CN107052033A - The method that a kind of microwave reinforced nano zero valence iron/SODIUM PERCARBONATE repairs organochlorine pesticide pollution soil - Google Patents
The method that a kind of microwave reinforced nano zero valence iron/SODIUM PERCARBONATE repairs organochlorine pesticide pollution soil Download PDFInfo
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- CN107052033A CN107052033A CN201611201630.0A CN201611201630A CN107052033A CN 107052033 A CN107052033 A CN 107052033A CN 201611201630 A CN201611201630 A CN 201611201630A CN 107052033 A CN107052033 A CN 107052033A
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- Prior art keywords
- soil
- organochlorine
- sodium percarbonate
- nano zero
- zero valence
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- 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
Abstract
The invention belongs to organic polluted soil recovery technique field, a kind of method that organochlorine pesticide pollution soil is repaired in microwave reinforced nano zero valence iron and SODIUM PERCARBONATE collaboration is disclosed.This method according to certain liquid-solid ratio by organochlorine pesticide pollution soil by being made mud state soil mixed solution, a certain amount of surfactant, nano zero valence iron and SODIUM PERCARBONATE are added into solution, after microwaved and standing, the degradation rate of Organochlorine Pesticides In Soil reaches more than 80%.The present invention has advantages below：Process conditions are simple, operation requires low and treatment effeciency is high, oxidant consumption amount is few etc., it is adaptable to the reparation of the typical organochlorine pesticides contaminated soil such as DDT, BHC.
Description
Technical field
The invention belongs to organic contamination site remediation technology field, and in particular to one kind utilizes microwave reinforced nano zero valence iron
The method for repairing organochlorine pesticide pollution soil is cooperateed with SODIUM PERCARBONATE.
Background technology
Organo-chlorine pesticide with stable in physicochemical property, is difficult to degrade, easily in ring as one of persistence organic pollutant
The features such as being accumulated in border, its potential risk to ecological environment and health is always focus of concern.Due to organic
Chloro pesticide has a characteristics such as difficult degradation, high poison and high residue, and endangers human health easily by bioconcentration, China from
Nineteen eighty-three starts progressively to disable organo-chlorine pesticide.But, existing research shows, although most of organo-chlorine pesticide has been prohibited
With, but it still has extensive residual in soil environment, must carry out administering with repairing just for organochlorine pesticide pollution soil
Environment and health risk can be evaded or developed again.
Current organic contamination place often includes steam extraction, thermal desorption, rotary kiln, chemical leaching, chemistry with recovery technique
Redox, microorganism remediation and phytoremediation etc..Because the vapour pressure of most of organo-chlorine pesticides is relatively low, volatility is poor,
Therefore steam extraction and thermal desorption effect be not good；Disposal technology energy consumption is higher altogether for rotary kiln, and has to follow-up exhaust-gas treatment
Higher technical requirements, therefore limited in actual applications by larger；Chemical leaching method is needed to follow-up ring waste
It can be discharged after carrying out advanced treating, otherwise easily produce secondary pollution；Although microorganism remediation technology and phytoremediation technology
Cost is low, but remediation efficiency is also very low, and effect is also unstable.
Chemical oxidization method to most organic pollutants because having degradation capability rapidly and efficiently in organic polluted soil
Widely paid close attention in reparation.Common oxidants have Fenton reagent, ozone, potassium permanganate, potassium ferrate and activation persulfuric acid
Salt etc., wherein Fenton reagent are widely used because having preferable degradation capability to most organic pollutants.It is classical
Fenton reagent be made up of Fe (II) and hydrogen peroxide, Fe (II) can catalyzing hydrogen peroxide decompose and produce the stronger hydroxyl of oxidisability
Free radical (OH), realizes the fast degradation to organic pollution.However, it is dirty to repair organo-chlorine pesticide using classical Fenton reagent
Often there is following problem during dye soil：First, organo-chlorine pesticide primary attachment in soil, on the soil organism, makes
Contact effect of the Fenton reagent with organo-chlorine pesticide in soil be not good, so as to influence Fenton reagent to the drop of organo-chlorine pesticide
Solve efficiency；Second, Fenton reagent, often without selectivity, causes Fenton reagent in nothing to the Oxidative Degradation of organic compound
When method is fully contacted with organo-chlorine pesticide, redox reaction easily is produced with the soil organism first, so as to waste substantial amounts of
Fenton reagent；3rd, Fenton's reaction need to can just have preferable effect in acid condition, but there is soil stronger soda acid to buffer
Property, thus Fe (II) be oxidized after the Fe (III) that produces be easy to precipitation；4th, the hydrogen peroxide in Fenton reagent is in soil
It is also easy to produce decomposition, generation oxygen and water after transition metal ion catalyst, Clay Minerals And Clay Oxides catalysis or microbial action.
Above reason generally require to add when causing to use classical Fenton reagent remedying soil polluted by organic chloride substantial amounts of hydrogen peroxide with
Improve contact effect with organo-chlorine pesticide, thus significantly improve rehabilitation cost, while relatively low pH value must also be also kept,
Exist to soil physico-chemical property and adversely affect.In addition, Fenton reagent is difficult to take off to organo-chlorine pesticide of the part containing phenyl ring
Chlorine and open loop mineralising, under the reducing conditions could effectively dechlorination by needs.
Therefore, when repairing organochlorine pesticide pollution soil using Fenton process, it is necessary to classical Fenton process is improved, overcome
The problem of contact effect difference and Fe (III) of the organo-chlorine pesticide with Fenton reagent are easily precipitated, is Fenton-type reagent oxidative degradation soil
Earth organo-chlorine pesticide creates favourable reaction condition.The key for solving problem above is the presence shape for changing soil organo-chlorine pesticide
State, promotes desorption and the solubilising of organo-chlorine pesticide, promotes it to be changed into free state from ADSORPTION STATE, so as to improve soil organochlorine agriculture
The contacting efficiency of medicine and Fenton reagent, is that Fenton reagent oxidative degradation soil organo-chlorine pesticide creates favorable conditions.For being difficult to
The organo-chlorine pesticide of oxidative degradation, then can carry out dechlorination to it using reducing agent first, but reduction reaction is to organochlorine
The degraded of agricultural chemicals is not often thorough, it is possible to create stronger intermediate product, and recycling Fenton reagent is further degraded its dechlorination
Reduzate, realizes the thorough degraded to organochlorine pollutant.
Studied for many years by applicant, SODIUM PERCARBONATE is cooperateed with using ultrasound-enhanced nano zero valence iron the invention discloses one kind
The method for repairing organochlorine pesticide pollution soil, it is possible to achieve to the typical organochlorine pesticides contaminated soil such as DDT, BHC
Rapidly and efficiently reparation.
The content of the invention
The invention provides a kind of side using ultrasound-enhanced nano zero valence iron/SODIUM PERCARBONATE remedying soil polluted by organic chloride
Method, solve classical Fenton reagent in soil easily with the soil organism reaction, wastage is larger, need strong acid reaction condition
The problems such as, with advantages such as process conditions are simple, degraded is thorough, the fast, non-secondary pollutions of degradation speed, it can be widely applied to drop drop
The reparation of the organochlorine pesticide pollution soil such as tears, BHC.
Specific operation scheme is as follows：Soil and water are mixed into mud state soil mixed solution, liquid-solid ratio and pH are controlled
It is made as in certain limit, a certain amount of nano ferriferrous oxide and percarbonate is added into soil mixed liquor, microwave is positioned over
In chemical reactor, the degradation rate of Organochlorine Pesticides In Soil can reach more than 85% after one section of reaction time.
Described soil Organochlorine Pesticides are more than 5mg/kg.
Described mud state soil mixed solution pH value is between 8-12, pH value is adjusted using hydrochloric acid and sodium hydroxide.
The liquid-solid ratio (mass ratio) of described mud state soil mixed solution is 2:1~10:Between 1.
Described surfactant need to have preferably compatibility and non-secondary pollution risk with percarbonate, can use
The biodegradable surfactant such as Tween 80, Triton X-100, saponin, dosage is soil organo-chlorine pesticide mole matter
10-50 times of amount.
The particle diameter of described nano zero valence iron is less than 50nm, and dosage is usually the 0.5~2% of soil quality.
Described SODIUM PERCARBONATE dosage is the 0.5%~5% of soil quality.
Described microwave power is 100~750W.
The described reaction time is 10~30m.
In this reaction system, ultrasonic effect is to promote soil organo-chlorine pesticide to desorb from organic matter to enter the soil liquid
In, it is allowed to be changed into free state from ADSORPTION STATE；The effect of surfactant promotes the organo-chlorine pesticide of desorption in liquid phase of soil
Dissolving.Ultrasound and the coefficient result of surfactant, change absorption solution of the organo-chlorine pesticide in soil mixed solution
Balance is inhaled, promotes a large amount of organo-chlorine pesticide desorptions to be transferred in the soil liquid, improves contact of the organo-chlorine pesticide with Fenton-type reagent
Effect, is that nano zero valence iron/SODIUM PERCARBONATE system soil organo-chlorine pesticide of fully degrading creates favourable reaction condition.Nanometer zero
The effect of valency iron, which is not only, to carry out dechlorination to organo-chlorine pesticide, and it is oxidized the Fe (II) produced can also be with crossing carbon
Sour sodium decomposes the hydrogen peroxide composition Fenton reagent produced, and further the dechlorination product of degraded organo-chlorine pesticide, solves oxygen
Change reaction and some organo-chlorine pesticides are difficult to the problem of dechlorination open loop, also overcome that reduction reaction rate is slow, it is halfway to degrade
Problem.
Embodiment
Below with reference to example, the present invention is further elaborated, but present invention application is not limited to this.
Organochlorine pesticide pollution soil is repaired using this method in example 1 and example 2.Wherein, remained in soil
Organo-chlorine pesticide by ultrasonic extraction, quantitative detection is carried out to it using Shimadzu gas chromatograph.
Example 1：
10g BHC content is placed in 250ml conical flask for 50mg/kg contaminated soil, 50mL water is added, is made
Mud state soil mixed solution, it is 10 to adjust soil mixed solution pH value with hydrochloric acid and sodium hydroxide, into soil mixed solution
Add 0.2g Triton X-100,0.1g nano zero valence iron and 0.2g SODIUM PERCARBONATEs.Mud state soil mixed liquor is put into microwave
In chemical reactor, the degraded hexachloro cyclohexane rate that ultrasonic power is set to stand after 200W, microwave treatment 15m in 6h, soil reaches
More than 85%.
Example 2：
The contaminated soil 10g for taking DDT level to be 50mg/kg, is placed in 250ml conical flask, adds 50mL water, system
Into mud state soil mixed solution, it is 11 to adjust soil mixed solution pH value with hydrochloric acid and sodium hydroxide, to soil mixed solution
In add the SODIUM PERCARBONATE of 0.2g Tween 80,0.15g nano zero valence iron and 0.25g.Conical flask is put into microwave chemical anti-
Answer device, the DDT degradation rate that microwave power is set to stand after 200W, microwave treatment 15m in 6h, soil reached 85% with
On.
Claims (8)
1. the method that a kind of microwave reinforced nano zero valence iron/SODIUM PERCARBONATE repairs organochlorine pesticide pollution soil, its feature includes
Following steps：Organochlorine pesticide pollution soil is made the mud state soil mixed solution of certain solid-to-liquid ratio, added into solution
After surfactant, nano zero valence iron and SODIUM PERCARBONATE, microwaved and standing, the degradation rate of Organochlorine Pesticides In Soil reaches
To more than 85%.
2. according to the method described in claim 1, it is characterised in that the content of the Organochlorine Pesticides In Soil be 5mg/kg with
On.
3. according to the method described in claim 1, it is characterised in that the liquid-solid ratio of soil mixed solution is 2:1~10:1.
4. according to the method described in claim 1, it is characterised in that described soil mixed solution pH value is 8~12.
5. according to the method described in claim 1, it is characterised in that described surfactant is that Qula is led to or tween, is added
Measure as the 0.5%~2% of soil quality.
6. according to the method described in claim 1, it is characterised in that described nano zero valence iron particle diameter is less than 50nm, dosage
For the 0.5%~2% of soil quality.
7. according to the method described in claim 1, it is characterised in that described SODIUM PERCARBONATE consumption is the 0.5% of soil quality
~5%.
8. according to the method described in claim 1, it is characterised in that described microwave power is 100~750W, during microwave treatment
Between be 10~30m, time of repose be 3~24h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611201630.0A CN107052033A (en) | 2016-12-22 | 2016-12-22 | The method that a kind of microwave reinforced nano zero valence iron/SODIUM PERCARBONATE repairs organochlorine pesticide pollution soil |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611201630.0A CN107052033A (en) | 2016-12-22 | 2016-12-22 | The method that a kind of microwave reinforced nano zero valence iron/SODIUM PERCARBONATE repairs organochlorine pesticide pollution soil |
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| CN107052033A true CN107052033A (en) | 2017-08-18 |
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| CN201611201630.0A Pending CN107052033A (en) | 2016-12-22 | 2016-12-22 | The method that a kind of microwave reinforced nano zero valence iron/SODIUM PERCARBONATE repairs organochlorine pesticide pollution soil |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112139236A (en) * | 2020-09-17 | 2020-12-29 | 南开大学 | Method for restoring pesticide-polluted soil by using microwave-enhanced Fenton oxidation technology |
| CN112877071A (en) * | 2021-01-14 | 2021-06-01 | 北京高能时代环境技术股份有限公司 | Remediation agent and remediation method for remediation of organochlorine pesticide contaminated soil |
| CN115010237A (en) * | 2021-03-03 | 2022-09-06 | 苏州同达澄澈环境科技有限公司 | Method for removing black and odorous water body bottom mud in river channel by coupling iron-based biochar with percarbonate |
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| CN102380505A (en) * | 2011-08-08 | 2012-03-21 | 同济大学 | Method for repairing heavy metal-polluted soil or sludge with nano-zero-valent iron (nZVI) |
| CN104117532A (en) * | 2013-04-23 | 2014-10-29 | 苏州中科慧盛生物科技有限公司 | Nano-material repairing agent restoring heavy-metal polluted soil and restoring method using same |
| CN204182674U (en) * | 2014-11-07 | 2015-03-04 | 上海市环境科学研究院 | A kind of prosthetic device being applicable to chloro organic polluted soil |
| CN104511476A (en) * | 2013-10-08 | 2015-04-15 | 南京农业大学 | Method for increasing speed of oxidative degradation of organic pollutant in soil |
| CN105290099A (en) * | 2014-11-07 | 2016-02-03 | 上海市环境科学研究院 | Preparing method and use method of chlorinated organic compound polluted soil repairing agent |
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Patent Citations (5)
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| CN102380505A (en) * | 2011-08-08 | 2012-03-21 | 同济大学 | Method for repairing heavy metal-polluted soil or sludge with nano-zero-valent iron (nZVI) |
| CN104117532A (en) * | 2013-04-23 | 2014-10-29 | 苏州中科慧盛生物科技有限公司 | Nano-material repairing agent restoring heavy-metal polluted soil and restoring method using same |
| CN104511476A (en) * | 2013-10-08 | 2015-04-15 | 南京农业大学 | Method for increasing speed of oxidative degradation of organic pollutant in soil |
| CN204182674U (en) * | 2014-11-07 | 2015-03-04 | 上海市环境科学研究院 | A kind of prosthetic device being applicable to chloro organic polluted soil |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112139236A (en) * | 2020-09-17 | 2020-12-29 | 南开大学 | Method for restoring pesticide-polluted soil by using microwave-enhanced Fenton oxidation technology |
| CN112877071A (en) * | 2021-01-14 | 2021-06-01 | 北京高能时代环境技术股份有限公司 | Remediation agent and remediation method for remediation of organochlorine pesticide contaminated soil |
| CN115010237A (en) * | 2021-03-03 | 2022-09-06 | 苏州同达澄澈环境科技有限公司 | Method for removing black and odorous water body bottom mud in river channel by coupling iron-based biochar with percarbonate |
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