heavily polluted site based on biogas residues as claimed in claim 1, wherein the water sprayed on the surface of the heavily polluted site 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 of heavily polluted site Zn 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 small holes in the mesh geomembrane is 1-100mm, and the distance between the holes is 0.01-10 m.
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