CN111892152A - Method for degrading chlorohydrocarbon by activating persulfate through natural polyphenol-reduced iron powder - Google Patents
Method for degrading chlorohydrocarbon by activating persulfate through natural polyphenol-reduced iron powder Download PDFInfo
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- CN111892152A CN111892152A CN202010695578.9A CN202010695578A CN111892152A CN 111892152 A CN111892152 A CN 111892152A CN 202010695578 A CN202010695578 A CN 202010695578A CN 111892152 A CN111892152 A CN 111892152A
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- iron powder
- reduced iron
- persulfate
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- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
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- 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
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- 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
Abstract
The invention discloses a method for degrading chlorohydrocarbon by activating persulfate through natural polyphenol-reduced iron powder, which comprises the following steps: 1) adding stabilized micron-sized reduced iron powder of polyphenol into sewage containing chlorohydrocarbon; 2) adding persulfate into the mixed solution obtained in the step 1), and fully mixing, wherein: in the stabilized micron-sized reduced iron powder containing polyphenol, the molar percentage of polyphenol to the reduced iron powder is (0.2-2): 50; the molar ratio of the persulfate to the chlorohydrocarbon is (10-100): 1; the molar ratio of the micron-sized reduced iron powder to the persulfate is (1/3-5): 1. the polyphenol substance obviously improves the dechlorination effect on the chlorinated hydrocarbon substance, prolongs the reaction activity, greatly improves the degradation speed of the chlorinated hydrocarbon, has low cost and can be prepared in a large scale.
Description
Technical Field
The invention relates to the field of treatment of chlorinated hydrocarbon pollutants in underground water, in particular to a method for degrading chlorinated hydrocarbon in underground water by activating persulfate through natural polyphenol-reduced iron powder.
Background
Chlorinated hydrocarbons have stable physical and chemical properties, high density, and are insoluble in water, and are widely used in mechanical manufacturing and chemical production. The chlorinated hydrocarbon can enter the environment through volatilization, leakage, waste discharge and other modes, is easy to accumulate in organisms, and has carcinogenicity, teratogenicity and mutagenicity, thereby bringing harm to the environment and human health. There is therefore a great need to degrade chlorinated hydrocarbon materials in contaminated soils and waters.
Persulfate advanced oxidation technology has been widely used to treat a variety of environmental pollutants. Although persulfate salts have strong oxidizing properties, unactivated persulfate salts have low reactivity. Many methods have been developed for activating persulfates, including thermal activation, photo activation, transition metal ion activation, base activation, and organic activation, among others.
The nanometer zero-valent iron activated persulfate is an emerging activation technology, and can release Fe during dechlorination reaction2+Fortifying persulfate with reacted Fe3+Reaction of Fe2+The concentration is effectively regulated and controlled. The existing method realizes the control of the particle size of the synthesized nano particles by adding polyphenol and improves the stability of the nano zero-valent iron, but still has the problems of difficult large-scale preparation, high cost and the like. The nano zero-valent iron is easy to aggregate and deactivate, and the production and storage cost is high, so that the large-scale application of the nano zero-valent iron is greatly limited.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for degrading chlorinated hydrocarbons by activating persulfate through natural polyphenol-reduced iron powder, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for degrading chlorohydrocarbon by activating persulfate through natural polyphenol-reduced iron powder comprises the following steps:
1) adding stabilized micron-sized reduced iron powder of polyphenol into sewage containing chlorohydrocarbon;
2) adding persulfate into the mixed solution obtained in the step 1), fully mixing,
wherein:
in the stabilized micron-sized reduced iron powder containing polyphenol, the molar percentage of polyphenol to the reduced iron powder is (0.2-2): 50;
the molar ratio of the persulfate to the chlorohydrocarbon is (10-100): 1;
the molar ratio of the micron-sized reduced iron powder to the persulfate is (1/3-5): 1.
preferably, in the stabilized micron-sized reduced iron powder containing polyphenol, the molar percentage of polyphenol to reduced iron powder is (0.5-1): 50.
preferably, the molar ratio of the persulfate to the chlorohydrocarbon is (20-80): 1.
Preferably, the molar ratio of the micron-sized reduced iron powder to the persulfate is (1-4): 1.
The chlorinated hydrocarbon is at least one of chloroethylene, dichloroethylene, trichloroethylene, tetrachloroethylene and chloroform.
The natural polyphenol is at least one of tannic acid, procyanidine and anthocyanidin.
The persulfate is at least one of sodium persulfate, potassium persulfate, ammonium persulfate and sodium peroxymonosulfate.
In the step 2), before adding the persulfate, the pH value of the mixed solution is 3.0-11.0, preferably 7.0-9.0.
In the step 2), the reaction temperature is 15-40 ℃, and preferably 25-30 ℃.
The micron-sized reduced iron powder with stable polyphenol is prepared by the following method:
1) weighing polyphenol, and dissolving with ultrapure water to obtain polyphenol water solution;
2) and adding the commercial micron-sized reduced iron powder into the polyphenol water solution, and fully reacting.
Compared with the prior art, the method has the following beneficial effects:
the invention constructs a high-efficiency dechlorination system of persulfate activated by natural polyphenol-reduced iron powder. The natural polyphenol is a substance existing in a large amount in nature, has small secondary influence on the environment, and has wide application prospect for actual environmental pollution treatment. The polyphenol can be used as a chelating agent to chelate iron ions formed in the dechlorination process, inhibit the formation of iron mud on the surface of the reduced iron powder, maintain the concentration of HO & in the system, and compared with the method for activating persulfate by using single reduced iron powder, the polyphenol can obviously improve the dechlorination effect on chlorinated hydrocarbon substances and prolong the reaction activity.
Compared with the traditional system using ferrous iron to activate persulfate, the degradation speed of the reaction system of the invention to chlorohydrocarbon is greatly improved, and the degradation rate of over 99 percent can be reached after the reaction is carried out for 160 min.
In addition, the reaction system has very good effect in a wide temperature range. The invention uses the micron-sized reduced iron powder to replace the nano zero-valent iron, reduces the preparation cost, has the advantages of large-scale preparation, simple production and transportation conditions and the like, and has wide application prospect.
Drawings
FIG. 1 is a graph of contaminant degradation rates for some of the examples of the present invention and for a comparative example.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
The preparation method of the micron-sized reduced iron powder with stable polyphenol comprises the following steps: weighing a certain mass of polyphenol, dissolving with ultrapure water, and performing ultrasonic treatment for 5 minutes to ensure complete dissolution to prepare an aqueous solution of polyphenol. Adding the commercial micron-sized reduced iron powder into the aqueous solution of the polyphenol and uniformly mixing. Wherein the mol percentage of the polyphenol to the micron-sized reduced iron powder is (0.5-1): 50. by this method, polyphenol-stabilized reduced iron powder suspension solutions of different loading amounts can be prepared for use in the following examples and comparative examples.
Example 1 tannin stabilized reduced iron powder to strengthen persulfate to degrade Water sample containing chloroform
Sequentially adding the micron-sized reduced iron powder suspension solution with stable tannic acid and sodium persulfate into a chloroform solution (the concentration is 20mg/L), setting the rotating speed of a water bath shaker to be 120r/min, setting the temperature to be 25 ℃, and reacting for 90 min. Wherein the mol ratio (mol Fe/PS) of the reduced iron powder to the sodium persulfate is 4:1, the mol percentage (mol% TA/Fe) of the tannic acid to the reduced iron powder is 0.018; the molar ratio of sodium persulfate to chloroform was 50: 1. The above reaction was carried out in a 250mL screw-top flask.
After the reaction was started, 2mL of the reaction solution was extracted at regular time intervals using a 5mL syringe, taken out and immediately quenched with methanol, the centrifuge tube containing the sample solution was placed on a strong magnet, iron particles were separated by magnetic force, the upper layer solution was filtered through a 0.22 μm filter, and the sample was measured using a headspace gas chromatography-mass spectrometer to obtain the concentration of chloroform. After 90min of reaction, the degradation efficiency of chloroform was 94.45%.
Example 2 reduced iron powder enhanced sodium persulfate degradation chloroform-containing water sample
Sequentially adding micron-sized reduced iron powder with stable tannic acid and sodium persulfate into a chloroform solution (with the concentration of 20mg/L), setting the rotating speed of a water bath shaker to be 120r/min, setting the temperature to be 40 ℃, and reacting for 90 min. Wherein, the mol ratio (mol percent Fe/PS) of the reduced iron powder to the sodium persulfate is 4:1, and the mol percent (mol percent TA/Fe) of the tannic acid to the reduced iron powder is 0.014; the molar ratio of sodium persulfate to chloroform is 50: 1; the above reaction was carried out in a 250mL screw-top flask.
After the reaction is started, extracting 2mL of reaction solution at fixed time intervals by using a 5mL syringe, taking out the reaction solution, immediately adding methanol to quench the reaction, placing a centrifugal tube filled with the sampling solution on a strong magnet, separating iron particles by using magnetic force, filtering the upper layer solution through a 0.22 micrometer filter membrane, and measuring a sample by using a headspace gas chromatography-mass spectrometer to obtain the concentration of chloroform; after 90min of reaction, the degradation efficiency of chloroform was 90.98%.
Example 3 tannin-stabilized reduced iron powder enhanced sodium persulfate degradation chloroform-containing real water sample
The method comprises the steps of sequentially adding a micron-sized reduced iron powder suspension solution with stable tannic acid and sodium persulfate into an actual water sample (the water sample is collected from a certain polluted site in Tianjin city, the main pollutant in the water sample is chloroform, and simultaneously various organic matters interfere) with the initial concentration of 78.55mg/L and containing chloroform pollution, setting the rotating speed of a water bath shaker to be 120r/min, setting the temperature to be 25 ℃, and reacting for 90 min. Wherein mol Fe/PS is 2:1, and mol% TA/Fe is 0.014; the molar ratio of sodium persulfate to chloroform is 20: 1; the above reaction was carried out in a 250mL screw-top flask.
After the reaction is started, extracting 2mL of reaction solution at fixed time intervals by using a 5mL syringe, taking out the reaction solution, immediately adding methanol to quench the reaction, placing a centrifugal tube filled with the sampling solution on a strong magnet, separating iron particles by using magnetic force, filtering the upper layer solution through a 0.22 micrometer filter membrane, and measuring a sample by using a headspace gas chromatography-mass spectrometer to obtain the concentration of chloroform; after 90min of reaction, the degradation efficiency of chloroform was 89.82%.
Comparative example 1 direct degradation of chloroform-containing Water sample by reduced iron powder
Directly taking commercially available micron-sized reduced iron powder, adding the micron-sized reduced iron powder into a chloroform solution (with the concentration of 20mg/L), setting the rotating speed of a water bath shaker at 120r/min, setting the temperature at 25 ℃, and reacting for 90 min. The molar ratio of the added reduced iron powder to the chloroform is 100; the above reaction was carried out in a 250mL screw-top flask.
After the reaction is started, extracting 2mL of reaction solution at fixed time intervals by using a 5mL syringe, placing a centrifugal tube filled with the sampling solution on a strong magnet, separating iron particles by using magnetic force, filtering the upper layer solution by using a 0.22-micrometer filter membrane, and measuring a sample by using a headspace gas chromatography-mass spectrometer to obtain the concentration of chloroform; after 90min of reaction, the degradation efficiency of chloroform was 20.50%.
Comparative example 2 reduced iron powder-reinforced sodium persulfate degradation chloroform-containing water sample
Sequentially adding the micron-sized reduced iron powder suspension solution with stable tannic acid and sodium persulfate into a chloroform solution (the concentration is 20mg/L), setting the rotating speed of a water bath shaker to be 120r/min, setting the temperature to be 15 ℃, and reacting for 90 min. Wherein, the mol ratio (mol percent Fe/PS) of the reduced iron powder to the sodium persulfate is 4:1, and the mol percent (mol percent TA/Fe) of the tannic acid to the reduced iron powder is 0.014; the molar ratio of sodium persulfate to chloroform is 50: 1; the above reaction was carried out in a 250mL screw-top flask.
After the reaction is started, extracting 2mL of reaction solution at fixed time intervals by using a 5mL syringe, taking out the reaction solution, immediately adding methanol to quench the reaction, placing a centrifugal tube filled with the sampling solution on a strong magnet, separating iron particles by using magnetic force, filtering the upper layer solution through a 0.22 micrometer filter membrane, and measuring a sample by using a headspace gas chromatography-mass spectrometer to obtain the concentration of chloroform; after 90min of reaction, the degradation efficiency of chloroform was 82.2%.
Comparative example 3 degradation of Water sample containing chloroform by reduced iron powder reinforced persulfate stabilized by tannic acid
The micron-sized reduced iron powder suspension solution and sodium persulfate are sequentially added into a chloroform solution (with the concentration of 20mg/L), the rotating speed of a water bath shaker is set to be 120r/min, the temperature is set to be 25 ℃, and the reaction time is 90 min. Wherein the mol ratio (mol Fe/PS) of the reduced iron powder to the sodium persulfate is 3: and 2, the molar ratio of the sodium persulfate to the chloroform is 50: 1; the above reaction was carried out in a 250mL screw-top flask.
After the reaction is started, extracting 2mL of reaction solution at fixed time intervals by using a 5mL syringe, taking out the reaction solution, immediately adding methanol to quench the reaction, placing a centrifugal tube filled with the sampling solution on a strong magnet, separating iron particles by using magnetic force, filtering the upper layer solution through a 0.22 micrometer filter membrane, and measuring a sample by using a headspace gas chromatography-mass spectrometer to obtain the concentration of chloroform; after 90min of reaction, the degradation efficiency of chloroform was 80.43%.
The degradation rates measured under the different reaction conditions are shown in the following table:
| examples/comparative examples | Reaction temperature C | mol Fe/PS | mol％TA/Fe | The degradation rate% |
| Example 1 | 25 | 4 | 0.018 | 94.45 |
| Example 2 | 40 | 4 | 0.014 | 90.98 |
| Example 3 | 25 | 2 | 0.014 | 89.82 |
| Comparative example 1 | 25 | Pure Fe | 0 | 20.5 |
| Comparative example 2 | 15 | 4 | 0.014 | 82.2 |
| Comparative example 3 | 25 | 1.5 | 0 | 80.43 |
From the data in the table, it can be seen that the natural polyphenol-reduced iron powder reinforced sodium persulfate has an excellent degradation effect on chloroform.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for degrading chlorohydrocarbon by activating persulfate through natural polyphenol-reduced iron powder comprises the following steps:
1) adding stabilized micron-sized reduced iron powder of polyphenol into sewage containing chlorohydrocarbon;
2) adding persulfate into the mixed solution obtained in the step 1), fully mixing,
wherein:
in the stabilized micron-sized reduced iron powder containing polyphenol, the molar percentage of polyphenol to the reduced iron powder is (0.2-2): 50;
the molar ratio of the persulfate to the chlorohydrocarbon is (10-100): 1;
the molar ratio of the micron-sized reduced iron powder to the persulfate is (1/3-5): 1.
2. the method of claim 1, wherein: in the stabilized micron-sized reduced iron powder containing polyphenol, the molar percentage of polyphenol to the reduced iron powder is (0.5-1): 50.
3. the method of claim 1, wherein: the molar ratio of the persulfate to the chlorinated hydrocarbon is (20-80): 1.
4. the method of claim 1, wherein: the molar ratio of the micron-sized reduced iron powder to the persulfate is (1-4): 1.
5. the method of claim 1, wherein: the chlorinated hydrocarbon is at least one of chloroethylene, dichloroethylene, trichloroethylene, tetrachloroethylene and chloroform.
6. The method of claim 1, wherein: the natural polyphenol is at least one of tannic acid, procyanidine and anthocyanidin.
7. The method of claim 1, wherein: the persulfate is at least one of sodium persulfate, potassium persulfate, ammonium persulfate and sodium peroxymonosulfate.
8. The method of claim 1, wherein: in the step 2), before adding the persulfate, the pH of the mixed solution is 3.0-11.0, preferably 7.0-9.0.
9. The method of claim 1, wherein: in the step 2), the reaction temperature is 15-40 ℃, and preferably 25-30 ℃.
10. The method according to any one of claims 1-9, wherein: the micron-sized reduced iron powder with stable polyphenol is prepared by the following method:
1) weighing polyphenol, and dissolving with ultrapure water to obtain polyphenol water solution;
2) and adding the commercial micron-sized reduced iron powder into the polyphenol water solution, and fully reacting.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103288200A (en) * | 2013-07-01 | 2013-09-11 | 华东理工大学 | Method for removing hydrochloric ether contained in underground water and soil mud system through chemical reduction |
| CN109019819A (en) * | 2018-09-04 | 2018-12-18 | 上海格林曼环境技术有限公司 | For the reduction medicament of chlorohydrocarbon polluted underground water in-situ immobilization and its preparation and application method |
| CN109942072A (en) * | 2019-04-23 | 2019-06-28 | 天津华勘环保科技有限公司 | A kind of method of natural polyphenol activation persulfate degradating chloro hydrocarbon |
| CN109942071A (en) * | 2019-04-23 | 2019-06-28 | 天津华勘环保科技有限公司 | A kind of method that extraction and nanometer iron metal that tannic acid is stable strengthens persulfate degradation open chain chlorohydrocarbon |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288200A (en) * | 2013-07-01 | 2013-09-11 | 华东理工大学 | Method for removing hydrochloric ether contained in underground water and soil mud system through chemical reduction |
| CN109019819A (en) * | 2018-09-04 | 2018-12-18 | 上海格林曼环境技术有限公司 | For the reduction medicament of chlorohydrocarbon polluted underground water in-situ immobilization and its preparation and application method |
| CN109942072A (en) * | 2019-04-23 | 2019-06-28 | 天津华勘环保科技有限公司 | A kind of method of natural polyphenol activation persulfate degradating chloro hydrocarbon |
| CN109942071A (en) * | 2019-04-23 | 2019-06-28 | 天津华勘环保科技有限公司 | A kind of method that extraction and nanometer iron metal that tannic acid is stable strengthens persulfate degradation open chain chlorohydrocarbon |
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Application publication date: 20201106 |