CN103624077A - Novel soil purifying agent and application thereof to polybrominated diphenyl ethers (PBDEs) contaminated soil restoration - Google Patents
Novel soil purifying agent and application thereof to polybrominated diphenyl ethers (PBDEs) contaminated soil restoration Download PDFInfo
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- CN103624077A CN103624077A CN201310636248.2A CN201310636248A CN103624077A CN 103624077 A CN103624077 A CN 103624077A CN 201310636248 A CN201310636248 A CN 201310636248A CN 103624077 A CN103624077 A CN 103624077A
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Abstract
The invention discloses a novel soil purifying agent and application thereof to polybrominated diphenyl ethers (PBDEs) contaminated soil restoration. As PBDEs has a strong hydrophobicity and is easy to adsorb intensively by soil, and very low in bio-availability, the treatment of the PBDEs contaminated soil is very difficult. To solve the problem, an anionic surfactant and iron group compound which are environment-friendly, cheap and easy to get are utilized to form a metal complex, namely the soil purifying agent, according to the molar ratio of (1:3)-(1:5); after being uniformly mixed with the soil, the soil purifying agent is added with humic acid, and soaked by water, then the soil purifying agent can be used for efficiently and rapidly purifying contaminated soil while the soil property is not changed and the bio-availability is improved. The novel soil purifying agent is suitable for PBDEs contaminated soil restoration, and has an excellent application prospect on the aspect of large-scale engineering application.
Description
Technical field
The invention belongs to the aryl halide organic pollutants processing technology field of environmental protection, relate to a kind of new soil cleanser, and the application that this soil sanitation agent is repaired for PBDE contaminated soil.
Background technology
PBDE (PBDEs) is a kind of widely used brominated flame-retardant, is applied to a plurality of fields such as electronic product, weaving, construction material and the vehicles.But PBDEs, as a kind of additive flame retardant, is combined on product with physics mode, owing to lacking the constraint effect of chemical bond, be easy to be discharged in environment in production, use, disposal process.In various surrounding mediums and organism, detect PDBEs at present, distribution is extend over the entire globe almost, even in Arctic, can monitor the PBDEs of some bromo, and its concentration in environment increases rapidly in decades in the past.
As persistence organic pollutant, PBDEs is difficult degradation in environment, holdup time is long, there is stronger lipophilicity, biological accumulation, persistence and bio-toxicity, although the acute toxicity of PBDEs is lower, it is accumulated in vivo after class reaches certain level and can be disturbed thyroid hormone by food chain, hinders the normal development of human and animal's brain and central nervous system and has potential carcinogenicity.In addition PBDEs can generate hypertoxic many bromines of carcinogenic substance dibenzodioxin English and polybrominated dibenzo-furan when burning and pyrolytic, and ecological environment and health are all constituted a serious threat.
Along with the environmental problem of PBDEs is subject to everybody extensive concern day by day, the upper research of the degradation technique for PBDEs both at home and abroad deepens continuously.PBDEs chemical constitution is similar to Polychlorinated biphenyls, and it is difficult to oxidized, is but relatively easily reduced debrominate, and current processing research is substantially all debrominate research, and the debrominate of high bromo Biphenyl Ether is generated to low bromo homologue, mainly concentrates in light degradation and biological treatment.
Biological species method is because environmental friendliness degree is high, process mechanism and means ecological natural and be well received by the public, but most of organic matter water solubilities are little, often by soil strong adsorption, the bioavailability of organic pollution (Bioavailability) is very low, this greatly limited microorganism to organic degraded or plant to organic absorption and accumulation, and PBDEs has toxicity and inhibitory action to microorganism, rely on separately bioanalysis degraded to be difficult to reach good treatment effect.Light degradation method is current for a kind of methods maximum in PBDEs Study on processing method, but its reaction rate is slower, as increased cost by ultraviolet as light source, is unsuitable for engineering application; In addition, photodissociation process can generate many bromines dibenzodioxin English (PBDDs) and many bromines dibenzo furan (PBDFs), causes secondary pollution.Fixation can reduce heavy metal animal migration and biological effectiveness, but some fixative itself exists secondary pollution, and long-term fixed effect is unstable, and existing a lot of fixative is not obvious for the regulation effect of calcareous contaminated soil.Therefore in the urgent need to finding a kind of restorative procedure of the PBDEs of being suitable for contaminated soil.
As strong-hydrophobicity organic matter (HOCs), PBDEs is easily by soil strong adsorption, and bioavailability (Bioavailability) is very low, and this makes the processing of PBDEs contaminated soil very difficult.Solubilising wash-out is the prerequisite that HOCs contaminated soil is repaired, and how to impel the desorb of adsorption by soil state PBDEs, increases the solvability of PBDEs in soil, becomes the key of development PBDEs contaminated soil recovery technique, raising remediation efficiency.
Summary of the invention
One of object of the present invention is according to the deficiencies in the prior art, provides a kind of cheap, synthetic simple, can effectively repair the new soil cleanser of PBDEs contaminated soil.
Two of object is preparation methods of this new soil cleanser of entity.
Three of object is to provide the application of this new soil cleanser in repairing PBDE contaminated soil.
For achieving the above object, the present invention is by the following technical solutions: a kind of new soil cleanser, described cleanser is the complex compound of anionic surfactant and iron group compound, the mol ratio 1:3～1:5 of surfactant and iron group compound.
Described cationic surface active agent is a kind of in AEO sulfuric acid, AEO sulfosuccinic acid monoesters disodium or sodium abietate.
Described iron group compound is ferric iron compound, cobalt compound or nickel compound.
Described iron group compound is a kind of in ferric sulfate, iron hydroxide, bodied ferric sulfate.
A kind of preparation method of new soil cleanser, comprise the following steps: the mixed aqueous solution of preparation anionic surfactant and iron group compound, the mol ratio of surfactant and iron group compound is 1:3～1:5, the volume of water is 200mL, the total concentration of surfactant and iron group compound is 8000～10000mg/L, in about 70 ℃ 2 h that reflux, during backflow, with NaOH, regulating mixed aqueous solution pH is 5～6, the cooling rear suction filtration of reactant liquor, with appropriate absolute ethyl alcohol repeated washing, dry, obtain metal complex powder.
The application that new soil cleanser is repaired for PBDE contaminated soil, comprises the following steps:
(1) PBDE contaminated soil is crushed to and is less than 2cm, soil is built heap and is processed, and mound height is higher than 0.3m, below paving plastic film with antiseep, add the new soil cleanser of contaminated soil quality 8%～20%, mix;
(2) in the contaminated soil that is mixed with new soil cleanser, add humic acid and water, the mass ratio of added water and contaminated soil is 1:1～2:1, stirs, and soaks after 1～2d, collects filtrate;
(3) filtrate of collecting is used to Ca (OH)
2or KOH regulates filtrate pH value to 9.0～10.0, add flocculant, standing, filter, filtrate directly or after supplementing water time step 2 recycle;
(4) soil after processing, natural air drying, cultivates crops for the later stage.
Described humic acid is humic acid coal or humic acid in peat.
Described flocculant is polyacrylamide.
Tool of the present invention has the following advantages:
(1) new soil cleanser provided by the invention is comprised of anion surfactant and iron group compound, improvement for PBDEs contaminated soil screens, can promotion be rapidly and efficiently adsorbed on the dissolving of the PBDEs on soil, improve bioavailability, be convenient to subsequent treatment.
(2) select environmental friendliness, anion surfactant cheap and easy to get, in the situation that guaranteeing efficient solubilising power, can significantly reduce reagent dosage, effectively overcome the suction-operated of soil, being down to minimum on the impact of soil property simultaneously.Selecting iron in iron group compound is the chief component element of soil itself, can not bring the problem of secondary pollution to soil after adding soil to.Process after soil, adding of ferro element, can maintain the stable of soil texture; And without new harmful element, add, be conducive to the later stage to cultivate crops.
(3) soil sanitation agent and humic acid are used in combination, and the clearance of PBDEs can be improved to 20%～30%.The abundant raw material of humic acid in peat, synthetic convenient, therefore the contaminated soil cleanser using, its manufacturing price is cheap, can also increase the surcharge of peat.
(4) application of new soil cleanser provided by the invention being repaired for contaminated soil, with respect to additive method, is more suitable for the PBDE in soil is processed, and is applicable to engineering application.
The specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.
New soil cleanser, metal complex for surfactant and iron group compound, preparation method is: the mixed aqueous solution of preparation anionic surfactant and iron group compound, the mol ratio of surfactant and iron group compound is 1:3～1:5, the volume of water is 200mL, the total concentration of surfactant and iron group compound is 8000～10000mg/L, in about 70 ℃ 2 h that reflux, during backflow, with NaOH, regulating mixed aqueous solution pH is 5～6, the cooling rear suction filtration of reactant liquor, with appropriate absolute ethyl alcohol repeated washing, dry, obtain metal complex powder.
Surfactant is environmental friendliness, anion surfactant cheap and easy to get, as AEO sulfuric acid, AEO sulfosuccinic acid monoesters disodium, sodium abietate etc.Iron group compound is ferric iron compound, cobalt compound or nickel compound, preferentially selects ferric iron compound.Ferric iron compound is as ferric sulfate, iron hydroxide, bodied ferric sulfate, preferred polymeric ferric sulfate.
The application that this new soil cleanser is repaired for PBDEs contaminated soil, comprises the following steps:
(1) PBDE contaminated soil is crushed to and is less than 2cm, soil is built heap and is processed, and mound height is not higher than 0.3m, paving plastic film is with antiseep below, add new soil cleanser, the cleanser of interpolation accounts for 8%～20% of contaminated soil quality, mixes;
(2) in the contaminated soil that is mixed with new soil cleanser, add humic acid and water, the mass ratio of added water and contaminated soil is 1:1～2:1, humic acid is humic acid coal or humic acid in peat, the soil sanitation agent of using and the mass ratio of humic acid have no particular limits, 3:2～3:40 is good, and 3:5～3:20 is best.Stir, soak after 1～2d, collect filtrate;
(3) filtrate of collecting is used to Ca (OH)
2or KOH regulates filtrate pH value to 9.0～10.0, add flocculant, flocculant is polyacrylamide (PAM), standing, filter, filtrate directly or after supplementing water time step 2 recycle;
(4) soil after processing, natural air drying, cultivates crops for the later stage.
Although the present invention with preferred embodiment openly as above; but embodiment is not for limiting the present invention, be anyly familiar with this skill person, without departing from the spirit and scope of the invention; from working as, can make various changes or retouch, but equally within protection scope of the present invention.What therefore protection scope of the present invention should be defined with the application's claim protection domain is as the criterion.
Claims (8)
1. a new soil cleanser, is characterized in that: described cleanser is the complex compound of anionic surfactant and iron group compound the mol ratio 1:3～1:5 of surfactant and iron group compound.
2. new soil cleanser according to claim 1, is characterized in that: described anionic surfactant is a kind of in AEO sulfuric acid, AEO sulfosuccinic acid monoesters disodium or sodium abietate.
3. new soil cleanser according to claim 1, is characterized in that: described iron group compound is ferric iron compound, cobalt compound or nickel compound.
4. new soil cleanser according to claim 1, is characterized in that: described iron group compound is a kind of in ferric sulfate, iron hydroxide, bodied ferric sulfate.
5. the preparation method of new soil cleanser according to claim 1, it is characterized in that comprising the following steps: the mixed aqueous solution of preparation anionic surfactant and iron group compound, the mol ratio of surfactant and iron group compound is 1:3～1:5, the volume of water is 200mL, the total concentration of surfactant and iron group compound is 8000～10000mg/L, in about 70 ℃ 2 h that reflux, during backflow, with NaOH, regulating mixed aqueous solution pH is 5～6, the cooling rear suction filtration of reactant liquor, with appropriate absolute ethyl alcohol repeated washing, dry, obtain metal complex powder.
6. the application that new soil cleanser according to claim 1 is repaired for PBDE contaminated soil, is characterized in that comprising the following steps:
(1) PBDE contaminated soil is crushed to and is less than 2cm, soil is built heap and is processed, and mound height is higher than 0.3m, below paving plastic film with antiseep, add the new soil cleanser of contaminated soil quality 8%～20%, mix;
(2) in the contaminated soil that is mixed with new soil cleanser, add humic acid and water, the mass ratio of added water and contaminated soil is 1:1～2:1, stirs, and soaks after 1～2d, collects filtrate;
(3) filtrate of collecting is used to Ca (OH)
2or KOH regulates filtrate pH value to 9.0～10.0, add flocculant, standing, filter, filtrate directly or after supplementing water time step 2 recycle;
(4) soil after processing, natural air drying, cultivates crops for the later stage.
7. the application that new soil cleanser according to claim 6 is repaired for PBDE contaminated soil, is characterized in that: described humic acid is humic acid coal or humic acid in peat.
8. the application that new soil cleanser according to claim 6 is repaired for PBDE contaminated soil, is characterized in that: described flocculant is polyacrylamide.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103934265A (en) * | 2014-04-01 | 2014-07-23 | 江苏大学 | Method for restoring soil contaminated by poly-brominated diphenyl ether by combining solubilization of surface active agent and microwave irradiation technology |
| CN104174639A (en) * | 2014-07-28 | 2014-12-03 | 中国科学院南京土壤研究所 | Chemical elution-plant combined remediation method of polybrominated diphenyl ether and heavy metal compound contaminated soil |
| CN105268735A (en) * | 2015-11-12 | 2016-01-27 | 浙江大学 | Method for restoring polluted soil in situ |
| CN110240250A (en) * | 2019-06-06 | 2019-09-17 | 南京融众环境工程研究院有限公司 | A kind of method of degrading decabromodiphenyl ether |
| CN114833189A (en) * | 2022-03-25 | 2022-08-02 | 包禾欣 | Purifying agent and preparation process and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001205248A (en) * | 2000-01-27 | 2001-07-31 | Hazama Gumi Ltd | Soil cleaning agent and soil cleaning method |
| JP3265528B2 (en) * | 1995-09-20 | 2002-03-11 | 同和鉱業株式会社 | Treatment of soil contaminated by heavy metals |
| JP2003080221A (en) * | 2001-09-11 | 2003-03-18 | Eco-System Engineering Co Ltd | Purifying method of underground soil |
| EP1661864A1 (en) * | 2004-11-29 | 2006-05-31 | Toda Kogyo Corporation | Purifying agent for purifying soil or ground water, process for producing the same, and method for purifying soil or ground water using the same |
| CN101003389A (en) * | 2007-01-15 | 2007-07-25 | 四川大学 | Method for preparing Nano particles of monodisperse, ultra paramagnetic ferroferric oxide |
| CN101318711A (en) * | 2008-07-11 | 2008-12-10 | 天津大学 | Method for preparing nano-lamellar structured Fe2O3 and application thereof |
| CN101554660A (en) * | 2008-04-08 | 2009-10-14 | 南开大学 | Nanometer iron powder stable in air and preparation method thereof |
-
2013
- 2013-12-03 CN CN201310636248.2A patent/CN103624077B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3265528B2 (en) * | 1995-09-20 | 2002-03-11 | 同和鉱業株式会社 | Treatment of soil contaminated by heavy metals |
| JP2001205248A (en) * | 2000-01-27 | 2001-07-31 | Hazama Gumi Ltd | Soil cleaning agent and soil cleaning method |
| JP2003080221A (en) * | 2001-09-11 | 2003-03-18 | Eco-System Engineering Co Ltd | Purifying method of underground soil |
| EP1661864A1 (en) * | 2004-11-29 | 2006-05-31 | Toda Kogyo Corporation | Purifying agent for purifying soil or ground water, process for producing the same, and method for purifying soil or ground water using the same |
| CN101003389A (en) * | 2007-01-15 | 2007-07-25 | 四川大学 | Method for preparing Nano particles of monodisperse, ultra paramagnetic ferroferric oxide |
| CN101554660A (en) * | 2008-04-08 | 2009-10-14 | 南开大学 | Nanometer iron powder stable in air and preparation method thereof |
| CN101318711A (en) * | 2008-07-11 | 2008-12-10 | 天津大学 | Method for preparing nano-lamellar structured Fe2O3 and application thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103934265A (en) * | 2014-04-01 | 2014-07-23 | 江苏大学 | Method for restoring soil contaminated by poly-brominated diphenyl ether by combining solubilization of surface active agent and microwave irradiation technology |
| CN103934265B (en) * | 2014-04-01 | 2016-05-25 | 江苏大学 | A kind of surface active agent solubilization is repaired the method for PBDE contaminated soil in conjunction with Microwave Radiation in Manufacturing |
| CN104174639A (en) * | 2014-07-28 | 2014-12-03 | 中国科学院南京土壤研究所 | Chemical elution-plant combined remediation method of polybrominated diphenyl ether and heavy metal compound contaminated soil |
| CN104174639B (en) * | 2014-07-28 | 2016-10-05 | 中国科学院南京土壤研究所 | PBDE and the chemical removal-plant combined repairing method of heavy-metal composite pollution soil |
| CN105268735A (en) * | 2015-11-12 | 2016-01-27 | 浙江大学 | Method for restoring polluted soil in situ |
| CN105268735B (en) * | 2015-11-12 | 2018-02-02 | 浙江大学 | A kind of method of in-situ immobilization contaminated soil |
| CN110240250A (en) * | 2019-06-06 | 2019-09-17 | 南京融众环境工程研究院有限公司 | A kind of method of degrading decabromodiphenyl ether |
| CN114833189A (en) * | 2022-03-25 | 2022-08-02 | 包禾欣 | Purifying agent and preparation process and application thereof |
| CN114833189B (en) * | 2022-03-25 | 2023-12-01 | 苏州精衡科技有限公司 | Purifying agent and preparation process and application thereof |
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Effective date of registration: 20171212 Address after: 350000, Fujian, Fuzhou province Taijiang District peak street, Fu Liang road 379 Wuyi oasis area (formerly Wuyi oasis phase two), 31, 32 building connection 1 layer 08 storefront Patentee after: Fujian fertile environment protection Co.,Ltd. Address before: Zhenjiang City, Jiangsu Province, 212013 Jingkou District Road No. 301 Patentee before: Jiangsu University |
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Address after: 350108, No. 2, No. 2, No. 2 Science Park, Fuzhou University Science Park, Minhou County, Minhou County, Shanghai Patentee after: Fujian fertile soil environmental protection group Co.,Ltd. Address before: Shop 08, floor 1, connecting building 31 and 32, No. 379, Fuguang South Road, Aofeng street, Taijiang District, Fuzhou City, Fujian Province Patentee before: Fujian fertile environment protection Co.,Ltd. |
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