CN106040736A - 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 PDFInfo
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- CN106040736A CN106040736A CN201610370417.6A CN201610370417A CN106040736A CN 106040736 A CN106040736 A CN 106040736A CN 201610370417 A CN201610370417 A CN 201610370417A CN 106040736 A CN106040736 A CN 106040736A
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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 8
- 238000000034 method Methods 0.000 title abstract description 20
- 230000008878 coupling Effects 0.000 title abstract description 3
- 238000010168 coupling process Methods 0.000 title abstract description 3
- 238000005859 coupling reaction Methods 0.000 title abstract description 3
- 238000011066 ex-situ storage Methods 0.000 title abstract 2
- 239000002689 soil Substances 0.000 claims abstract description 42
- 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 22
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 10
- 238000009412 basement excavation Methods 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 8
- 239000007787 solid Substances 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000009825 accumulation Methods 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000011259 mixed solution 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
- 239000010909 process residue Substances 0.000 claims 1
- 102000004169 proteins and genes Human genes 0.000 claims 1
- 108090000623 proteins and genes Proteins 0.000 claims 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 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
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000002068 microbial inoculum Substances 0.000 abstract description 3
- 239000012466 permeate Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 9
- 241000894006 Bacteria Species 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 4
- 238000005842 biochemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 238000005507 spraying Methods 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
- 238000005987 sulfurization reaction Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 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
- 239000007788 liquid Substances 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
- 231100000614 poison Toxicity 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
- 239000013589 supplement Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 239000003440 toxic substance Substances 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 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
Technical field
The present invention provides a kind of method of novel process Sb contaminated soil, and biogas residue, carbon source and sulfate are configured to medicament
It is applied to, containing in Sb soil, use special maintenance method subsequently, can reduce Sb efficiently, avoid the two of sulfate simultaneously
Secondary pollution, belongs to field of environment protection.
Background technology
Owing to mining, Metallurgical Waste Water arbitrarily discharge, cause a large amount of soil and polluted by Sb.Process the soil in antimony at present
Method the most defective.High-temperature melting method cost is high, and power consumption is big.Bioanalysis is long for reaction time, and easily causes adventive bacterium
The secondary pollution of agent.Solidification method effect is unstable, and soil is easily caused secondary pollution by firming agent.The patent No.
201510056406.6 describe a kind of curing containing heavy metal soil, but the method use substantial amounts of material, cost
Higher, on the other hand solidification effect is unstable, and the calcium oxide as added the most easily occurs carbonation so that alkali
Property solidification effect reduce.
Summary of the invention
For the deficiencies in the prior art, the present invention uses a kind of heavily contaminated place Sb based on biogas residue in situ and dystopy coupling removing toxic substances
Method, is configured to biogas residue, carbon source and sulfate pharmacy application in containing in Sb soil, uses special construction and maintenance side subsequently
Formula, makes ecosystem revivification microbial inoculum gradually permeate the ground, and is reduced by deep layer polluted soil Sb.This method can be with low cost and the most right
The place containing Sb that pollution depth is higher is repaired, 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 being 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 Sb soil remediation medicament；
(2) top layer, Sb place 1-10m soil will be contained be excavated, lay the soil with mesh bottom the place after excavation subsequently
Work film, 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, uses step (1) institute subsequently
State medicament spray mixing, mixed proportion be the mass ratio containing Sb 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；Sprayed to place every 1-200 days the soil remediation medicine described in step (1) simultaneously
Agent or carbon source solution, the accumulation organic carbon in spraying agent or carbon source solution and the whole place ratio containing Sb total amount is wanted for several times
Ask and be not less than 0.5:1；Require the annual average rainfall in place at more than 200mm, the not enough then mode of employing surface sprinkling water
Supplement, enable medicament constantly to lower floor's seepage flow.
This method is added by special ecological medicament and special place maintenance, promotes place to be formed on a large scale with sulphuric acid
Salt reducing bacteria is main flora, and first this flora can utilize carbon source effectively to reduce Sb, makes full use of sulfate, by its turn simultaneously
Turning to sulfide, effectively reduction Sb is simultaneously, and Sb is converted into more stable sulfuration Sb precipitation.
Comparing traditional containing Sb 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 Sb；
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 Sb, and not result in ecological problem；
3. the Sb after reduction and sulfate reducting bacteria metabolite sulfide form sulfuration Sb precipitation so that in soil, Sb is more steady
Fixed, it 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 being 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, as 0.7:1, mixes
After solution reaction 2 days, it is thus achieved that Sb soil remediation medicament；
(2) top layer, Sb place 10m soil will be contained be excavated, lay the geotechnique with mesh bottom the place after excavation subsequently
Film, excavation place surrounding is laid impervious material, is built up semiclosed stockyard；
(3) by the soil breaking in step (2) to below 5mm, mixing with step (1) described medicament subsequently, mixed proportion is for containing
Sb soil is 1:0.5 with the mass ratio of medicament, and the semiclosed stockyard closing being subsequently placed to step (2) is stored 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 place；Initial 100 days every 2 days to the soil remediation medicine described in place sprinkling irrigation step (1)
Agent or carbon source solution, the later stage is separated by natural law more than 20 days, for several times the accumulation organic carbon in spraying agent or carbon source solution with
The whole place ratio containing Sb total amount requires to be not less than 0.5:1；By natural precipitation and artificial spray, make the average fall that place is annual
The water yield is at 500mm.After engineering construction 2 years, more than 20 meters soil Sb content of deep layer are below 2mg/kg, and subsoil water amount containing Sb is less than
0.1mg/L。
Embodiment 2:
(1) sodium sulfate, biogas residue or carbon source solution being 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 molten
Liquid reacts 1 day, it is thus achieved that Sb soil remediation medicament；
(2) top layer, Sb place 5m soil will be contained be excavated, lay the geotechnique with mesh bottom the place after excavation subsequently
Film, excavation place surrounding is laid impervious material, is built up semiclosed stockyard；
(3) by the soil breaking in step (2) to below 5mm, mixing with step (1) described medicament subsequently, mixed proportion is for containing
Sb soil is 1:0.5 with the mass ratio of medicament, and the semiclosed stockyard closing being subsequently placed to step (2) is stored 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 place；Initial 100 days every 2 days to the soil remediation medicine described in place sprinkling irrigation step (1)
Agent or carbon source solution, the later stage is separated by natural law more than 20 days, for several times the accumulation organic carbon in spraying agent or carbon source solution with
The whole place ratio containing Sb total amount requires to be not less than 0.5:1；By natural precipitation and artificial spray, make the average fall that place is annual
The water yield is at 500mm.After engineering construction 1 year, more than 40 meters soil Sb content of deep layer are below 2mg/kg, and subsoil water amount containing Sb is less than
0.1mg/L。
Above example is only in order to illustrate technical scheme, rather than is limited；Although with reference to aforementioned reality
Execute example the present invention has been described in detail, for the person of ordinary skill of the art, still can be to aforementioned enforcement
Technical scheme described in example is modified, or wherein portion of techniques feature is carried out equivalent；And these are revised or replace
Change, 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 Sb 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 being 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 Sb soil remediation medicament；
(2) top layer, Sb place 1-10m soil will be contained be excavated, lay the soil with mesh bottom the place after excavation subsequently
Work film, 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, uses step (1) described subsequently
Medicament spray mixing, mixed proportion be the mass ratio containing Sb soil Yu medicament be 1:(0.1-0.8), subsequently enter the phase of storing up；
(4) storing up period, in 5-100 days in the early stage, holding soil moisture content is in 5-60% scope, simultaneously every 1-200 days to field
Soil remediation medicament described in ground implantation step (1) or carbon source solution, inject the accumulation in medicament or carbon source solution for several times
Organic carbon and the whole place ratio containing Sb total amount requires to be not less than 0.5:1；Require the annual average rainfall in place 200mm with
On, not enough then employing surface sprinkling water mode is supplemented, and enables medicament constantly to lower floor's seepage flow.
A kind of heavily contaminated place Sb based on biogas residue is in situ and dystopy couples detoxification, and it is special
Levy and be, described biogas residue be agricultural, grocery trade debirs carry out the solid in dry type, half dry type and wet type anaerobic fermentation process
Residue.
A kind of heavily contaminated place Sb based on biogas residue is in situ and dystopy couples detoxification, and it is special
Levying and be, described carbon source solution can be containing organic solution such as ethanol, saccharide, protein, starch, it is also possible to for containing work
The solution of the organic solid wastes such as industry organic waste, changing food waste, it is also possible to for industrial and municipal organic wastewater, described sulphuric acid
Sodium can be substituted by the material of other containing sulfate.
A kind of heavily contaminated place Sb based on biogas residue is in situ and dystopy couples detoxification, and it is special
Levying and be, 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 Sb based on biogas residue is in situ and dystopy couples detoxification, and it is special
Levying and be, step (2) described laying can be difficult for biological degradation material with the geomembrane material of mesh, it is possible to is biodegradation material
Material；Aperture equivalent diameter in mesh geomembrane between 1-100mm, Kong Yukong at 0.01-10m.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610370417.6A CN106040736B (en) | 2016-05-30 | 2016-05-30 | Heavy pollution site Sb in-situ and ex-situ coupling detoxification method based on biogas residues |
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| CN201610370417.6A CN106040736B (en) | 2016-05-30 | 2016-05-30 | Heavy pollution site Sb in-situ and ex-situ coupling detoxification method based on biogas residues |
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| CN106040736B CN106040736B (en) | 2021-04-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110591716A (en) * | 2018-06-13 | 2019-12-20 | 岳西县九方农业有限公司 | Stabilization repair material suitable for heavy metal pollution of tailing waste stone and preparation method |
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2016
- 2016-05-30 CN CN201610370417.6A patent/CN106040736B/en active Active
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