CN105945052A - Pb in-situ and ectopic coupling detoxification method for heavily polluted site - Google Patents
Pb in-situ and ectopic coupling detoxification method for heavily polluted site Download PDFInfo
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- CN105945052A CN105945052A CN201610370389.8A CN201610370389A CN105945052A CN 105945052 A CN105945052 A CN 105945052A CN 201610370389 A CN201610370389 A CN 201610370389A CN 105945052 A CN105945052 A CN 105945052A
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 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 abstract description 3
- 238000010168 coupling process Methods 0.000 title abstract description 3
- 238000005859 coupling reaction Methods 0.000 title abstract description 3
- 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
- 239000010802 sludge Substances 0.000 claims abstract description 8
- 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
- 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
- 239000007787 solid 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000010794 food waste Substances 0.000 claims 1
- 238000002513 implantation Methods 0.000 claims 1
- 239000010815 organic waste Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 102000004169 proteins and genes Human genes 0.000 claims 1
- 108090000623 proteins and genes Proteins 0.000 claims 1
- 239000010865 sewage Substances 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
- 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
- 238000011066 ex-situ storage Methods 0.000 abstract 1
- 241000894006 Bacteria Species 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 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
- 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
- 230000000813 microbial effect Effects 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention adopts a Pb 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 Pb-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 Pb in deep polluted soil. The method can be used for repairing the Pb-containing site with high pollution depth at low cost and high efficiency, and simultaneously treats waste with waste to treat sludge.
Description
Technical field
The present invention provides a kind of method of novel process Pb contaminated soil; mud, carbon source and sulfate are configured to pharmacy application in containing in Pb soil, use special maintenance method subsequently, Pb can be fixed 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 Pb.The method processing leaded soil at present is 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 Pb in situ and dystopy coupling detoxification, mud, carbon source and sulfate are configured to pharmacy application in containing in Pb soil, use special construction and maintenance method subsequently, make ecosystem revivification microbial inoculum gradually permeate the ground, deep layer polluted soil Pb is reduced.The place containing Pb that pollution depth is higher can be repaired by this method with low cost and efficiently, and mud is processed by the treatment of wastes with processes of wastes against one another simultaneously.It comprises the steps of
(1) sodium sulfate, mud or carbon source solution are mixed according to a certain percentage, after making mixing, solution dewatered sludge 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 Pb soil remediation medicament；
(2) will contain top layer, Pb 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 Pb 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 Pb 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 fix Pb, make full use of sulfate simultaneously, it is translated into sulfide, Pb simultaneously, is converted into more stable sulfuration Pb precipitation by the most fixing Pb.
Comparing traditional containing Pb agent, soil treatment method, this method has a following advantage:
1. the sulfate reducting bacteria sulphate reducing in sludge microbial agent, generates sulfide, can be while more efficient fixing Pb；
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 Pb, and does not results in ecological problem；
3. the Pb after reduction and sulfate reducting bacteria metabolite sulfide form sulfuration Pb precipitation so that in soil, Pb is more stable, is significantly better than other biochemical process；
4. this method uses mud 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, mud or carbon source solution are mixed according to a certain percentage, after making mixing, solution dewatered sludge 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 Pb soil remediation medicament；
(2) will contain top layer, Pb 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 Pb 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 Pb 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 P in soil b content of deep layer are below 2mg/kg, and subsoil water amount containing Pb is less than 0.1mg/L.
Embodiment 2:
(1) sodium sulfate, mud or carbon source solution are mixed according to a certain percentage, after making mixing, solution dewatered sludge 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 Pb soil remediation medicament；
(2) will contain top layer, Pb 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 Pb 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 Pb 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 P in soil b content of deep layer are below 2mg/kg, and subsoil water amount containing Pb 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 Pb is in situ and dystopy couples a detoxification, it is characterized in that, comprises the steps of
(1) sodium sulfate, mud or carbon source solution are mixed according to a certain percentage, after making mixing, solution dewatered sludge 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 Pb soil remediation medicament；
(2) will contain top layer, Pb 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 Pb 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 Pb 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.
2. one heavily contaminated place Pb as claimed in claim 1 is in situ and dystopy couples detoxification, it is characterized in that, described mud is anaerobic sludge produced by sewage treatment anaerobic technique, it is possible to the double oxygen mud of admixture part.
3. a kind of heavily contaminated place Pb as claimed in claim 1 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.
4. a kind of heavily contaminated place Pb as claimed in claim 1 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.
5. a kind of heavily contaminated place Pb as claimed in claim 1 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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| Application Number | Priority Date | Filing Date | Title |
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| CN201610370389.8A CN105945052B (en) | 2016-05-30 | 2016-05-30 | Pb in-situ and ectopic coupling detoxification method for heavily polluted site |
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| CN201610370389.8A CN105945052B (en) | 2016-05-30 | 2016-05-30 | Pb in-situ and ectopic coupling detoxification method for heavily polluted site |
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| CN105945052B CN105945052B (en) | 2020-10-27 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| RU2803894C1 (en) * | 2022-11-02 | 2023-09-21 | Федеральное государственное бюджетное научное учреждение "Всероссийский научно-исследовательский институт агрохимии имени Д.Н. Прянишникова" | Method for detoxifying soil contaminated with heavy metals |
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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 |
| 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 |
| CN103981142A (en) * | 2013-12-05 | 2014-08-13 | 青岛理工大学 | Method for continuously culturing alkaline waste repair bacterial liquid containing Cr (VI) |
| CN105598144A (en) * | 2016-03-22 | 2016-05-25 | 安徽工程大学 | Restoration method of polluted soil |
-
2016
- 2016-05-30 CN CN201610370389.8A patent/CN105945052B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1445031A (en) * | 2002-03-15 | 2003-10-01 | 林裕城 | Recycling handles method for dirty mire containing heavy metals |
| CN1676635A (en) * | 2005-03-01 | 2005-10-05 | 同济大学 | Process for separating and recovering sludge and heavy metals 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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| RU2803894C1 (en) * | 2022-11-02 | 2023-09-21 | Федеральное государственное бюджетное научное учреждение "Всероссийский научно-исследовательский институт агрохимии имени Д.Н. Прянишникова" | Method for detoxifying soil contaminated with heavy metals |
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| CN105945052B (en) | 2020-10-27 |
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Effective date of registration: 20240608 Address after: 201100 room 0155, 2 / F, jilou, No. 555, Dongchuan Road, Minhang District, Shanghai Patentee after: SHANGHAI JIERANG SOIL ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Country or region after: China Address before: 266033 No. 2 Changjiang Road, Qingdao economic and Technological Development Zone, Shandong Patentee before: Qingdao University of Technology Country or region before: China |
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