CN106001088A - Pb in-situ and heterotopic coupling detoxifying method for heavily-contaminated site based on biogas residues - Google Patents

Pb in-situ and heterotopic coupling detoxifying method for heavily-contaminated site based on biogas residues Download PDF

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Publication number
CN106001088A
CN106001088A CN201610370419.5A CN201610370419A CN106001088A CN 106001088 A CN106001088 A CN 106001088A CN 201610370419 A CN201610370419 A CN 201610370419A CN 106001088 A CN106001088 A CN 106001088A
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place
soil
organic
situ
solution
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CN106001088B (en
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张大磊
李瑞栋
王欣玉
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SHANGHAI JIERANG SOIL ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd.
Qingdao University of Technology
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Qingdao University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/08Reclamation of contaminated soil chemically
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/10Reclamation of contaminated soil microbiologically, biologically or by using enzymes
    • B09C1/105Reclamation of contaminated soil microbiologically, biologically or by using enzymes using fungi or plants
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/40Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C2101/00In situ

Abstract

The invention discloses a Pb in-situ and heterotopic coupling detoxifying method for a heavily-contaminated site based on biogas residues. The biogas residues, a carbon source and sulfate are prepared into a reagent to be applied to Pb-containing soil; and then a special construction and curing manner is adopted for reduction ecological bactericide to gradually permeate into the ground, and therefore Pb of the contaminated soil on the deep layer is reduced. By means of the method, the Pb-containing site which is high in contamination depth can be repaired efficiently with low cost, meanwhile, waste is used for treating waste, and the biogas residues are treated.

Description

A kind of heavily contaminated place Pb based on biogas residue is in situ and dystopy couples detoxification
Technical field
The present invention provides a kind of method of novel process Pb contaminated soil; biogas residue, 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 based on biogas residue in situ and dystopy coupling detoxification, biogas residue, 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 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 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 biogas residue microbial inoculum, 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 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 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, 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 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 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 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.
A kind of heavily contaminated place Pb 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 Pb 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 Pb 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 Pb 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.
CN201610370419.5A 2016-05-30 2016-05-30 Heavily-polluted site Pb in-situ and ex-situ coupling detoxification method based on biogas residues Active CN106001088B (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050232702A1 (en) * 2002-06-07 2005-10-20 Koji Fujita Contamination diffusion preventing structure in contaminated area
CN102500612A (en) * 2011-10-28 2012-06-20 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
CN103981097A (en) * 2013-12-05 2014-08-13 青岛理工大学 Preparation method of remediation flora for Cr (VI) contaminated site from sludge
CN104759466A (en) * 2014-01-08 2015-07-08 湖北科技学院 Soil heavy metal ex-situ remediation method based on molecular combination
CN105032912A (en) * 2015-07-17 2015-11-11 中国科学院武汉岩土力学研究所 In-situ repair method for shallow-buried heavy metal pollution site
CN105598144A (en) * 2016-03-22 2016-05-25 安徽工程大学 Restoration method of polluted soil

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050232702A1 (en) * 2002-06-07 2005-10-20 Koji Fujita Contamination diffusion preventing structure in contaminated area
CN102500612A (en) * 2011-10-28 2012-06-20 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
CN103981097A (en) * 2013-12-05 2014-08-13 青岛理工大学 Preparation method of remediation flora for Cr (VI) contaminated site from sludge
CN104759466A (en) * 2014-01-08 2015-07-08 湖北科技学院 Soil heavy metal ex-situ remediation method based on molecular combination
CN105032912A (en) * 2015-07-17 2015-11-11 中国科学院武汉岩土力学研究所 In-situ repair method for shallow-buried heavy metal pollution site
CN105598144A (en) * 2016-03-22 2016-05-25 安徽工程大学 Restoration method of polluted soil

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