CN113264575A - Electrochemical coupling granulation ZVI/Fe3O4Method for removing Cr (VI) in underground water by using AC material - Google Patents
Electrochemical coupling granulation ZVI/Fe3O4Method for removing Cr (VI) in underground water by using AC material Download PDFInfo
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
-
- 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
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4616—Power supply
- C02F2201/4617—DC only
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- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses electrochemical coupling granulation ZVI/Fe3O4The method for removing Cr (VI) in underground water by using/AC material includes uniformly mixing reduced iron powder and active carbon, placing the mixture into a ball milling tank, adding zirconia balls, introducing high-purity argon into the tank, placing the tank into a ball mill for ball milling to obtain ZVI/AC material, carrying out acid treatment on the collected ball-milled material, drying, and calcining in a tubular high-temperature sintering furnace to obtain ZVI/Fe3O4a/AC composite material; ZVI/Fe prepared by ball milling-calcining method3O4the/AC composite material is used as a filling medium of the permeable reactive wall reactor and is coupled with an electrodynamic system to establish the coordination of the PRB-electrodynamic systemThe system can efficiently remove Cr (VI) in the groundwater. The invention utilizes electrochemical coupling granulation ZVI/Fe3O4The effect of the/AC material on removing Cr (VI) in underground water is obvious.
Description
Technical Field
The invention belongs to the technical field of treatment methods of heavy metal pollutants in water, and particularly relates to electrochemical coupling granulation ZVI/Fe3O4Method for removing Cr (VI) in underground water by using AC material.
Background
In recent years, with the continuous development of industrial modernization, the industrial processes of fuel, electroplating, mining, smelting and the like are further accelerated. In the process of the industrial progress, a large amount of discharged heavy metal wastewater becomes an important pollution source of environmental problems, wherein the pollution of harmful heavy metal chromium is the most prominent, and the phenomenon that the content of chromium in underground water in many areas of China exceeds the standard exists. Chromium and chromium compounds are listed as environmental priority pollutants and are often detected in various industrial wastewater of electroplating, wood preservation, leather tanning, paint and pigment production and the like, the chromium-containing wastewater generated in large-scale production activities of the industries has extremely high toxicity, and once underground water is polluted by the chromium wastewater, the ecological balance and the human health are seriously threatened.
The zero-valent iron is widely applied to the field of environmental pollution restoration due to the characteristics of small particles, large specific surface area, high reaction activity and the like. However, the zero-valent iron is easily passivated and agglomerated, so that the application of the zero-valent iron in practical application is limited. The iron-carbon micro-electrolysis is a water treatment technology with high efficiency, strong universality, low energy consumption and low cost, can improve the biodegradability of refractory pollutants, and has wide application prospect. Zero-valent iron and Fe (II) which can produce main substances of reducing Cr (VI) in the micro-electrolysis process3O4The redox sites on the surface are favorable for the transmission of electrons, and Fe is realized3+And Fe2+The reaction cycle of (2). The existence of the external electric field provides a favorable environment for the continuous transfer of electrons, and the redox reaction is maintained to be carried out by the synergistic system.
Permeable Reactive Barrier (PRB) is one of the innovative technologies for in-situ remediation of polluted groundwater, and is also the most mature in-situ remediation technology at present. The implementation of PRBs refers to the embedding of a reactive medium in a direction perpendicular to the flow direction of contaminated groundwater for intercepting and converting the contaminants into less harmful compounds or immobilizing them in a reactive medium by a physicochemical reaction. The invention adopts a mechanical ball milling-calcining method to prepare the granulated ZVI/Fe3O4Filling medium of permeable reactive wall reactor made of/AC materialAnd the PRB-electrodynamic force system is established by coupling the electric power system to efficiently remove Cr (VI) in the underground water.
Disclosure of Invention
The invention solves the technical problem of providing the electrochemical coupling granulation ZVI/Fe3O4Method for removing Cr (VI) in groundwater by AC material, and the method can prepare granular ZVI/Fe with good stability in large quantity3O4a/AC composite material, and preparation of ZVI/Fe3O4the/AC composite material has lower cost and excellent performance of treating Cr (VI) in underground water.
The invention adopts the following technical scheme to solve the technical problems, namely, electrochemically coupled granulated ZVI/Fe3O4The method for removing Cr (VI) in underground water by using the/AC material is characterized by comprising the following specific steps:
step S1: uniformly mixing reduced iron powder with the average particle size of 45 mu m and active carbon according to the mass ratio of 2:1, pouring the mixture into a ball milling tank, adding zirconia grinding balls, and performing intermittent alternate positive and negative rotation ball milling for 8 hours under the mechanical ball milling condition with the rotation speed of 375r/min to obtain a ball milling mixture;
step S2: washing the ball-milling mixture obtained in the step S1 with ethanol, immersing the ball-milling mixture into a nitric acid solution with the mass concentration of 5%, mechanically stirring for 40min, washing the ball-milling mixture to be neutral with pure water, drying for 2h with a vacuum drying oven, and calcining for 30min at 300 ℃ in a tubular furnace to obtain ZVI/Fe3O4a/AC composite material;
step S3: ZVI/Fe obtained in step S23O4Dispersing the/AC composite material in ethanol, then placing the mixture in a water bath at 70 ℃, dropwise adding 2mL of polytetrafluoroethylene concentrated dispersion liquid with the mass concentration of 60% as a binder, mechanically stirring while dropwise adding until the material is pasty, transferring the material into a cylindrical mold with the diameter of 5mm, and cutting the cylindrical mold into cylindrical particles with the length of 2mm after cooling and forming;
step S4: uniformly mixing the cylindrical particles obtained in the step S3 with standard sand in a mass ratio of 1:5, filling a PRB reaction column, filling the standard sand at two ends of the column respectively, embedding two parallel graphite electrode plates into two sides of a reaction medium at a distance of 30mm, and coupling an electrodynamic force system to establish a synergistic system of the PRB-electrodynamic force system so as to efficiently remove Cr (VI) in underground water.
Further defined, the mass ratio of the zirconia grinding balls to the mixture in step S1 is 35:1, wherein the zirconia grinding balls comprise zirconia grinding balls with a diameter of 1.1mm and zirconia grinding balls with a diameter of 5mm in a mass ratio of 1: 3.
Further, in the step S1, the process of intermittent alternate forward and reverse ball milling is that the forward ball milling is performed for 10min and the intermittent stop is performed for 5S, and then the reverse ball milling is performed for 10min and the intermittent stop is performed for 5S, and the above steps are repeated until the cumulative ball milling time is equal to the set ball milling time.
Further limiting, in the step S2, N is introduced into the calcined product2The protective gas is used for preventing the material from being oxidized in the calcining process, the calcining temperature rise program is to heat the material from room temperature to 300 ℃ at the temperature rise rate of 2 ℃/min, keep the temperature for 30min, and then cool the material to the room temperature at the same temperature drop rate.
Further limiting, the height of the PRB reaction column in the step S4 is 180mm, the diameter is 35mm, two parallel graphite electrode plates are embedded into two sides of the reaction medium at a distance of 30mm to provide direct current power, and before each experiment, the electrode plates are soaked in dilute nitric acid solution to be cleaned.
Compared with the prior art, the invention has the following beneficial effects: the invention prepares the ZVI/Fe by a mechanical ball milling-calcining method3O4The material/AC is granulated, has simple process and low cost, and can prepare ZVI/Fe with large yield3O4Granulating composite material with/AC, coupling electrochemistry with ZVI/Fe3O4the/AC granulated composite material is rarely applied to the environment, and has excellent performance when being used for treating heavy metal pollutants in water.
Drawings
FIG. 1 is ZVI/Fe obtained in example 13O4XRD pattern of/AC material;
FIG. 2 is ZVI/Fe obtained in example 13O4SEM image of/AC material;
FIG. 3 is ZVI/Fe after reaction in example 43O4SEM image of/AC material.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Step S1: uniformly mixing reduced iron powder with the average particle size of 45 mu m and active carbon according to the mass ratio of 2:1, pouring the mixture into a ball milling tank, adding zirconia grinding balls, and performing intermittent alternate forward and reverse ball milling for 8 hours under the mechanical ball milling condition of the rotating speed of 375r/min to obtain a ball milling mixture, wherein the mass ratio of the zirconia grinding balls to the mixture is 35:1, the zirconia grinding balls comprise zirconia grinding balls with the diameter of 1.1mm and zirconia grinding balls with the diameter of 5mm, the mass ratio of the zirconia grinding balls to the mixture is 1:3, the intermittent alternate forward and reverse ball milling process is that forward ball milling is performed for 10min, the intermittent stop is performed for 5s, then reverse ball milling is performed for 10min, the intermittent stop is performed for 5s, and the steps are repeated until the accumulated ball milling time is equal to the set ball milling time;
step S2: washing the ball-milling mixture obtained in the step S1 with ethanol, immersing the ball-milling mixture into a nitric acid solution with the mass concentration of 5%, mechanically stirring for 40min, washing the ball-milling mixture to be neutral with pure water, drying for 2h with a vacuum drying oven, and calcining for 30min at 200-300 ℃ in a tube furnace to obtain ZVI/Fe3O4The composite material is prepared by introducing N into the composite material during calcination2As a protective gas to prevent the material from being oxidized in the calcining process, the calcining temperature-rising program is to heat the material from room temperature to 300 ℃ at the temperature-rising rate of 2 ℃/min, keep the temperature for 30min, and then cool the material to the room temperature at the same temperature-lowering rate;
step S3: ZVI/Fe obtained in step S23O4Dispersing the/AC composite material in ethanol, then placing the mixture in a water bath at 70 ℃, dropwise adding 2mL of polytetrafluoroethylene concentrated dispersion liquid with the mass concentration of 60% as a binder, mechanically stirring the mixture while dropwise adding until the material is pasty, transferring the material into a cylindrical mold with the diameter of 5mm, and cutting the cylindrical mold into cylindrical particles with the length of 2mm after cooling and forming.
The zirconia grinding balls are ground by two zirconia balls with the diameters of 1.1mm and 5mm in a matching way, and the balls are ground in a ball milling processThe mass ratio of the materials is 35:1, the ball milling tanks are required to be guaranteed before use, the tank bodies and the auxiliary devices are completely dried, and the mass of zirconia grinding balls in the four ball milling tanks is kept consistent as much as possible; pouring the ball-milling material out of the ball-milling tank, and separating the ball-milling material and the milling balls by using a magnet; as can be seen from the XRD pattern (FIG. 1), ZVI/Fe before reaction3O4Diffraction peak at 2 θ =36.5 ° for the/AC material attributed to Fe3O4And zero-valent iron appears at 2 θ =44.8 °, 65.2 °. It can be seen from the SEM image (fig. 2) that the prepared zero-valent iron and activated carbon are tightly combined, and a large degree of deformation and breakage occurs. A large number of octahedral particles adhere closely to the sheet after high temperature calcination.
Example 2
Granulating ZVI/Fe3O4The method comprises the steps of uniformly mixing an/AC material and standard sand in a mass ratio of 1:5, filling a PRB reaction column, and filling the standard sand at two ends of the column respectively. Preparing 10mg/L Cr (VI) solution from underground water as an inlet solution, pumping the inlet solution from a lower sample inlet at the flow rate of 2.4mL/min, loading 5mA micro current on a graphite electrode, and reacting at room temperature for 2000BV (15 min is needed to complete one BV). The effluent was collected periodically from the upper sampling port and analyzed for cr (vi) immediately after filtration through a 0.45 μm aqueous needle filter (polyethersulfone). The Cr (VI) removing rate is kept above 93 percent in the whole operation period, and the Cr (VI) concentration in the effluent is always less than 0.7 mg/L.
Example 3
Continuous observation of ZVI/Fe3O4the/AC-PRB-EK is filled in the column for 36 days, and the amount of treated water and the Cr (VI) concentration of discharged water are recorded every 12 hours. For the Cr (VI) polluted wastewater with the total volume of 60L, the volume of the treated water is 1.71L/12h in the first 26 days, and the removal rate of the Cr (VI) is more than 90 percent. But clogging began to occur on day 27 and the cr (vi) concentration in the effluent increased. By day 36, the effluent yield was reduced to 79.5% of the initial treatment yield, the Cr (VI) concentration was 2.6mg/L, and the removal rate was reduced to 74% of the initial removal rate. At this point the external point source was disconnected and the reaction column was then rinsed with 0.1mol/L hydrochloric acid solution for 5h and then with distilled water until the effluent was neutral. Because part of Fe-Cr solid precipitate is dissolved in acid, the porosity of the filler is increased, and the blockage situation is causedThe improvement is obtained, the water yield per 12h is 94.1% of the initial water yield, and the Cr (VI) treatment efficiency is only improved to 84.2%, which is probably that the weak acid corrosion causes the reduction of the active sites on the surface of the filler. It follows that it is necessary to periodically wash with a weak acid to maintain proper operation of the PRB-EK reactor.
Example 4
The column is dismantled, a proper amount of material is taken, nitrogen is used for drying, electron microscope scanning analysis is carried out, the surface appearance and the change of the reacted material are known, fig. 3 is an electron microscope scanning image of the reacted material, and as can be seen from the image, the surface of a reaction product is much smoother than that of the material before reaction, and a plurality of grape-shaped clusters are gathered in the reaction product.
Example 5
The improved Tessier step-by-step extraction program is used for analyzing PRB filler reaction products after 36 days of continuous operation, and the result shows that chromium mainly exists in a stable residue state, can only be leached in a strong oxidation or strong acid environment, is not easy to release into an external environment, has small influence on the environment, shows that heavy metal chromium in the PRB filler has small threat on the external environment, has low environmental risk, and ensures the relative safety of the system.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (5)
1. Electrochemical coupling granulation ZVI/Fe3O4The method for removing Cr (VI) in underground water by using the/AC material is characterized by comprising the following specific steps:
step S1: uniformly mixing reduced iron powder with the average particle size of 45 mu m and active carbon according to the mass ratio of 2:1, pouring the mixture into a ball milling tank, adding zirconia grinding balls, and performing intermittent alternate positive and negative rotation ball milling for 8 hours under the mechanical ball milling condition with the rotation speed of 375r/min to obtain a ball milling mixture;
step (ii) ofS2: washing the ball-milling mixture obtained in the step S1 with ethanol, immersing the ball-milling mixture into a nitric acid solution with the mass concentration of 5%, mechanically stirring for 40min, washing the ball-milling mixture to be neutral with pure water, drying for 2h with a vacuum drying oven, and calcining for 30min at 300 ℃ in a tubular furnace to obtain ZVI/Fe3O4a/AC composite material;
step S3: ZVI/Fe obtained in step S23O4Dispersing the/AC composite material in ethanol, then placing the mixture in a water bath at 70 ℃, dropwise adding 2mL of polytetrafluoroethylene concentrated dispersion liquid with the mass concentration of 60% as a binder, mechanically stirring while dropwise adding until the material is pasty, transferring the material into a cylindrical mold with the diameter of 5mm, and cutting the cylindrical mold into cylindrical particles with the length of 2mm after cooling and forming;
step S4: uniformly mixing the cylindrical particles obtained in the step S3 with standard sand in a mass ratio of 1:5, filling a PRB reaction column, filling the standard sand at two ends of the column respectively, embedding two parallel graphite electrode plates into two sides of a reaction medium at a distance of 30mm, and coupling an electrodynamic force system to establish a synergistic system of the PRB-electrodynamic force system so as to efficiently remove Cr (VI) in underground water.
2. The electrochemically coupled particulated ZVI/Fe of claim 13O4A method for removing Cr (VI) in underground water by using/AC material is characterized in that: in the step S1, the mass ratio of the zirconia grinding balls to the mixture is 35:1, wherein the zirconia grinding balls comprise zirconia grinding balls with the diameter of 1.1mm and zirconia grinding balls with the diameter of 5mm, and the mass ratio of the zirconia grinding balls to the mixture is 1: 3.
3. The electrochemically coupled particulated ZVI/Fe of claim 13O4A method for removing Cr (VI) in underground water by using/AC material is characterized in that: and step S1, the process of intermittent alternating forward and reverse ball milling is that the forward ball milling is carried out for 10min and the intermittent stop is carried out for 5S, then the reverse ball milling is carried out for 10min and the intermittent stop is carried out for 5S, and the steps are repeated until the cumulative ball milling time is equal to the set ball milling time.
4. The electrochemically-coupled particulated ZV of claim 1I/Fe3O4A method for removing Cr (VI) in underground water by using/AC material is characterized in that: introducing N during the calcination in the step S22The protective gas is used for preventing the material from being oxidized in the calcining process, the calcining temperature rise program is to heat the material from room temperature to 300 ℃ at the temperature rise rate of 2 ℃/min, keep the temperature for 30min, and then cool the material to the room temperature at the same temperature drop rate.
5. The electrochemically coupled particulated ZVI/Fe of claim 13O4A method for removing Cr (VI) in underground water by using/AC material is characterized in that: in the step S4, the PRB reaction column is 180mm in height and 35mm in diameter, two parallel graphite electrode plates are embedded into two sides of a reaction medium at a distance of 30mm to provide direct current power, and before each experiment, the electrode plates are soaked in a dilute nitric acid solution to be cleaned.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103862037A (en) * | 2014-02-27 | 2014-06-18 | 浙江大学 | Preparation method and preprocessing method of biomaterial-embedded zero-valent-iron-ferroferric-oxide double-nanometer system |
| CN107352555A (en) * | 2017-06-15 | 2017-11-17 | 河南师范大学 | A kind of wet type solid phase mechanical attrition method prepares Fe0The method of the composites of/ZSM 5 |
| CN108862537A (en) * | 2018-06-25 | 2018-11-23 | 河南师范大学 | Hydroxy functionalized Modified lift Fe0/Fe3O4Method of the composite material to Cr in waste water (VI) removal capacity |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103862037A (en) * | 2014-02-27 | 2014-06-18 | 浙江大学 | Preparation method and preprocessing method of biomaterial-embedded zero-valent-iron-ferroferric-oxide double-nanometer system |
| CN107352555A (en) * | 2017-06-15 | 2017-11-17 | 河南师范大学 | A kind of wet type solid phase mechanical attrition method prepares Fe0The method of the composites of/ZSM 5 |
| CN108862537A (en) * | 2018-06-25 | 2018-11-23 | 河南师范大学 | Hydroxy functionalized Modified lift Fe0/Fe3O4Method of the composite material to Cr in waste water (VI) removal capacity |
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