CN112320919B - Water body restoration method based on zero-valent iron silicide activated persulfate - Google Patents
Water body restoration method based on zero-valent iron silicide activated persulfate Download PDFInfo
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- CN112320919B CN112320919B CN202011112107.7A CN202011112107A CN112320919B CN 112320919 B CN112320919 B CN 112320919B CN 202011112107 A CN202011112107 A CN 202011112107A CN 112320919 B CN112320919 B CN 112320919B
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
Abstract
A water body restoration method based on zero-valent iron silicide activated persulfate comprises the following steps: treating organic wastewater by using micrometer zero-valent iron silicide as a catalytic activator and persulfate as an oxidant, wherein the molar ratio of the catalytic activator to the oxidant is 1: 0.5-3. The invention adds the zero-valent iron silicide and the persulfate into the pollution to be treated to carry out the oxidation removal of the organic pollutants, and the surface of the zero-valent iron silicide is rich in silanol groups (≡ Si-OH). The method can solve the problems that the iron-based material is easy to inactivate and the late release of ferrous ions is insufficient in the traditional persulfate system, has high restoration efficiency and is environment-friendly, and is suitable for the treatment and restoration of various organic polluted wastewater and groundwater.
Description
Technical Field
The invention belongs to the technical field of preparation of environmental materials and restoration of polluted water, and particularly relates to a water restoration method based on zero-valent iron silicide activated persulfate.
Background
The technology of activating persulfate by using the zero-valent iron has become a very promising technology in the aspect of treatment of organic pollutant wastewater difficult to degrade by using the strong electron-donating capability of the zero-valent iron. The technology can generate sulfate radicals stronger than hydroxyl radicals, and has longer service life and certain selectivity. The heterogeneous activation technology based on zero-valent iron can solve the problems that the reaction rate in a homogeneous ferrous system cannot be controlled, the ferric ions are quickly hydrolyzed and precipitated, anions capable of quenching free radicals are introduced, secondary pollution caused by iron-containing sludge and the like.
However, in the activation technology based on zero-valent iron, an oxidation layer formed on the surface of the zero-valent iron after oxidation inhibits the zero-valent iron from continuously releasing ferrous iron, thereby causing the reduction of the catalytic activity of the system. In order to solve the problem, researchers build a galvanic cell effect by loading bimetal on zero-valent iron to promote the corrosion dissolution of the zero-valent iron and improve the catalytic activity of the zero-valent iron. In addition, the activation efficiency of the zero-valent iron catalytic material can be enhanced by changing the surface properties of the zero-valent iron, such as surface vulcanization of the zero-valent iron, regulation of the corrosion behavior of the zero-valent iron and the release rate of ferrous iron. Both the synthesized bimetal loaded zero-valent iron and the surface sulfur modified zero-valent iron can not avoid the problem of secondary pollution caused by the dissolution of toxic metals or sulfur elements in the reaction process. Therefore, the problem to be solved by exploring a green and efficient technology and improving the oxidation activity of the zero-valent iron activated persulfate is always solved.
Disclosure of Invention
The invention aims to disclose a water body restoration method based on zero-valent iron silicide activated persulfate, which aims to overcome the defects of easy inactivation, poor cycle performance and secondary pollutant dissolution in the existing iron-based activated persulfate technology.
In order to achieve the purpose, the invention discloses a water body remediation method based on zero-valent iron silicide activated persulfate, which is characterized in that micron zero-valent iron silicide is used as a catalytic activator, persulfate is used as an oxidant to treat organic wastewater, and the molar ratio of the catalytic activator to the oxidant is 1: 0.5-3.
The water body restoration method is characterized in that the micron zero-valent iron silicide is prepared by mixing soluble silicate and micron iron powder according to the proportion of 0.02-20% of the mole of silicon/iron, and then performing ball milling, separation and drying respectively.
In the water body repairing method, the soluble silicate is one or more of sodium silicate, potassium metasilicate, layered crystal sodium disilicate, layered crystal potassium disilicate and a plurality of layered crystal composite silicates.
The water body restoration method comprises the step of preparing the micron iron powder into the water body, wherein the micron iron powder is micron-sized reduced iron powder, raw iron powder, foam iron powder and/or iron powder, and the particle size of the iron powder is 100-800 meshes.
The water body restoration method comprises the step of ball milling for 2-20 hours at the rotating speed of 300-.
The water body restoration method comprises the step of preparing persulfate, wherein the persulfate is potassium monopersulfate, sodium monopersulfate, ammonium monopersulfate, potassium persulfate, sodium persulfate and/or ammonium persulfate.
The water body remediation method is characterized in that the pH value of the organic wastewater treatment system is controlled to be 3-10.
The water body remediation method is characterized in that the organic wastewater comprises but is not limited to organic polluted water bodies of chlorinated organic matters, antibiotics and polycyclic aromatic hydrocarbons.
Compared with the prior art, the invention has the following beneficial effects:
the silicified zero-valent iron used in the invention is green and nontoxic, has low cost, and does not have the problem of secondary pollution in the repair process. Due to the coordination of the special silanol groups of the silicified shell, Fe (III) generated by oxidation can accept electrons at the interface to be reduced, and the continuous supply of Fe (II) is realized.
The method has the advantages of simple process, convenient operation and mild reaction conditions, and can realize the high-efficiency treatment of various refractory organic wastewater.
Drawings
FIG. 1 shows a process for preparing silicified micro zero valent iron (Si-mZVI) based on the present inventionBM) Grinding with ordinary unsilicided ball iron (ZVI)BM) An X-ray photoelectron spectroscopy signature; wherein, a) is an X-ray photoelectron spectrum of silicified micron zero-valent iron and ordinary unsilicided ball-milled iron; b) is an X-ray photoelectron spectrum of silicified micron zero-valent iron.
FIG. 2 is an infrared spectrum of the micron zero-valent iron silicide prepared by the present invention and ordinary unsilicided ball-milled iron.
FIG. 3 is a comparison of performance of silicided micron zero valent iron in example 1, based on the present invention, with conventional unsilicided ball milled iron treated sulfadimethy pyrimidine.
Figure 4 is a comparison of the performance of dichlorophenol treated with different micrometer zero valent iron-silicided persulfate salts in example 2 according to the present invention.
Detailed Description
The invention is further described below with reference to the figures and examples.
The invention provides a water body restoration method based on zero-valent iron silicide activated persulfate, which aims to solve the defects of easy inactivation, poor cycle performance and secondary pollutant dissolution in the existing iron-based activated persulfate technology and is applied to restoration and treatment of organic pollutants in water bodies.
The technical principle of the invention is based on the heterogeneous phase persulfate activation technology of zero-valent iron, and the problems that the reaction rate cannot be controlled in a homogeneous phase ferrous activation persulfate system, the rapid hydrolysis and precipitation of iron ions, the introduction of anions capable of quenching free radicals, secondary pollution caused by iron-containing sludge and the like can be relieved. However, the activation technology based on zero-valent iron still has the problem that the oxidation layer formed on the surface of the oxidized zero-valent iron inhibits the zero-valent iron from continuously releasing ferrous iron, so that the catalytic activity of the system is reduced. According to the method, silicate modified zero-valent iron is used as an activating agent, and the efficiency of activating persulfate to generate free radicals is doubly enhanced based on the characteristics that the surface property and the electron supply capacity of micron zero-valent iron can be changed after silicification, and the release of ferrous ions can be promoted by the corrosion galvanic cell effect formed by a surface silicification layer in a solution. The generated sulfate radical with strong oxidizing property and the hydroxyl radical generated by the reaction of the sulfate radical and the water can realize the non-selective mineralization and decomposition of organic pollution. Because the silicified oxidation shell layer has the capability of coordinating iron ions and better supplying electrons, Fe (III) ions generated in the degradation reaction process can be reduced into Fe (II) at the interface of the silicified oxidation shell layer, and the repair efficiency is improved.
The technical scheme provided by the invention is as follows:
the method comprises the steps of preparing micrometer zero-valent iron silicide by ball milling silicate and micrometer iron powder, treating organic wastewater by using the micrometer zero-valent iron silicide as a catalytic activator and persulfate as an oxidant, wherein the molar ratio of the activator to the oxidant is 1: 0.5-3.
The silicate is soluble silicate or layered crystalline silicate, such as sodium/potassium silicate, and various combinations of layered crystalline sodium/potassium silicates of different moduli.
The micron iron powder is reduced iron powder, raw iron powder, foam iron powder, iron filings and the like, and the particle size range is 800 meshes in 100-mesh and preferably 400 meshes in 200-mesh.
The mixing proportion of the ball milling raw materials is 0.02-20% of iron powder (calculated by iron) by mol (calculated by silicon) of soluble silicate, and is preferably 1-10%.
The ball milling can adopt planetary ball milling equipment, and the ball milling rotating speed is 300-; the ball milling time is 2-20h, preferably 4-10 h.
The zero-valent iron silicide has the key characteristic that the surface interface is rich in silanol groups.
The persulfate can be one or a mixture of more of potassium peroxymonosulfate, sodium peroxymonosulfate, ammonium peroxymonosulfate, potassium persulfate, sodium persulfate or ammonium persulfate.
The mol ratio of the activating agent to the oxidant is 1:0.5-3, preferably 1:1.5-2.1, and the pH value of the organic wastewater treatment system is controlled to be 3-10.
The organic wastewater comprises but is not limited to chlorinated organic matters, antibiotics, polycyclic aromatic hydrocarbons and other organic polluted water bodies.
Example 1
Mixing 10 g of reduced micron iron powder and 0.64g of layered sodium disilicate, placing the mixture into a ball milling tank, ball milling for 4 hours in a vacuum environment, wherein the ball milling speed is 550rpm/min, and preparing unsilicided ball milling iron (mZVI) by the same ball milling methodBM) For comparison, washing and drying. Performing X-ray photoelectron spectroscopy and infrared spectroscopy analysis on the chemical compositions of the two surfaces (shown in FIG. 1 and FIG. 2), and analyzing Si-mZVIBMSignificant silicon content was present at the surface interface.
100mL of simulated antibiotic (sulfadimidine) polluted water with the concentration of 10mg/L is taken as a restoration object, and 0.02g of the prepared ball mill iron and 1.5mM sodium persulfate are added into the water. Shaking table reaction at 200rpm/min under constant temperature, periodically sampling, and measuring sulfadimidine content by high performance liquid chromatography, with the result shown in FIG. 3. After reacting for 32min, the removal rate of sulfamethazine in a zero-valent iron system subjected to silicification ball milling treatment reaches 100%, the removal rate of hexavalent chromium in an iron grinding system without silicification balls is less than 20%, and only a small amount of persulfate and iron silicide are removed.
Example 2
Taking 10 g of reduced micron iron powder, respectively adding 0 g, 0.16 g, 0.33 g, 0.66 g, 1 g and 2.6g of sodium silicate, mixing, placing in a ball milling tank, ball milling for 5 hours in a vacuum environment, wherein the ball milling speed is 550rpm/min, washing and drying, respectively marking as mZVIBM、1#Si-mZVIBM、2#Si-mZVIBM、3#Si-mZVIBM、4#Si-mZVIBMAnd 5# Si-mZVIBM。
Using 100mL of simulated dichlorophenol polluted water with the concentration of 10mg/L as a restoration object, adding 0.03g of the prepared ball-milled iron sample and 2mM potassium persulfate into the water, carrying out table shaking reaction at the rotation speed of 200rpm/min under a constant temperature condition, and measuring the content of dichlorophenol by using a liquid phase after sampling periodically, wherein the result is shown in figure 4. After 60min of reaction, 4# Si-mZVIBMAnd 5# Si-mZVIBMThe removal rate of the dichlorophenol reaches 95 percent, and 2# Si-mZVIBM、3#Si-mZVIBMThe removal efficiency of the activated persulfate to dichlorophenol is lower, and the removal of dichlorophenol by all the silicified zero-valent iron activated persulfate systems is stronger than that of non-silicified ball milling iron mZVIBM。
Claims (5)
1. A water body restoration method based on zero-valent iron silicide activated persulfate comprises the following steps: treating organic wastewater by using micrometer zero-valent iron silicide as a catalytic activator and persulfate as an oxidant, wherein the molar ratio of the catalytic activator to the oxidant is 1: 0.5-3;
the micron zero-valent iron silicide is prepared by mixing soluble silicate and micron iron powder according to the mol ratio of silicon to iron of 0.02-20%, and then respectively performing ball milling, separation and drying;
the ball milling process is to ball mill for 2-20h at the rotating speed of 300-;
the organic wastewater comprises organic polluted water bodies of chlorinated organic matters, antibiotics and polycyclic aromatic hydrocarbons.
2. The method for remediating water as defined in claim 1, wherein the soluble silicate is one or more of sodium silicate, potassium metasilicate, layered crystalline sodium disilicate, layered crystalline potassium disilicate, and layered crystalline complex silicates.
3. The water restoration method as claimed in claim 1, wherein the micron iron powder is micron-sized reduced iron powder, raw iron powder, foam iron powder and/or iron filings, and the particle size of the iron powder is 100-800 mesh.
4. The method for restoring a water body according to claim 1, wherein the persulfate is potassium monopersulfate, sodium monopersulfate, ammonium monopersulfate, potassium persulfate, sodium persulfate, and/or ammonium persulfate.
5. The method for remediating a water body as claimed in claim 1, wherein the pH of the organic wastewater treatment system is controlled to 3 to 10.
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| CN202011112107.7A CN112320919B (en) | 2020-10-16 | 2020-10-16 | Water body restoration method based on zero-valent iron silicide activated persulfate |
| US17/451,151 US11850664B2 (en) | 2020-10-16 | 2021-10-15 | Silicified modified zero-valent iron and its preparation method and application |
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| CN113480030B (en) * | 2021-04-30 | 2022-12-06 | 中南大学 | Method for removing hexavalent chromium and/or organic matters |
| CN113880219A (en) * | 2021-10-27 | 2022-01-04 | 武汉理工大学 | Method for degrading organic dye wastewater through photo-assisted carbide slag ferrosilicon catalysis |
| CN114291992B (en) * | 2021-12-29 | 2022-07-19 | 华中师范大学 | Preparation combination for removing municipal sludge antibiotic resistance genes and application |
| CN114735799A (en) * | 2022-03-03 | 2022-07-12 | 浙江工业大学 | Sodium silicate modified zero-valent iron composite material and preparation method and application thereof |
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| CN102633349A (en) * | 2011-12-16 | 2012-08-15 | 华南理工大学 | Method for treating track non-degradable organisms in water by aid of heterogenous sulfate radical oxidation |
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| US9577257B2 (en) * | 2013-09-18 | 2017-02-21 | Guiqing Huang | Methods of making low cost electrode active materials for secondary batteries from ilmenite |
| CN105198067A (en) * | 2015-09-30 | 2015-12-30 | 中山大学 | Method for treating water by using zero-valent iron-nickel bi-metal activated persulfate |
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| CN102633349A (en) * | 2011-12-16 | 2012-08-15 | 华南理工大学 | Method for treating track non-degradable organisms in water by aid of heterogenous sulfate radical oxidation |
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| CN110589951A (en) * | 2019-09-19 | 2019-12-20 | 大连理工大学 | Method for degrading polycyclic aromatic hydrocarbon by activating persulfate through zero-valent iron |
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