CN103624077B - A kind of new soil cleanser and the application for PBDE contaminated soil remediation thereof - Google Patents
A kind of new soil cleanser and the application for PBDE contaminated soil remediation thereof Download PDFInfo
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- CN103624077B CN103624077B CN201310636248.2A CN201310636248A CN103624077B CN 103624077 B CN103624077 B CN 103624077B CN 201310636248 A CN201310636248 A CN 201310636248A CN 103624077 B CN103624077 B CN 103624077B
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Abstract
The invention discloses a kind of new soil cleanser, and this soil sanitation agent is used in the application of PBDE contaminated soil remediation.PBDEs is due to strong-hydrophobicity, and easily by soil strong adsorption, bioavailability is very low, and this makes the process of PBDEs contaminated soil very difficult.For this problem, the present invention utilizes environmental friendliness, anion surfactant cheap and easy to get and iron group compound to form metal complex by the mol ratio of 1:3 ~ 1:5, i.e. soil sanitation agent, mix with soil, add humic acid, after being soaked in water, not changing soil property, improving while bioavailability, efficiently, purifying contaminated soil fast.This method is applicable to the reparation of PBDEs contaminated soil, has good application prospect in large-scale engineering applications.
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 this soil sanitation agent is used for the application of PBDE contaminated soil remediation.
Background technology
PBDE (PBDEs) is a kind of widely used brominated flame-retardant, is applied to multiple fields such as electronic product, weaving, construction material and the vehicles.But PBDEs, as a kind of additive flame retardant, is be combined on product for physically, owing to lacking the constraint effect of chemical bond, be easy to be discharged in environment in production, use, disposal process.In various surrounding medium and organism, detect PDBEs at present, distribution is extend over the entire globe almost, even can monitor the PBDEs of some bromo in Arctic, and its concentration in the environment increases rapidly in decades in the past.
As persistence organic pollutant, PBDEs is difficult degradation in the environment, holdup time is long, there is stronger lipophilicity, biological accumulation, persistence and bio-toxicity, although the acute toxicity of PBDEs is lower, it can disturb thyroid hormone after reaching certain level by food chain accumulation class in vivo, hinders the normal development of human and animal's brain and central nervous system and has potential carcinogenicity.In addition PBDEs can generate hypertoxic carcinogenic substance many bromines dibenzodioxin English and polybrominated dibenzo-furan when burning and pyrolytic, all constitutes a serious threat to ecological environment and health.
Environmental problem along with PBDEs is subject to everybody extensive concern day by day, and the research of the upper degradation technique for PBDEs deepens continuously both at home and abroad.PBDEs chemical constitution is similar to Polychlorinated biphenyls, and it is difficult to oxidized, is but relatively easily reduced debrominate, and current treatment research is substantially all debrominate research, and the debrominate of high bromobiphenyl ether is generated low bromo homologue, mainly concentrates in light degradation and biological treatment.
Biological species method due to environmental friendliness degree high, treatment mechanism and means ecological natural and be well received by the public, but most of organic matter water solubility is little, often by soil strong adsorption, the bioavailability (Bioavailability) of organic pollution is very low, which greatly limits microorganism to organic degraded or plant to organic absorption and accumulation, and PBDEs has toxicity and inhibitory action to microorganism, bioanalysis degraded is relied on separately to be difficult to reach good treatment effect.Light degradation method is at present for a kind of methods maximum in PBDEs Study on processing method, but its reaction rate is comparatively slow, as increased cost by ultraviolet as light source, is unsuitable for engineer applied; In addition, photolysis step can generate many bromines dibenzodioxin English (PBDDs) and many bromines dibenzo furan (PBDFs), causes secondary pollution.Fixation can reduce heavy metals mobilization 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 being suitable for PBDEs 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 process of PBDEs contaminated soil very difficult.Solubilising wash-out is the prerequisite of HOCs contaminated soil remediation, how to impel the desorb of adsorption by soil state PBDEs, increases the solvability of PBDEs in soil, becomes development PBDEs contaminated soil remediation technology, improves the key of remediation efficiency.
Summary of the invention
An object of the present invention is according to the deficiencies in the prior art, provide a kind of cheap, synthesis is simple, effectively can 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 this new soil cleanser and is repairing the application in PBDE contaminated soil.
For achieving the above object, the present invention is by the following technical solutions: a kind of new soil cleanser, and 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 the one 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 the one 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 DEG C backflow 2 h, during backflow, NaOH regulates mixed aqueous solution pH to be 5 ~ 6, suction filtration after reactant liquor cooling, with appropriate absolute ethyl alcohol repeated washing, drying, obtains metal complex powder.
New soil cleanser is used for an application for PBDE contaminated soil remediation, comprises the following steps:
(1) be crushed to by PBDE contaminated soil and be less than 2cm, soil is built heap and is processed, mound height not 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 being mixed with new soil cleanser, add humic acid and water, added water and the mass ratio of contaminated soil are 1:1 ~ 2:1, stir, and after soaking 1 ~ 2d, collect filtrate;
(3) by the filtrate of collecting with Ca (OH)
2or KOH regulates filtrate pH value to 9.0 ~ 10.0, adds flocculant, leave standstill, filter, filtrate directly or return step 2 after supplementing water and recycle;
(4) soil after process, 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 made up of anion surfactant and iron group compound, improvement for PBDEs contaminated soil screens, promotion rapidly and efficiently can be 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, significantly can reduce reagent dosage when ensureing efficient solubilising power, simultaneously, effectively overcoming the suction-operated of soil, being down to minimum on the impact of soil property.Select iron in iron group compound to be the main component of soil itself, the problem of secondary pollution after adding soil to, can not be brought to soil.After process soil, adding of ferro element, the stable of soil texture can be maintained; And add without new harmful element, being conducive to the later stage cultivates crops.
(3) soil sanitation agent and humic acid combinationally use, and the clearance of PBDEs can be improved 20% ~ 30%.The abundant raw material of humic acid in peat, synthesis is convenient, therefore the contaminated soil cleanser used, its manufacturing price is cheap, can also increase the surcharge of peat.
(4) new soil cleanser provided by the invention is used for the application of contaminated soil remediation, relative to additive method, is more suitable for and the PBDE in soil is processed, be applicable to engineer applied.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
New soil cleanser, for the metal complex of 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 DEG C backflow 2 h, during backflow, NaOH regulates mixed aqueous solution pH to be 5 ~ 6, suction filtration after reactant liquor cooling, 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 as ferric sulfate, iron hydroxide, bodied ferric sulfate, preferred polymeric ferric sulfate.
This new soil cleanser is used for the application of PBDEs contaminated soil remediation, comprises the following steps:
(1) be crushed to by PBDE contaminated soil and be 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 being mixed with new soil cleanser, humic acid and water is added, added water and the mass ratio of contaminated soil are 1:1 ~ 2:1, humic acid is humic acid coal or humic acid in peat, the soil sanitation agent used 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, after soaking 1 ~ 2d, collect filtrate;
(3) by the filtrate of collecting with Ca (OH)
2or KOH regulates filtrate pH value to 9.0 ~ 10.0, add flocculant, flocculant is polyacrylamide (PAM), leaves standstill, and filters, and filtrate directly or return step 2 after supplementing water and recycle;
(4) soil after process, 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, being anyly familiar with this those skilled in the art, without departing from the spirit and scope of the invention; can make various changes or retouch from working as, but same within protection scope of the present invention.What therefore protection scope of the present invention should define with the claims of the application is as the criterion.
Claims (5)
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;
Described anionic surfactant is the one in AEO sulfosuccinic acid monoesters disodium or sodium abietate;
Described iron group compound is cobalt compound or nickel compound; Or be one in ferric sulfate, iron hydroxide, bodied ferric sulfate.
2. 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 DEG C backflow 2 h, during backflow, NaOH regulates mixed aqueous solution pH to be 5 ~ 6, suction filtration after reactant liquor cooling, with appropriate absolute ethyl alcohol repeated washing, dry, obtain metal complex powder.
3. new soil cleanser according to claim 1 is used for the application of PBDE contaminated soil remediation, it is characterized in that comprising the following steps:
(1) be crushed to by PBDE contaminated soil and be less than 2cm, soil is built heap and is processed, mound height not 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 being mixed with new soil cleanser, add humic acid and water, added water and the mass ratio of contaminated soil are 1:1 ~ 2:1, stir, and after soaking 1 ~ 2d, collect filtrate;
(3) by the filtrate of collecting with Ca (OH)
2or KOH regulates filtrate pH value to 9.0 ~ 10.0, adds flocculant, leave standstill, filter, filtrate directly or return step (2) after supplementing water and recycle;
(4) soil after process, natural air drying, cultivates crops for the later stage.
4. new soil cleanser according to claim 3 is used for the application of PBDE contaminated soil remediation, it is characterized in that: described humic acid is humic acid coal or humic acid in peat.
5. new soil cleanser according to claim 3 is used for the application of PBDE contaminated soil remediation, it is characterized in that: described flocculant is polyacrylamide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| 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 |
| 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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| CN101554660A (en) * | 2008-04-08 | 2009-10-14 | 南开大学 | Nanometer iron powder stable in air and preparation method thereof |
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| JP3265528B2 (en) * | 1995-09-20 | 2002-03-11 | 同和鉱業株式会社 | Treatment of soil contaminated by heavy metals |
| JP3612258B2 (en) * | 2000-01-27 | 2005-01-19 | 株式会社間組 | Soil purification agent and soil purification method |
| JP2003080221A (en) * | 2001-09-11 | 2003-03-18 | Eco-System Engineering Co Ltd | Purifying method of underground soil |
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|---|---|---|---|---|
| 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 |
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| CN101318711A (en) * | 2008-07-11 | 2008-12-10 | 天津大学 | Method for preparing nano-lamellar structured Fe2O3 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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