CN104692515A - Method for removing chloro-olefin in water through strengthening activating calcium peroxide - Google Patents
Method for removing chloro-olefin in water through strengthening activating calcium peroxide Download PDFInfo
- Publication number
- CN104692515A CN104692515A CN201510057349.3A CN201510057349A CN104692515A CN 104692515 A CN104692515 A CN 104692515A CN 201510057349 A CN201510057349 A CN 201510057349A CN 104692515 A CN104692515 A CN 104692515A
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- Prior art keywords
- chloro
- calcium peroxide
- alkenes
- citric acid
- add
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Classifications
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for removing chloro-olefin in water through strengthening activating calcium peroxide, for removing the chloro-olefin contaminant existed in the underground water by using the oxidation of the calcium peroxide (CaO2), and belongs to the technical field of environmental management. In the treating process, in the existence of the calcium peroxide, the ferric ion is added for activating the oxidizing agent, the citric acid is added for reinforcing the activation effect and then the chloro-olefin contaminant is oxidized. The method has the advantages that the calcium peroxide is used as a novel green oxidizing agent and has the characteristics of strong oxidizing ability, high stability and long oxidizing effect; by adopting the ferric ion and the citric acid, the calcium peroxide can be continuously and effectively activated and the timeliness of the oxidation can be increased; the pollution of the underground water caused by the chloro-olefin can be effectively green repaired and treated without intermediate product accumulation or secondary pollution.
Description
[technical field]
The present invention relates to water-treatment technology field, specifically, is that a kind of reinforcement activates the method that chloro-alkenes in water removed by calcium peroxide.
[background technology]
Underground water is one of of paramount importance Freshwater resources on the earth.Along with developing rapidly of industrial or agricultural, increasing underground water is contaminated.Be widely used in the chlorinated hydrocarbon organic solvents such as the trieline in the modern industry such as degreasing, dry-cleaning, zellon, chloroform, frequently detected in underground water all over the world, become the main source of groundwater pollution already.Again because it has " three cause " effect, wherein the overwhelming majority has been classified as the hazardous contaminant of priority acccess control by various countries.The popularity polluted in view of underground environment chlorinated hydrocarbon and chlorinated hydrocarbon pollutent are to the strong hazardness of environmental ecology, and Chinese scholars has extensively carried out control and the repairing and treating technology of the chlorinated hydrocarbon pollutent in groundwater environment.
At present, domestic and international polluted underground water recovery technique is mainly divided into showering and in-situ immobilization two kinds of operating method.Showering needs excavate soil or extract underground water out, costly, is generally applicable to the place that Polluted area is less.In-situ immobilization is cost-saved, simple to operate, little to environmental disruption.Existing based technique for in-situ remediation mainly comprises situ heat treatment, microorganism remediation, phytoremediation, permeable coefficient tensor and in situ chemical oxidation technology etc.In situ chemical oxidation is that oxygenant is directly injected underground, can effective degradable organic pollutant fast, is one of Remedy Technology of Contaminated Groundwater of current most potentiality.
The oxygenant that in situ chemical oxidation technology is commonly used comprises permanganate, Fenton reagent, ozone and persulphate etc.Wherein Fenton reagent can be oxidized most of organism because of it, has non-selectivity, is swift in response, processes thoroughly, the feature such as raw material economics is easy to get, easy and simple to handle, reaction conditions is gentle, non-secondary pollution, becomes more promising based technique for in-situ remediation.But H
2o
2there is unstable, and high density H
2o
2operation has certain risk, limit Fenton reagent in position chemical oxidation repair in application.Calcium peroxide (CaO
2) be a kind of novel in situ chemical oxidation agent, it is the superoxide of calcium, and Yin Yi and water react and discharges H
2o
2, be commonly called as Solid hydrogen peroxide.CaO
2for strong oxidizer, having that cost is low, safe to use, a feature of operative temperature wide ranges, pollution-free, free from extraneous odour, is a kind of desirable Green Oxidant.In addition, CaO
2do not have toxicity to microorganism, therefore the compatibility of itself and bioremediation technology is higher, comes into one's own gradually in underground water pollution control field.
With Fenton reacting phase seemingly, Fe
2+for effective activation CaO
2one of means, but CaO
2with Fe
2+reaction is very rapid, causes the radius of influence of oxygenant in underground to reduce, and CaO
2with Fe
2+the optimal ph of reaction, between 2 ~ 4, need add a large amount of acid solution and keep solution ph, the destructible ecosystem when original position uses.Therefore need exploitation one can effective control CaO
2active rate, strengthens the radius of influence that its original position uses, and can expand the new technology of reacting applicable pH value range.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of reinforcement to activate the method that chloro-alkenes in water removed by calcium peroxide.This technology uses Fe
3+activation CaO
2, Fe
3+can continue slowly to generate Fe
2+, maintain CaO
2activation efficiency, extends oxygenant action time; Add the concentration that citric acid improves solvability iron, improve the validity of iron, expand the pH scope of application, strengthening activation effect.
The object of the invention is to be achieved through the following technical solutions:
Strengthen activating the method that chloro-alkenes in water removed by calcium peroxide, its concrete steps are, are add the calcium peroxide (CaO that relative chloro-alkenes molar ratio is 4: 1 ~ 8: 1 in 20mg/L chloro-alkenes polluted underground water solution to concentration
2) pressed powder reacts, then add ferric sulfate (Fe
2(SO
4)
3) calcium peroxide is activated, then add citric acid (C
6h
8o
7) strengthening activation effect, sample from reactor in the different time periods, by the chloro-alkenes concentration of gas Chromatographic Determination sample, find that, after above-mentioned reaction process, chloro-alkenes removal effect is remarkable.
Described chloro-alkenes is trieline (TCE) and zellon (PCE);
Described reaction conditions is: controlling temperature of reaction is 18 DEG C, and carry out magnetic agitation to reaction process, rotating speed is 600r/min simultaneously;
Described calcium peroxide (CaO
2) be a kind of novel in situ chemical oxidation agent.
Described oxygenant activation method: add ferric sulfate pressed powder and activate, add citric acid solid particle to strengthen, the mol ratio of ferric sulfate and calcium peroxide between 1: 1 ~ 2: 1, citric acid and ferric sulfate mol ratio best results between 1: 2 ~ 1: 4;
Compared with prior art, positively effect of the present invention is:
(1) operation is simple and Be very effective in the present invention;
(2) calcium peroxide is cheap, can directly prepare as oxygenant;
(3) calcium peroxide stability is strong, is convenient to actual shipment and operation;
(4) ferric sulfate is cheap, stable in properties, obvious to calcium peroxide activation effect, can continue to produce Fe
2+, maintain calcium peroxide activation, improve the radius of influence that original position uses;
(5) citric acid add the advantageous pH range having expanded reaction process, improve the validity of solvability iron ion, enhance activation effect;
(6) do not have secondary pollution to produce in chemical oxidation of gold of the present invention, final product is carbonic acid gas and water;
(7) the calcium peroxide oxidation capacity used in the present invention is strong, and the molar ratio of chloro-alkenes is 4: 1 ~ 8: 1 time, and chloro-alkenes clearance can reach 99.9%;
(8) reaction process of the present invention is affected by environment less, and the environment be applicable to is wider, and product nontoxicity, is convenient to subsequent disposal, has wide application prospect.
[embodiment]
A kind of reinforcement of the present invention is below provided to activate the embodiment that the method for chloro-alkenes in water removed by calcium peroxide.
Embodiment 1
Be in the 250mL aqueous solution of 20mg/L at trieline (TCE) starting point concentration, add 14.6mg CaO successively
2, 60.8mg Fe
2(SO
4)
3with 16.0mg citric acid, fully stir in chemical oxidation of gold, it is 18 DEG C that simultaneous reactions temperature controls, reaction times 90min, respectively 5,10,20,30,60,90min carries out sampling extraction, then use TCE concentration in gas chromatographic analysis sample, result reaches 99.9% through TCE clearance after 90min of the technology of the present invention process.
Embodiment 2
Be in the 250mL aqueous solution of 20mg/L at trieline (TCE) starting point concentration, add 14.6mg CaO successively
2, 60.8mg Fe
2(SO
4)
3with 32.0mg citric acid, fully stir in chemical oxidation of gold, it is 18 DEG C that simultaneous reactions temperature controls, reaction times 90min, respectively 5,10,20,30,60,90min carries out sampling extraction, then use TCE concentration in gas chromatographic analysis sample, result reaches 99% through TCE clearance after 90min of the technology of the present invention process.
Embodiment 3
Be in the 250mL aqueous solution of 20mg/L at trieline (TCE) starting point concentration, add 29.3mg CaO successively
2, 60.8mg Fe
2(SO
4)
3with 16.0mg citric acid, fully stir in chemical oxidation of gold, it is 18 DEG C that simultaneous reactions temperature controls, reaction times 90min, respectively 5,10,20,30,60,90min carries out sampling extraction, then use TCE concentration in gas chromatographic analysis sample, result reaches 99.9% through TCE clearance after 60min of the technology of the present invention process.
Embodiment 4
Be in the 250mL aqueous solution of 20mg/L at zellon (PCE) starting point concentration, add 14.6mg CaO successively
2, 60.8mg Fe
2(SO
4)
3with 16.0mg citric acid, fully stir in chemical oxidation of gold, it is 18 DEG C that simultaneous reactions temperature controls, reaction times 90min, respectively 5,10,20,30,60,90min carries out sampling extraction, then use PCE concentration in gas chromatographic analysis sample, result reaches 99.9% through PCE clearance after 90min of the technology of the present invention process.
Embodiment 5
Be in the 250mL aqueous solution of 20mg/L at zellon (PCE) starting point concentration, add 29.3mg CaO successively
2, 60.8mg Fe
2(SO
4)
3with 16.0mg citric acid, fully stir in chemical oxidation of gold, it is 18 DEG C that simultaneous reactions temperature controls, reaction times 90min, respectively 5,10,20,30,60,90min carries out sampling extraction, then use PCE concentration in gas chromatographic analysis sample, result reaches 99% through PCE clearance after 60min of the technology of the present invention process.
Embodiment 6
Be in the 250mL aqueous solution of 20mg/L at zellon (PCE) starting point concentration, add 29.3mg CaO successively
2, 121.7mg Fe
2(SO
4)
3with 32.0mg citric acid, fully stir in chemical oxidation of gold, it is 18 DEG C that simultaneous reactions temperature controls, reaction times 90min, respectively 5,10,20,30,60,90min carries out sampling extraction, then use PCE concentration in gas chromatographic analysis sample, result reaches 99% through PCE clearance after 90min of the technology of the present invention process.
Method of the present invention is in treating processes, ensures CaO
2under existent condition, oxide treatment is carried out to chloro-alkenes; Add Fe simultaneously
3+oxygenant is activated, adds citric acid strengthening chemical oxidation of gold.The superiority of present method is: the method is simple, Be very effective; CaO
2as a kind of oxygenant of green, have extremely strong oxidation capacity, oxygenizement is lasting, and the radius of influence is large; Fe
2(SO
4)
3can continuous activation CaO
2, strengthened by citric acid chelating rear stability; The removal efficiency of chloro-alkenes is high, and trieline and zellon were removed substantially completely in 90 minutes, and removal efficiency reaches 99%; The method does not have intermediate product to accumulate, non-secondary pollution and cheap.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (5)
1. strengthen activating the method that chloro-alkenes in water removed by calcium peroxide, it is characterized in that, concrete steps are, add calcium peroxide pressed powder and react in the polluted underground water solution containing chloro-alkenes, then add ferric sulfate and activate oxygenant; Add citric acid and ferric ion chelating, strengthening activation effect; Realize the oxidation removal of chloro-alkenes in polluted underground water.
2. a kind of reinforcement as claimed in claim 1 activates the method that chloro-alkenes in water removed by calcium peroxide, and it is characterized in that, described chloro-alkenes is pollutent common in polluted underground water: trieline and zellon.
3. a kind of reinforcement as claimed in claim 1 activates the method that chloro-alkenes in water removed by calcium peroxide, and it is characterized in that, described reaction conditions is: fully mix and blend, temperature of reaction controls at 18 DEG C.
4. a kind of reinforcement as claimed in claim 1 activates the method that chloro-alkenes in water removed by calcium peroxide, it is characterized in that, in the calcium peroxide pressed powder added and the aqueous solution, the molar ratio of chloro-alkenes is 4: 1 ~ 8: 1.
5. a kind of reinforcement as claimed in claim 1 activates the method that chloro-alkenes in water removed by calcium peroxide, it is characterized in that, described oxygenant activation method: add ferric sulfate pressed powder and activate, add citric acid solid particle to strengthen, the mol ratio of ferric sulfate and calcium peroxide is 1: 1 ~ 2: 1, and the mol ratio of citric acid and ferric sulfate is 1: 2 ~ 1: 4.
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Cited By (15)
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---|---|---|---|---|
CN105906073A (en) * | 2016-06-29 | 2016-08-31 | 江苏艾特克环境工程设计研究院有限公司 | Oxidant for treating chemical wastewater and preparation method thereof |
CN106517705A (en) * | 2016-12-07 | 2017-03-22 | 宁波大红鹰学院 | Polluted riverway bottom sediment repairing agent and preparation method and application thereof |
CN106673173A (en) * | 2017-02-22 | 2017-05-17 | 上海广联环境岩土工程股份有限公司 | In-situ oxidizing well for treating chlorinated hydrocarbon-polluted underground water |
CN106966484A (en) * | 2017-03-31 | 2017-07-21 | 常州大学 | A kind of nanometer Fe3O4/CaO2The method for repairing the pollution of underground water benzene homologues |
CN107321782A (en) * | 2016-04-29 | 2017-11-07 | 上海市环境科学研究院 | A kind of method that EDTA complexings ferrous ion activation calper calcium peroxide removes soil petrochina hydrocarbon |
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CN108059228A (en) * | 2017-12-20 | 2018-05-22 | 苏州科技大学 | A kind of method of sulfamido antiseptic in removal livestock breeding wastewater |
CN108380663A (en) * | 2018-04-25 | 2018-08-10 | 上海化工研究院有限公司 | The method that class Fenton oxidation method removes half volatile organic contaminant in soil |
CN109081422A (en) * | 2018-08-27 | 2018-12-25 | 南京泽辉环保科技有限公司 | A method of utilizing low-concentration ammonia-nitrogen in ozone and micro calper calcium peroxide removal water body |
CN109133316A (en) * | 2017-06-19 | 2019-01-04 | 湖南大学 | A method of using calper calcium peroxide oxidation pre-treatment containing emerging pollutant waste water |
CN109304363A (en) * | 2018-10-29 | 2019-02-05 | 东华大学 | A kind of chemical remediation medicament and its application method suitable for oil-polluted soils |
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CN112537839A (en) * | 2020-11-17 | 2021-03-23 | 同济大学 | Method for remedying heavy metal pollution of underground water in river network area by using calcium peroxide-pyrite |
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CN108059228A (en) * | 2017-12-20 | 2018-05-22 | 苏州科技大学 | A kind of method of sulfamido antiseptic in removal livestock breeding wastewater |
CN108380663A (en) * | 2018-04-25 | 2018-08-10 | 上海化工研究院有限公司 | The method that class Fenton oxidation method removes half volatile organic contaminant in soil |
CN109081422A (en) * | 2018-08-27 | 2018-12-25 | 南京泽辉环保科技有限公司 | A method of utilizing low-concentration ammonia-nitrogen in ozone and micro calper calcium peroxide removal water body |
CN109304363A (en) * | 2018-10-29 | 2019-02-05 | 东华大学 | A kind of chemical remediation medicament and its application method suitable for oil-polluted soils |
CN109354253A (en) * | 2018-11-28 | 2019-02-19 | 同济大学 | Method that is a kind of while removing pumping plant useless Organic substance in water and phosphorus |
CN111217481A (en) * | 2020-01-20 | 2020-06-02 | 湖南金旅环保股份有限公司 | Pharmaceutical wastewater pretreatment method combining iron-carbon micro-electrolysis and Fenton-like system |
CN112537839A (en) * | 2020-11-17 | 2021-03-23 | 同济大学 | Method for remedying heavy metal pollution of underground water in river network area by using calcium peroxide-pyrite |
CN113072164A (en) * | 2021-04-25 | 2021-07-06 | 上海交通大学 | Activated carbon for enhancing Fenton-like reaction removal efficiency and preparation and use methods thereof |
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