CN106955706A - A kind of NZVI/CaO2The method of phthalic acid ester in Synergistic degradation underground water - Google Patents
A kind of NZVI/CaO2The method of phthalic acid ester in Synergistic degradation underground water Download PDFInfo
- Publication number
- CN106955706A CN106955706A CN201710206389.9A CN201710206389A CN106955706A CN 106955706 A CN106955706 A CN 106955706A CN 201710206389 A CN201710206389 A CN 201710206389A CN 106955706 A CN106955706 A CN 106955706A
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- CN
- China
- Prior art keywords
- phthalic acid
- acid ester
- underground water
- method described
- nzvi
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
Abstract
The invention belongs to field of underground water pollution repair, the method for disclosing phthalic acid ester in a kind of utilization nano zero valence iron/calper calcium peroxide degraded underground water.This method is by controlling under certain pH conditions, nano zero valence iron and calper calcium peroxide are added to phthalic acid ester polluted underground water, phthalic acid ester degradation rate can reach more than 95% in acid condition in underground water, and more than 80% can be reached in neutral conditions.The present invention has advantages below：Process conditions are simple, operation requires that low and catalysis material can be recycled, and can be applied to the in-situ immobilization of phthalic acid ester polluted underground water or processing of drawing water is repaired.
Description
The invention belongs to advanced oxidation groundwater treatment engineering field, and in particular to one kind utilizes CaO2/ NZVI collaboration drops
The method for solving phthalic acid ester in underground water.
Background technology
Phthalic acid ester (also known as phthalate ester, PAEs) class environmental hormone is that output is big, wide application artificial synthesized
One of organic compound, is also one of most important organic micro-pollutant in water environment.Current world PAEs annual production is extremely
Less in 2,000,000 more than t.China accounts for therein more than 70%.PAEs is mainly used as the plasticizer of plastic products, and it is in the plastic
Content be only second to high polymer, such as mass fraction in polyvinyl chloride (PVC) is up to 20%~50%.PAEs is used as plasticizer
While plastics are softened, it can gradually discharge, into environmental and biological materials, environmental and biological materials be made from plastics
Into potential hazard.Numerous studies show that, with PAEs extensive use, they can be entered by breathing, diet and skin contact
In humans and animals body, the effect of similar female hormone is played in human body with animal body, endocrine is may interfere with, with " three cause "
Effect.
The characteristics of concentration is low in water environment for phthalic acid ester, toxicity is big, with regard to processing method validity and practicality
Property for, high-level oxidation technology be remove the pollutant effective ways, by the pollutant in waste water pass through chemically react aoxidize
For micro- malicious or nontoxic material, or the form being easily separated from water is converted into, reaches the purpose of processing.Conventional advanced oxidation skill
Art has Fenton oxidation, ozone oxidation, potassium permanganate oxidation and activation persulfate oxidation etc., and wherein Fenton oxidation is because to major part
Organic pollution have degraded thoroughly, the advantage such as efficiency high, speed is fast and include in environmental improvement during underground water pollution is repaired
To being widely applied, but the hydrogen peroxide short life in classical Fenton oxidation, disperse uneven, localized rich in underground water and spend
Height, when contacting not good with pollutant, it is easy to occur selfdecomposition generation oxygen and water, cause a large amount of wastes of hydrogen peroxide, oxygen
The volatile organic contaminant that gas is also possible in stripping underground water, which is allowed to diffuse into aeration zone, causes the expansion of pollution range；It is fragrant
Pause and react or exothermic reaction, with the rise of temperature of reaction system, it is anti-that hydrogen peroxide selfdecomposition reaction can gradually substitute Fenton
Dominant advantage should be occupied, the invalid waste of hydrogen peroxide is further resulted in.Therefore hydrogen peroxide how is controlled in underground water
Concentration and diffuser efficiency are that the technology success is applied to the key that underground water pollution is repaired.
Calper calcium peroxide be it is a kind of can be sustained the solid peroxide of hydrogen peroxide, can slowly discharge in aqueous
Hydrogen oxide, therefore the hydrogen peroxide in classical Fenton reagent is substituted using calper calcium peroxide, liquid hydrogen peroxide and Fe can be overcome
(II) Fenton-type reagent is constituted, the problem of can overcoming the short life in underground water makes it possible to and organic dirt in underground water
Dye thing is fully contacted, so as to improve class Fenton's reaction efficiency.Fenton or class Fenton sustained response also need to stable Fe (II)
Source is supplied, and Fe is used in classical Fenton reagent2+As catalyst, it generates Fe with hydroperoxidation3+, Fe3+Acid or near
Easily precipitated under neutrallty condition, it is difficult to be reduced to Fe2+To realize that it is reused, it is therefore desirable to can just hold in acid condition
Continue and produce Fenton's reaction, in addition Fe2+The strong oxidizing property hydroxyl radical free radical of Fenton's reaction generation can be also consumed, causes reaction efficiency to drop
Solution.Therefore scholar proposes to substitute ferrous salt to produce Fe using Zero-valent Iron2+And catalyzing hydrogen peroxide, Zero-valent Iron can be in acidity
Or slow generation Fe under near-neutral sulfite deinking2+, so as to control Fe in solution2+Concentration, reduces the generation of side reaction, so as to improve oxygen
The utilization ratio of agent.But common Zero-valent Iron is immiscible with the aqueous solution, it is unfavorable for improving its contacting efficiency with oxidant, if
Nano-scale particle is made in Zero-valent Iron, then can be suspended in the aqueous solution, so as to improve the contacting efficiency with oxidant, Jin Erti
The efficiency of high class Fenton's reaction.
The present invention discloses one kind and utilizes CaO on the basis of applicant studies for many years2/ NZVI Synergistic degradation underground water
The method of middle phthalic acid ester, realizes convenient, efficient degradation PAEs waste water.
The content of the invention
CaO is utilized the invention provides one kind2The method of phthalic acid ester in/NZVI Synergistic degradation underground water, is solved
There is H in groundwater remediation in classical Fenton process2O2The problem of easy decomposition, low utilization rate and big wastage, also overcome
Ferrous salt secondary pollution problems, with process conditions are simple, operation requires low feature, to can be widely applied to underground water have
The reparation of machine pollution.
The present invention utilizes CaO for one kind2The method of phthalic acid ester, particular technique in/NZVI Synergistic degradation underground water
Scheme is as follows：Calper calcium peroxide and nano zero valence iron are added into phthalic acid ester polluted underground water first, with hydrochloric acid and hydrogen-oxygen
Change sodium and adjust the pH of underground water, then be put in constant temperature oscillator and carry out degradation reaction.Phthalic acid ester in underground water after processing
Clearance highest can reach more than 95%.
The concentration of phthalic acid ester is 2~50mg/L in described waste water.
Described CaO2For 1~5 times of PAEs molal quantitys in waste water.
Described NZVI is 1~5 times of PAEs molal quantitys in waste water
Described pH is adjusted for 3~9, pH control hydrochloric acid and NaOH.
The temperature of described constant temperature oscillator is normal temperature, and rotating speed is 180r/min.
Described degradation time is 2~12h.
In the present invention, CaO2Main function be as H2O2Sustained release agent, its H slowly discharged2O2In iron-based material catalysis
Effect is lower to produce the hydroxyl radical free radical with strong oxidizing property.
In the present invention, the main function of nano zero valence iron (NZVI) is the slow generation Fe under oxidant effect2+, and with
CaO2It is sustained the H produced2O2Fenton-type reagent is constituted, because it is Nanometer grade catalysis material, with very big specific surface area, its
Surface and CaO2Catalysis produces great amount of hydroxy group free radical after contact, so as to improve oxidation efficiency.
Beneficial effects of the present invention：
Present invention process condition is simple, operation requires low, and PAEs degradation rates are high.It is effectively reduced in classical Fenton's reaction
H2O2It is a large amount of to waste and secondary pollution problem caused by excessive iron ion.
Embodiment
Below in conjunction with instantiation, the present invention is further illustrated, but embodiments of the present invention not limited to this.
Simulation dibutyl phthalate (DBP) underground aqueous solution is carried out using processing method of the present invention in embodiment 1
Processing, is extracted using carbon tetrachloride, using liquid chromatogram quantitative analysis.
Embodiment 1：
100mL DBP underground water (30mg/L) is prepared, 39mg/L calper calcium peroxides, 12mg/L nanometer are added into underground water
Zero-valent Iron, adjusts pH to 5, is reached in vibrating DBP degradation rates in 12h, underground water under normal temperature in 180r/min constant temperature oscillator
To 96.17%.
Claims (6)
1. a kind of NZVI/CaO2The method of phthalic acid ester in Synergistic degradation underground water, it is characterised in that comprise the following steps：
Calper calcium peroxide and nano zero valence iron are added into phthalic acid ester underground water first, waste water is controlled with hydrochloric acid and NaOH
PH, then be put in constant temperature oscillator and carry out degradation reaction.
2. according to the method described in claim 1, it is characterised in that in the waste water concentration of phthalic acid ester be 2~
50mg/L。
3. according to the method described in claim 1, it is characterised in that described pH is 3~9.
4. according to the method described in claim 1, it is characterised in that the SODIUM PERCARBONATE dosage is phthalic acid in waste water
1~5 times of ester molal quantity.
5. according to the method described in claim 1, it is characterised in that the nano zero valence iron average grain diameter 30-80nm, do not coat
Purity is more than 99.9%, and dosage is 1~5 times of phthalic acid ester molal quantity.
6. according to the method described in claim 1, it is characterised in that the temperature of the constant temperature oscillator is normal temperature, rotating speed is
180r/min, the concussion time is 2~12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710206389.9A CN106955706A (en) | 2017-03-31 | 2017-03-31 | A kind of NZVI/CaO2The method of phthalic acid ester in Synergistic degradation underground water |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710206389.9A CN106955706A (en) | 2017-03-31 | 2017-03-31 | A kind of NZVI/CaO2The method of phthalic acid ester in Synergistic degradation underground water |
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| CN106955706A true CN106955706A (en) | 2017-07-18 |
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| CN201710206389.9A Pending CN106955706A (en) | 2017-03-31 | 2017-03-31 | A kind of NZVI/CaO2The method of phthalic acid ester in Synergistic degradation underground water |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110697866A (en) * | 2019-11-05 | 2020-01-17 | 河北建设集团安装工程有限公司 | Method for removing odor in water by activating calcium peroxide with ferrous iron |
| CN112077138A (en) * | 2019-06-12 | 2020-12-15 | 天津大学 | Application of nano-iron in treating phthalate ester in sediment or soil |
| CN112429831A (en) * | 2020-09-30 | 2021-03-02 | 同济大学 | Method for remedying underground water heavy metal lead and cadmium combined pollution by calcium peroxide-zero-valent iron |
| CN112723518A (en) * | 2020-12-08 | 2021-04-30 | 华侨大学 | Method for degrading antibiotics in water by using zero-valent metal activated peracetic acid |
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| EP2450114A1 (en) * | 2010-11-08 | 2012-05-09 | Biorem Engineering SARL | Gel comprising reactive oxidant release agent |
| CN102583827A (en) * | 2012-03-01 | 2012-07-18 | 中国环境科学研究院 | Repairing system for double-layer permeable reaction wall, preparation method and application |
| CN106493162A (en) * | 2016-12-22 | 2017-03-15 | 常州大学 | A kind of method that PAEs contaminated soils repaired by microwave reinforced calper calcium peroxide |
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2017
- 2017-03-31 CN CN201710206389.9A patent/CN106955706A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2450114A1 (en) * | 2010-11-08 | 2012-05-09 | Biorem Engineering SARL | Gel comprising reactive oxidant release agent |
| CN102583827A (en) * | 2012-03-01 | 2012-07-18 | 中国环境科学研究院 | Repairing system for double-layer permeable reaction wall, preparation method and application |
| CN106493162A (en) * | 2016-12-22 | 2017-03-15 | 常州大学 | A kind of method that PAEs contaminated soils repaired by microwave reinforced calper calcium peroxide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112077138A (en) * | 2019-06-12 | 2020-12-15 | 天津大学 | Application of nano-iron in treating phthalate ester in sediment or soil |
| CN110697866A (en) * | 2019-11-05 | 2020-01-17 | 河北建设集团安装工程有限公司 | Method for removing odor in water by activating calcium peroxide with ferrous iron |
| CN112429831A (en) * | 2020-09-30 | 2021-03-02 | 同济大学 | Method for remedying underground water heavy metal lead and cadmium combined pollution by calcium peroxide-zero-valent iron |
| CN112723518A (en) * | 2020-12-08 | 2021-04-30 | 华侨大学 | Method for degrading antibiotics in water by using zero-valent metal activated peracetic acid |
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Application publication date: 20170718 |