CN106001087B - Hg in-situ and ectopic coupling detoxification method for heavily polluted site - Google Patents
Hg in-situ and ectopic coupling detoxification method for heavily polluted site Download PDFInfo
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- CN106001087B CN106001087B CN201610370391.5A CN201610370391A CN106001087B CN 106001087 B CN106001087 B CN 106001087B CN 201610370391 A CN201610370391 A CN 201610370391A CN 106001087 B CN106001087 B CN 106001087B
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 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
- 239000002689 soil Substances 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- 239000010802 sludge Substances 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000003814 drug Substances 0.000 claims abstract description 13
- 238000011066 ex-situ storage Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000003860 storage Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 238000005067 remediation Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- 239000002910 solid waste Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 239000002352 surface water Substances 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000002068 microbial inoculum Substances 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 239000012466 permeate Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 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
- 239000002244 precipitate Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-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
- 239000002207 metabolite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 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
- B09C1/105—Reclamation of contaminated soil microbiologically, biologically or by using enzymes using fungi or plants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Soil Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Mycology (AREA)
- Botany (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention adopts an Hg in-situ and ex-situ coupling detoxification method for a heavily polluted site, sludge, a carbon source and sulfate are prepared into a medicament to be applied to Hg-containing soil, and then a special construction and maintenance mode is adopted to enable a reduction ecological microbial inoculum to gradually permeate underground to reduce deep polluted soil Hg. The method can be used for repairing the Hg-containing site with higher pollution depth at low cost and high efficiency, and simultaneously treats waste with waste to treat sludge.
Description
Technical Field
The invention provides a novel method for treating Hg-contaminated soil, which is characterized in that sludge, a carbon source and sulfate are prepared into a medicament to be applied to Hg-containing soil, and then a special maintenance mode is adopted, so that Hg 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 waste water, a large amount of soil is polluted by Hg. 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 an in-situ and ex-situ coupling detoxification method for heavy polluted site Hg, sludge, carbon source and sulfate are prepared into a medicament to be applied to Hg-containing soil, and then a special construction and maintenance mode is adopted to ensure that a reduction ecological microbial inoculum gradually permeates underground to reduce deep polluted soil Hg. The method can be used for repairing the Hg-containing site with higher pollution depth at low cost and high efficiency, and simultaneously treats waste with waste to treat sludge. Which comprises the following steps:
(1) mixing sodium sulfate, sludge or carbon source solution according to a certain proportion, enabling the dry sludge content of the mixed solution to be 0.1-20%, the solid content to be 0.5-25%, the organic carbon content 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 the Hg soil remediation agent;
(2) excavating soil with the surface layer of 1-10m of the Hg-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 crushed soil with the medicament in the step (1) according to the mass ratio of Hg-containing soil to the medicament of 1 (0.1-0.8), and then placing the mixture in the 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 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 Hg 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 sludge is anaerobic sludge generated by a sewage treatment anaerobic process, and part of facultative sludge can be added; the carbon source solution can be a solution containing alcohol, sugar, protein and starch, can also be a solution of organic solid 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.
According to the method, through special ecological agent addition and special site maintenance, a flora mainly comprising sulfate reducing bacteria is promoted to be formed in a large-scale site, the flora can firstly effectively reduce Hg by utilizing a carbon source, and simultaneously, sulfate is fully utilized and converted into sulfide, and Hg is effectively reduced and converted into more stable Hg sulfide precipitate.
Compared with the traditional Hg-containing soil treatment method, the method has the following advantages:
1. sulfate reducing bacteria in the sludge microbial inoculum reduce sulfate to generate sulfide, so that Hg 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 Hg, and does not cause ecological problems;
3. the reduced Hg and sulfide of a sulfate reducing bacteria metabolite form Hg sulfide precipitate, so that Hg in soil is more stable and is obviously superior to other biochemical processes;
4. the method uses the sludge and the organic waste 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, sludge or carbon source solution according to a certain proportion, enabling the dry sludge content of the mixed solution to be 0.1-5%, the solid content to be 0.5-5%, the organic carbon content 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 the Hg soil remediation agent;
(2) excavating 10m of soil on the surface layer of the Hg-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, mixing the crushed soil with the medicament in the step (1) in a mass ratio of Hg-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 Hg 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 2 years, the Hg content of the soil with the depth of more than 20 meters is lower than 2mg/kg, and the Hg content of underground water is lower than 0.1 mg/L.
Example 2:
(1) mixing sodium sulfate, sludge or carbon source solution according to a certain proportion, enabling the dry sludge content of the mixed solution to be 5-15%, the solid content to be 5-15%, the organic carbon content 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 the Hg soil remediation agent;
(2) excavating 5m of soil on the surface layer of the Hg-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, mixing the crushed soil with the medicament in the step (1) in a mass ratio of Hg-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 Hg 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 Hg content of the soil with the depth of more than 40 meters is lower than 2mg/kg, and the Hg 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. An in-situ and ex-situ coupling detoxification method for Hg in a heavily polluted site is characterized by comprising the following steps:
(1) mixing sodium sulfate, sludge or carbon source solution according to a certain proportion, enabling the dry sludge content of the mixed solution to be 0.1-20%, the solid content to be 0.5-25%, the organic carbon content 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 the Hg soil remediation agent;
(2) excavating soil with the surface layer of 1-10m of the Hg-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 crushed soil with the medicament in the step (1) according to the mass ratio of Hg-containing soil to the medicament of 1 (0.1-0.8), and then placing the mixture in 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 injecting the soil remediation agent or the carbon source solution in the step (1) into the site every 1-200 days, and requiring that the ratio of accumulated organic carbon in the agent or the carbon source solution to the total Hg 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 Hg in-situ and ex-situ coupling detoxification method for heavily polluted sites as claimed in claim 1, wherein the sludge is anaerobic sludge generated by anaerobic process of sewage treatment, and optionally some facultative sludge is added.
3. The in situ and ex situ coupling detoxification method for the heavily polluted site Hg according to claim 1, wherein the carbon source solution can be a solution containing alcohol, sugar, protein, starch, an organic solid waste solution, an industrial and municipal organic wastewater, and the sodium sulfate can be replaced by other sulfate.
4. The in situ and ex situ coupling detoxification method for heavily polluted site Hg as claimed in claim 1, wherein the water sprayed on the surface of the heavily polluted site Hg is replaced by an organic solution, and the organic carbon content of the organic solution is 10-1000 mg/L.
5. The Hg in-situ and ex-situ coupling detoxification method for the heavily polluted site as claimed in claim 1, wherein the geomembrane with meshes laid in the step (2) is made of 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.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103981097A (en) * | 2013-12-05 | 2014-08-13 | 青岛理工大学 | Method for preparing Cr (VI) polluted site remediation flora by using sludge |
| CN105598144A (en) * | 2016-03-22 | 2016-05-25 | 安徽工程大学 | Restoration method of polluted soil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100372951C (en) * | 2005-03-01 | 2008-03-05 | 同济大学 | Process for separating and recovering sludge and heavy metals in soil |
| CN101863706B (en) * | 2010-07-08 | 2012-09-19 | 李桓宇 | Organic composite fertilizer produced by using paper making sludge and manufacturing method thereof |
| CN102500612B (en) * | 2011-10-28 | 2013-06-05 | 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 |
| CN103978026B (en) * | 2013-12-05 | 2015-10-28 | 青岛理工大学 | Method for in-situ repairing Cr (VI) -containing site by utilizing organic waste |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103981097A (en) * | 2013-12-05 | 2014-08-13 | 青岛理工大学 | Method for preparing Cr (VI) polluted site remediation flora by using sludge |
| CN105598144A (en) * | 2016-03-22 | 2016-05-25 | 安徽工程大学 | Restoration method of polluted soil |
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