CN105945056A - Heavy pollution site Cd in-situ and ex-situ coupling detoxification method based on biogas residues - Google Patents
Heavy pollution site Cd in-situ and ex-situ coupling detoxification method based on biogas residues Download PDFInfo
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- CN105945056A CN105945056A CN201610370434.XA CN201610370434A CN105945056A CN 105945056 A CN105945056 A CN 105945056A CN 201610370434 A CN201610370434 A CN 201610370434A CN 105945056 A CN105945056 A CN 105945056A
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- 238000011065 in-situ storage Methods 0.000 title claims abstract description 10
- 238000001784 detoxification Methods 0.000 title claims abstract description 9
- 230000008878 coupling Effects 0.000 title claims abstract description 4
- 238000010168 coupling process Methods 0.000 title claims abstract description 4
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 4
- 238000000034 method Methods 0.000 title abstract description 20
- 238000011066 ex-situ storage Methods 0.000 title abstract 2
- 239000002689 soil Substances 0.000 claims abstract description 40
- 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
- 239000003814 drug 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 18
- 239000000243 solution Substances 0.000 claims description 23
- 238000009412 basement excavation Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000005067 remediation Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 239000007921 spray Substances 0.000 claims description 5
- 238000009825 accumulation Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000013589 supplement 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 2
- 229920002472 Starch Polymers 0.000 claims 1
- 238000006065 biodegradation reaction Methods 0.000 claims 1
- 150000001720 carbohydrates Chemical class 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 claims 1
- 238000000855 fermentation Methods 0.000 claims 1
- 230000004151 fermentation Effects 0.000 claims 1
- 239000010794 food waste Substances 0.000 claims 1
- 238000002513 implantation Methods 0.000 claims 1
- 239000010815 organic waste Substances 0.000 claims 1
- 102000004169 proteins and genes Human genes 0.000 claims 1
- 108090000623 proteins and genes Proteins 0.000 claims 1
- 239000002910 solid waste Substances 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- 239000008107 starch Substances 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 4
- 238000012423 maintenance Methods 0.000 abstract description 4
- 239000002068 microbial inoculum Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000012466 permeate Substances 0.000 abstract description 2
- 241000894006 Bacteria Species 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 4
- 238000005842 biochemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000002262 irrigation Effects 0.000 description 2
- 238000003973 irrigation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 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
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005516 engineering process Methods 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
- 238000005065 mining Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 125000000101 thioether group Chemical group 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 heavy pollution site Cd 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 Cd-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 Cd in deep polluted soil. The method can be used for repairing the Cd-containing site with high pollution depth at low cost and high efficiency, and simultaneously treats waste with waste and treats biogas residues.
Description
Technical field
The present invention provides a kind of method of novel process Cd contaminated soil; biogas residue, carbon source and sulfate are configured to pharmacy application in containing in Cd soil, use special maintenance method subsequently, can reduce Cd efficiently; avoid the secondary pollution of sulfate simultaneously, belong to field of environment protection.
Background technology
Owing to mining, Metallurgical Waste Water arbitrarily discharge, cause a large amount of soil and polluted by Cd.Process the method containing cadmium soil at present the most defective.High-temperature melting method cost is high, and power consumption is big.Bioanalysis is long for reaction time, and easily causes the secondary pollution of adventive microbial inoculum.Solidification method effect is unstable, and soil is easily caused secondary pollution by firming agent.The patent No. 201510056406.6 describes a kind of curing containing heavy metal soil, but the method using substantial amounts of material, relatively costly, on the other hand solidification effect is unstable, the most easily there is carbonation in the calcium oxide as added so that alkaline-curing effect reduces.
Summary of the invention
For the deficiencies in the prior art, the present invention uses a kind of heavily contaminated place Cd based on biogas residue in situ and dystopy coupling detoxification, biogas residue, carbon source and sulfate are configured to pharmacy application in containing in Cd soil, use special construction and maintenance method subsequently, make ecosystem revivification microbial inoculum gradually permeate the ground, deep layer polluted soil Cd is reduced.The place containing Cd that pollution depth is higher can be repaired by this method with low cost and efficiently, and biogas residue is processed by the treatment of wastes with processes of wastes against one another simultaneously.It comprises the steps of
(1) sodium sulfate, biogas residue or carbon source solution are mixed according to a certain percentage, after making mixing, solution dried biogas residues content is 0.1-20%, solid content 0.5-25%, organic carbon content 0.5-25%, the mass ratio of sulfate (remembering with SO4)/organic carbon is for (0-1): 1, mixed solution reaction 0-5 days, it is thus achieved that Cd soil remediation medicament；
(2) will contain top layer, Cd place 1-10m soil to be excavated, and lay the geomembrane with mesh subsequently bottom the place after excavation, excavation place surrounding is laid impervious material, is built up semiclosed stockyard；
(3) by the soil breaking in step (2) to below 10mm, it is laid on semiclosed stockyard, use subsequently step (1) described medicament spray mixing, mixed proportion be the mass ratio containing Cd soil Yu medicament be 1:(0.1-0.8)；
(4) store up period, keep soil moisture content in 5-60% scope in 5-100 days in the early stage, make biochemical reaction be carried out, amount reproduction sulfate reducting bacteria in the venue；Spraying to place every 1-200 days the soil remediation medicament described in step (1) or carbon source solution, the accumulation organic carbon in spraying agent or carbon source solution requires to be not less than 0.5:1 with the whole place ratio containing Cd total amount for several times simultaneously；Require the annual average rainfall in place at more than 200mm, not enough then use the mode of surface sprinkling water to supplement, enable medicament continuous to lower floor's seepage flow.
This method is added by special ecological medicament and special place maintenance, place is promoted to form the flora based on sulfate reducting bacteria on a large scale, first this flora can utilize carbon source effectively to reduce Cd, make full use of sulfate simultaneously, it is translated into sulfide, effectively reduction Cd is simultaneously, and Cd is converted into more stable sulfuration Cd precipitation.
Comparing traditional containing Cd agent, soil treatment method, this method has a following advantage:
1. the sulfate reducting bacteria sulphate reducing in biogas residue microbial inoculum, generates sulfide, can be while more efficient fixing Cd；
2. the sulfate reduction flora cultivated itself is indigenous flora, and natural tolerance is strong, easily multiplies on a large scale in place, can the most effectively fix Cd, and does not results in ecological problem；
3. the Cd after reduction and sulfate reducting bacteria metabolite sulfide form sulfuration Cd precipitation so that in soil, Cd is more stable, is significantly better than other biochemical process；
4. this method uses biogas residue and debirs as primary raw material, greatly reduces cost；
5. this method uses in-situ immobilization to deep soil, it is to avoid the excavation of deep soil, greatly reduces cost.
It is embodied as example as follows:
Embodiment 1:
(1) sodium sulfate, biogas residue or carbon source solution are mixed according to a certain percentage, after making mixing, solution dried biogas residues content is 0.1-5%, solid content 0.5-5%, organic carbon content 0.5-5%, the mass ratio of sulfate (remembering with SO4)/organic carbon is as 0.7:1, mixed solution reaction 2 days, it is thus achieved that Cd soil remediation medicament；
(2) will contain top layer, Cd place 10m soil to be excavated, and lay the geomembrane with mesh subsequently bottom the place after excavation, excavation place surrounding is laid impervious material, is built up semiclosed stockyard；
(3) by the soil breaking in step (2) to below 5mm, mix with step (1) described medicament subsequently, mixed proportion be the mass ratio containing Cd soil Yu medicament be 1:0.5, be subsequently placed to step (2) semiclosed stockyard close store up；
(4) store up period, keep soil moisture content in 5-60% scope in 20 days in the early stage, make biochemical reaction be carried out, amount reproduction sulfate reducting bacteria in the venue；Initial 100 days every 2 days to the soil remediation medicament described in place sprinkling irrigation step (1) or carbon source solution, later stage was separated by natural law more than 20 days, and the accumulation organic carbon in spraying agent or carbon source solution requires to be not less than 0.5:1 with the whole place ratio containing Cd total amount for several times；By natural precipitation and artificial spray, make the annual average precipitation in place at 500mm.After engineering construction 2 years, more than 20 meters soil Cd content of deep layer are below 2mg/kg, and subsoil water amount containing Cd is less than 0.1mg/L.
Embodiment 2:
(1) sodium sulfate, biogas residue or carbon source solution are mixed according to a certain percentage, after making mixing, solution dried biogas residues content is 5-15%, solid content 5-15%, organic carbon content 5-15%, the mass ratio of sulfate (remembering with SO4)/organic carbon is as 0.5:1, mixed solution reaction 1 day, it is thus achieved that Cd soil remediation medicament；
(2) will contain top layer, Cd place 5m soil to be excavated, and lay the geomembrane with mesh subsequently bottom the place after excavation, excavation place surrounding is laid impervious material, is built up semiclosed stockyard；
(3) by the soil breaking in step (2) to below 5mm, mix with step (1) described medicament subsequently, mixed proportion be the mass ratio containing Cd soil Yu medicament be 1:0.5, be subsequently placed to step (2) semiclosed stockyard close store up；
(4) store up period, keep soil moisture content in 5-60% scope in 20 days in the early stage, make biochemical reaction be carried out, amount reproduction sulfate reducting bacteria in the venue；Initial 100 days every 2 days to the soil remediation medicament described in place sprinkling irrigation step (1) or carbon source solution, later stage was separated by natural law more than 20 days, and the accumulation organic carbon in spraying agent or carbon source solution requires to be not less than 0.5:1 with the whole place ratio containing Cd total amount for several times；By natural precipitation and artificial spray, make the annual average precipitation in place at 500mm.After engineering construction 1 year, more than 40 meters soil Cd content of deep layer are below 2mg/kg, and subsoil water amount containing Cd is less than 0.1mg/L.
Above example is only in order to illustrate technical scheme, rather than is limited；Although the present invention being described in detail with reference to previous embodiment, for the person of ordinary skill of the art, still the technical scheme described in previous embodiment can be modified, or wherein portion of techniques feature is carried out equivalent；And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of claimed technical solution of the invention.
Claims (5)
1. heavily contaminated place Cd based on biogas residue is in situ and dystopy couples a detoxification, it is characterized in that, comprises the steps of
(1) sodium sulfate, biogas residue or carbon source solution are mixed according to a certain percentage, after making mixing, solution dried biogas residues content is 0.1-20%, solid content 0.5-25%, organic carbon content 0.5-25%, the mass ratio of sulfate (remembering with SO4)/organic carbon is for (0-1): 1, mixed solution reaction 0-5 days, it is thus achieved that Cd soil remediation medicament；
(2) will contain top layer, Cd place 1-10m soil to be excavated, and lay the geomembrane with mesh subsequently bottom the place after excavation, excavation place surrounding is laid impervious material, is built up semiclosed stockyard；
(3) by the soil breaking in step (2) to below 10mm, it is laid on semiclosed stockyard, use subsequently step (1) described medicament spray mixing, mixed proportion be the mass ratio containing Cd soil Yu medicament be 1:(0.1-0.8), subsequently enter the phase of storing up；
(4) store up period, keep soil moisture content in 5-60% scope in 5-100 days in the early stage, required to be not less than 0.5:1 with the whole place ratio containing Cd total amount to the soil remediation medicament described in place implantation step (1) or carbon source solution, the accumulation organic carbon injected for several times in medicament or carbon source solution every 1-200 days simultaneously；Require the annual average rainfall in place at more than 200mm, not enough then use the mode of surface sprinkling water to supplement, enable medicament continuous to lower floor's seepage flow.
A kind of heavily contaminated place Cd based on biogas residue in situ and dystopy coupling detoxification, is characterized in that, described biogas residue is that agricultural, grocery trade debirs carry out the solid residue in dry type, half dry type and wet type anaerobic fermentation process.
A kind of heavily contaminated place Cd based on biogas residue is in situ and dystopy couples detoxification, it is characterized in that, described carbon source solution can be containing organic solution such as ethanol, saccharide, protein, starch, can also be for the solution containing the industry organic solid waste such as organic waste, changing food waste, can also be industrial and municipal organic wastewater, described sodium sulfate can be substituted by the material of other containing sulfate.
A kind of heavily contaminated place Cd based on biogas residue is in situ and dystopy couples detoxification, it is characterized in that, the described water in Water spray can be substituted by organic solution, and the organic carbon content of organic solution is 10-1000mg/L.
A kind of heavily contaminated place Cd based on biogas residue is in situ and dystopy couples detoxification, it is characterized in that, step (2) described laying can be difficult for biological degradation material with the geomembrane material of mesh, it is possible to is biodegradation material；Aperture equivalent diameter in mesh geomembrane between 1-100mm, Kong Yukong at 0.01-10m.
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| CN104312591A (en) * | 2014-10-13 | 2015-01-28 | 贵州美瑞特环保科技有限公司 | Stabilized curing agent for heavy metal contaminated soil or solid waste treatment and treatment method |
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-
2016
- 2016-05-30 CN CN201610370434.XA patent/CN105945056B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101791624A (en) * | 2010-02-04 | 2010-08-04 | 中南大学 | Method for utilizing and disposing micro-electrolyzed waste residue of organic waste water and method for immobilizing arsenic and heavy metal in soil |
| CN102500612A (en) * | 2011-10-28 | 2012-06-20 | 中南大学 | Chemical leaching restoring method for soil polluted by heavy metals |
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Effective date of registration: 20231026 Address after: 250000 303A, 13, Zhong run Century City, No. 13777, ten road, Lixia District, Ji'nan, Shandong Patentee after: SHANDONG ENVIRONMENTAL PROTECTION INDUSTRY GROUP Co.,Ltd. Address before: 266033 No. 2 Changjiang Road, Qingdao economic and Technological Development Zone, Shandong Patentee before: Qingdao University of Technology |