CN105945056A - Heavy-polluted site Cd in-situ and ectopic coupling detoxification method based on biogas residues - Google Patents

Heavy-polluted site Cd in-situ and ectopic coupling detoxification method based on biogas residues Download PDF

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Publication number
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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place
soil
situ
organic
solution
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CN105945056B (en
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张大磊
李公伟
郝志鹏
赵昱皓
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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

Abstract

The invention discloses a heavy-polluted site Cd in-situ and ectopic coupling detoxification method based on biogas residues. The biogas residues, carbon sources and sulfate are prepared as medicament to apply to Cd-contained soil; and then, a special construction and curing mode is adopted to gradually permeate reducing ecologic fungicides underground so as to reduce deep contaminated soil Cd. The method can repair heavy-polluted Cd-contained sites with low cost and high efficiency, and treats wastes by using wastes to treat the biogas residues.

Description

A kind of heavily contaminated place Cd based on biogas residue is in situ and dystopy couples detoxification
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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Citations (8)

* Cited by examiner, † Cited by third party
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
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
CN103436265A (en) * 2013-08-23 2013-12-11 付融冰 Reductive degradable stabilizer of polluted soil, bottom mud and sludge as well as preparation method and using method of stabilizer
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
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
CN104671624A (en) * 2015-02-10 2015-06-03 江苏金山环保科技股份有限公司 Processing method of low-cost heavy metal-containing sludge
CN105598144A (en) * 2016-03-22 2016-05-25 安徽工程大学 Restoration method of polluted soil

Patent Citations (8)

* Cited by examiner, † Cited by third party
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
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
CN103436265A (en) * 2013-08-23 2013-12-11 付融冰 Reductive degradable stabilizer of polluted soil, bottom mud and sludge as well as preparation method and using method of stabilizer
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
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
CN104671624A (en) * 2015-02-10 2015-06-03 江苏金山环保科技股份有限公司 Processing method of low-cost heavy metal-containing sludge
CN105598144A (en) * 2016-03-22 2016-05-25 安徽工程大学 Restoration method of polluted soil

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