CN114409028B - Three-dimensional particle electrode for wastewater treatment and preparation method thereof - Google Patents
Three-dimensional particle electrode for wastewater treatment and preparation method thereof Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 84
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 238000005470 impregnation Methods 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 229910052709 silver Inorganic materials 0.000 claims description 16
- 229910052684 Cerium Inorganic materials 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 229910052718 tin Inorganic materials 0.000 claims description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 14
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 abstract 2
- 229910000420 cerium oxide Inorganic materials 0.000 abstract 1
- 229910000480 nickel oxide Inorganic materials 0.000 abstract 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract 1
- 229910001923 silver oxide Inorganic materials 0.000 abstract 1
- 229910001887 tin oxide Inorganic materials 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 16
- 239000012847 fine chemical Substances 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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
- C02F1/46—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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F2001/46133—Electrodes characterised by the material
-
- 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
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a three-dimensional particle electrode for wastewater treatment and a preparation method thereof. The three-dimensional particle electrode consists of columnar active carbon, tin oxide, cerium oxide, nickel oxide and silver oxide. The preparation method comprises the following steps: the preparation method comprises the steps of pretreatment of columnar activated carbon, preparation of tin dioxide sol, preparation of metal salt solution, impregnation, drying and roasting, and thus the three-dimensional particle electrode for wastewater treatment is obtained. The three-dimensional particle electrode prepared by the invention has the characteristics of stable property, high catalytic activity, long service life and the like, and is simple in process and easy to popularize and use.
Description
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to a three-dimensional particle electrode for wastewater treatment and a preparation method thereof. The three-dimensional particle electrode can be used for removing organic pollutants in wastewater.
Background
In recent years, electrocatalytic technology has been widely used in the field of wastewater treatment. The technique utilizes the oxidation reaction of anode and OH and ClO generated in the experimental process - And HClO and other active oxidizing substances directly and indirectly degrade pollutants in the wastewater. Electric powerThe catalytic oxidation technology has the advantages of simple operation, mild reaction condition, no secondary pollution and the like, has excellent degradation capability in the aspect of treating the difficult-degradation wastewater, and becomes a research hot spot in the field of sewage treatment. The traditional two-dimensional plate electrode has the defects of small surface-to-body ratio, high power consumption, low current efficiency, low mass transfer rate and the like, so the three-dimensional electrode is generated. The three-dimensional electrode requires that a particulate or scrap-like electrode material is filled between the electrodes. The particles become polarized during the energizing process and charge their surfaces, causing chemical reactions to occur on their surfaces. The particle electrodes can increase the surface-to-body ratio of the three-dimensional electrode, and the mass transfer process of substances is greatly improved due to smaller spacing between the particle electrodes, so that the electrocatalytic efficiency is further improved while the reaction rate is accelerated. Therefore, it is necessary to modify the structure of the three-dimensional electrode reactor or to study the particle electrode having higher catalytic activity.
The activated carbon has higher specific surface area, is one of the most effective adsorbents at present, and the adsorbed organic matters can be oxidized and degraded under the action of an electric field. When pure activated carbon is directly used as a particle electrode, the defects of low catalytic activity, poor stability, low current utilization efficiency and the like exist, so that the efficient and stable catalytic particle electrode needs to be developed.
Disclosure of Invention
The invention aims to solve the problems of the particle electrode, and provides a three-dimensional particle electrode for wastewater treatment and a preparation method thereof, which have the characteristics of high catalytic activity, strong stability, simple preparation method and the like.
The technical scheme adopted by the invention is as follows: the preparation method of the three-dimensional particle electrode for wastewater treatment comprises the following steps of:
(1) Pretreatment of columnar activated carbon: firstly, removing impurities such as ash and the like from columnar activated carbon through acid and alkali treatment, washing with deionized water, and drying to obtain activated carbon particles;
(2) Preparation of tin dioxide solThe preparation method comprises the following steps: dissolving tin tetrachloride and citric acid in deionized water according to a molar ratio of 3-6:1, stirring for 20-40 min at 40-60 ℃, then dropwise adding ammonia water solution until the pH value is 2-4, stirring until the reaction is finished, and standing overnight; removing the supernatant of the reactant, and dripping 0.1-0.5mol.L to the white precipitate -1 Dissolving oxalic acid, uniformly stirring at 35-45 ℃, dropwise adding oxalic acid until the pH value is 1.0-2.0, stopping dropwise adding, and continuously stirring until the reaction is finished to obtain tin dioxide sol;
(3) Preparation of metal salt solution: adding nitrate of cerium, nickel and silver into deionized water to obtain a metal salt impregnating solution; the molar ratio of cerium to nickel to silver is 2:2-5:5-8;
(4) Preparation of three-dimensional particle electrode: adding the activated carbon obtained in the step (1) into the tin dioxide sol obtained in the step (2), vibrating and impregnating for 3-6 hours in a shaking table, drying for 4-6 hours at 80-90 ℃, and roasting at 200-250 ℃ to obtain activated carbon particles loaded with middle-layer tin;
(5) Adding the active carbon particles loaded with the intermediate layer tin obtained in the step (4) into the metal salt impregnating solution obtained in the step (3), carrying out vibration impregnation for 3-6 h, and drying for 4-6 h at 80-100 ℃ to obtain active carbon particles loaded with active metals; finally, the three-dimensional particle electrode for wastewater treatment is obtained by temperature programming roasting under the protection of inert gas.
The invention also provides a three-dimensional particle electrode prepared by the preparation method, which is an AC/Sn/Ce-Ni-Ag three-dimensional particle electrode taking active carbon as a carrier and loaded with a tin intermediate layer, cerium, nickel and silver active layers.
The three-dimensional particle electrode for wastewater treatment and the preparation method thereof provided by the invention are characterized in that the method is characterized in that after impregnation, moisture is evaporated and escaped, salts of active components can be reserved on the inner surface of columnar active carbon, the metal salts are uniformly distributed in pores of a carrier, and the three-dimensional particle electrode is obtained after thermal decomposition and activation. The three-dimensional particle electrode prepared according to the preparation method has the advantages of simple operation, good stability and the like, has a good removal effect on COD in fine chemical wastewater, and is low in energy consumption.
Detailed Description
The present invention will be described in detail with reference to specific examples, but the examples do not limit the scope of the present invention.
Examples 1 to 4 are preparation of three-dimensional particle electrodes for wastewater treatment, example 5 is performance evaluation of the three-dimensional particle electrodes prepared in examples 1 to 4, and examples 6 to 8 are stability test of the prepared three-dimensional particle electrodes and advantages over the conventional preparation method.
Example 1
(1) Pretreatment of columnar activated carbon: firstly, columnar activated carbon is treated by acid and alkali to remove impurities such as ash and the like. And washing with deionized water and drying to obtain the activated carbon particles.
(2) Preparation of tin dioxide sol: 10.01g of tin tetrachloride and 1.0g of citric acid were added to 500mL of deionized water for dissolution, stirred at 40℃for 30 minutes, followed by dropwise addition of an aqueous ammonia solution to a pH of 2.03, stirred until the reaction was completed, and left standing overnight. The supernatant of the reaction was removed, and 0.15 mol.L was added dropwise to the white precipitate -1 Dissolving oxalic acid, stirring uniformly at 40 ℃, then dripping oxalic acid until the pH value is 1.01, stopping dripping, and continuing stirring until the reaction is finished to obtain the tin dioxide sol.
(3) Preparation of metal salt solution: nitrate of cerium, nickel and silver (molar ratio of cerium, nickel and silver is 2:3:5) was added to deionized water to obtain a metal salt impregnation solution.
(4) Preparation of three-dimensional particle electrode: adding the activated carbon obtained in the step (1) into the tin dioxide sol obtained in the step (2), vibrating and impregnating for 3 hours in a shaking table, drying for 5 hours at 83 ℃, and roasting at 210 ℃ to obtain activated carbon particles loaded with intermediate layer tin.
(5) Adding the active carbon particles loaded with the interlayer tin obtained in the step (4) into the metal salt impregnating solution obtained in the step (3), carrying out vibration impregnation for 3h, and drying for 6h at 80 ℃ to obtain active carbon particles loaded with active metals; finally, the three-dimensional particle electrode I for wastewater treatment is obtained by temperature programming roasting under the protection of inert gas.
Example 2
(1) Pretreatment of columnar activated carbon: firstly, treating columnar activated carbon by acid and alkali, removing impurities such as ash and the like, washing with deionized water, and drying to obtain activated carbon particles.
(2) Preparation of tin dioxide sol: 13.12g of tin tetrachloride and 1.13g of citric acid were added to 500mL of deionized water for dissolution, stirred at 40℃for 30 minutes, followed by dropwise addition of an aqueous ammonia solution until the pH was 2.56, stirred until the reaction was completed, and left standing overnight. The supernatant of the reaction was removed, and 0.2 mol.L was added dropwise to the white precipitate -1 Dissolving oxalic acid, stirring uniformly at 40 ℃, then dripping oxalic acid until the pH value is 1.31, stopping dripping, and continuing stirring until the reaction is finished to obtain the tin dioxide sol.
(3) Preparation of metal salt solution: nitrate of cerium, nickel and silver (molar ratio of cerium, nickel and silver is 2:3:7) was added to deionized water to obtain a metal salt impregnation solution.
(4) Preparation of three-dimensional particle electrode: adding the activated carbon obtained in the step (1) into the tin dioxide sol obtained in the step (2), vibrating and impregnating for 3 hours in a shaking table, drying for 6 hours at 80 ℃, and roasting at 205 ℃ to obtain activated carbon particles loaded with intermediate layer tin.
(5) Adding the active carbon particles loaded with the interlayer tin obtained in the step (4) into the metal salt impregnating solution obtained in the step (3), carrying out vibration impregnation for 3h, and drying for 5h at 90 ℃ to obtain active carbon particles loaded with active metals; finally, the three-dimensional particle electrode II for wastewater treatment is obtained by temperature programming roasting under the protection of inert gas.
Example 3
(1) Pretreatment of columnar activated carbon: firstly, treating columnar activated carbon by acid and alkali, removing impurities such as ash and the like, washing with deionized water, and drying to obtain activated carbon particles.
(2) Preparation of tin dioxide sol: 14.98g of stannic chloride and 1.49g of citric acid are added into 500mL of deionized water for dissolution, stirred for 30min at 40 ℃, then ammonia water solution is added dropwise until the pH is 3.68, the stirring is carried out until the reaction is finished, and the mixture is left standAnd (5) at night. The supernatant of the reaction was removed, and 0.25 mol.L was added dropwise to the white precipitate -1 Dissolving oxalic acid, stirring uniformly at 40 ℃, then dripping oxalic acid until the pH value is 1.81, stopping dripping, and continuing stirring until the reaction is finished to obtain the tin dioxide sol.
(3) Preparation of metal salt solution: nitrate of cerium, nickel and silver (molar ratio of cerium, nickel and silver is 2:4:7) was added to deionized water to obtain a metal salt impregnation solution.
(4) Preparation of three-dimensional particle electrode: adding the activated carbon obtained in the step (1) into the tin dioxide sol obtained in the step (2), vibrating and impregnating for 5 hours in a shaking table, drying for 4 hours at 90 ℃, and roasting at 250 ℃ to obtain activated carbon particles loaded with intermediate layer tin.
(5) Adding the active carbon particles loaded with the interlayer tin obtained in the step (4) into the metal salt impregnating solution obtained in the step (3), vibrating and impregnating for 5 hours, and drying for 5 hours at 90 ℃ to obtain active carbon particles loaded with active metals; finally, the three-dimensional particle electrode III for wastewater treatment is obtained by temperature programming roasting under the protection of inert gas.
Example 4
(1) Pretreatment of columnar activated carbon: firstly, treating columnar activated carbon by acid and alkali, removing impurities such as ash and the like, washing with deionized water, and drying to obtain activated carbon particles.
(2) Preparation of tin dioxide sol: 13.12g of tin tetrachloride and 1.48g of citric acid were added to 500mL of deionized water for dissolution, stirred at 40℃for 30 minutes, followed by dropwise addition of an aqueous ammonia solution until the pH was 3.96, stirred until the reaction was completed, and left standing overnight. The supernatant of the reaction was removed, and 0.50mol.L was added dropwise to the white precipitate -1 Dissolving oxalic acid, stirring uniformly at 40 ℃, then dripping oxalic acid until the pH value is 2.0, stopping dripping, and continuing stirring until the reaction is finished to obtain the tin dioxide sol.
(3) Preparation of metal salt solution: nitrate of cerium, nickel and silver (molar ratio of cerium, nickel and silver is 2:4:8) was added to deionized water to obtain a metal salt impregnation solution.
(4) Preparation of three-dimensional particle electrode: adding the activated carbon obtained in the step (1) into the tin dioxide sol obtained in the step (2), vibrating and impregnating for 6 hours in a shaking table, drying for 5 hours at the temperature of 85 ℃, and roasting at the temperature of 250 ℃ to obtain activated carbon particles loaded with intermediate layer tin.
(5) Adding the active carbon particles loaded with the interlayer tin obtained in the step (4) into the metal salt impregnating solution obtained in the step (3), vibrating and impregnating for 5 hours, and drying for 5 hours at 90 ℃ to obtain active carbon particles loaded with active metals; finally, the three-dimensional particle electrode IV for wastewater treatment is obtained by temperature programming roasting under the protection of inert gas.
Example 5
A three-dimensional electro-catalytic system is constructed by taking fine chemical wastewater of Shenzhen market as a treatment object and a DSA electrode as a working electrode and the particle electrodes prepared in the embodiments 1-4 of the invention, and an evaluation test is carried out in an organic glass electrolytic cell. Wherein the volume of the wastewater is 500mL, the current value is 5A, the voltage value is 2.9V, and the COD of the inflow water is 560 mg.L -1 The pH value is 7.23, and the ammonia nitrogen value and COD of the wastewater are measured after electrocatalytic degradation is carried out for 45min. Which is shown in table 1.
Table 1 results of evaluation of three-dimensional particle electrode properties
| Examples | 1 | 2 | 3 | 4 |
| COD removal Rate (%) | 85.65 | 86.34 | 91.12 | 88.23 |
And (3) constructing a two-dimensional electrode system by taking the DSA electrode as a working electrode, and carrying out an electrocatalytic degradation experiment on the fine chemical wastewater under the same condition, wherein the COD removal rate of the wastewater after 45min is only 18.32%. Therefore, the three-dimensional particle electrode for wastewater treatment prepared by the invention has higher catalytic efficiency.
Example 6
In contrast, the active metal loaded AC/Sn-Ce-Ni-Ag and AC/Ce-Ni-Ag particle electrodes were obtained using a one-step dipping method. Respectively preparing Sn, ce, ni, ag salt solution and Ce, ni and Ag salt solution, soaking, drying and roasting to obtain two particle electrodes.
Example 7
The AC/Sn/Ce-Ni-Ag in the embodiment 3, the AC/Sn-Ce-Ni-Ag and the AC/Ce-Ni-Ag in the embodiment 6 are respectively used as particle electrodes for treating fine chemical wastewater by electrocatalytic treatment. And (3) performing electrocatalytic treatment on 500mL of fine chemical wastewater by taking the DSA electrode as a working electrode, and treating for 45min under the condition that the current value is 5A. The COD removal rates of the fine chemical wastewater under the three systems are measured to be 91.12%, 60.53% and 50.29%, respectively. Therefore, the three-dimensional particle electrode for wastewater treatment prepared by the method has higher catalytic efficiency than the traditional dipping method.
Example 8
Stability test of three-dimensional particle electrode for wastewater treatment:
a three-dimensional electrocatalytic system is constructed by taking a DSA electrode as a working electrode and an AC/Sn/Ce-Ni-Ag particle electrode prepared in the embodiment 3 of the invention, 500mL of fine chemical wastewater is subjected to electrocatalytic treatment, the wastewater is filtered after being treated for 45min under the condition that the current value is 5A, and the obtained precipitate is washed and dried, and is repeatedly subjected to 5 times of electrocatalytic tests under the same condition. The COD removal rate of the wastewater is measured to be as follows: 91.12%, 88.13%, 86.89%, 83.11% and 82.56%. Similarly, the three-dimensional electro-catalytic system with the AC/Ce-Ni-Ag as the particle electrode has the COD removal rates of the fine chemical wastewater of five times continuously as follows: 50.29%, 46.92%, 42.36%, 33.18% and 20.89%. Therefore, the three-dimensional particle electrode for wastewater treatment prepared by the invention has higher stability and can be reused. And compared with the particle electrode prepared by the traditional method, the particle electrode has better stability.
Claims (2)
1. The preparation method of the three-dimensional particle electrode for wastewater treatment is characterized in that the three-dimensional particle electrode is prepared by the following steps:
(1) Pretreatment of columnar activated carbon: firstly, treating columnar activated carbon by acid and alkali, removing impurities, washing with deionized water, and drying to obtain activated carbon particles;
(2) Preparation of tin dioxide sol: dissolving tin tetrachloride and citric acid in deionized water according to a molar ratio of 3-6:1, stirring at 40-60 ℃ for 20-40 min, then dropwise adding an ammonia water solution until the pH value is 2-4, stirring until the reaction is finished, and standing overnight; removing the supernatant of the reactant, and dripping 0.1-0.5 mol.L to the white precipitate -1 Dissolving oxalic acid, uniformly stirring at 35-45 ℃, dropwise adding oxalic acid until the pH value is 1.0-2.0, stopping dropwise adding, and continuously stirring until the reaction is finished to obtain tin dioxide sol;
(3) Preparation of metal salt solution: adding nitrate of cerium, nickel and silver into deionized water to obtain a metal salt impregnating solution; the molar ratio of cerium to nickel to silver is 2:2-5:5-8;
(4) Preparation of three-dimensional particle electrode: adding the activated carbon obtained in the step (1) into the tin dioxide sol obtained in the step (2), vibrating and impregnating for 3-6 hours in a shaking table, drying for 4-6 hours at 80-90 ℃, and roasting at 200-250 ℃ to obtain activated carbon particles loaded with intermediate layer tin;
(5) Adding the activated carbon particles loaded with the interlayer tin obtained in the step (4) into the metal salt impregnating solution obtained in the step (3), carrying out vibration impregnation for 3-6 h, and drying for 4-6 h at 80-100 ℃ to obtain activated carbon particles loaded with the activated metal; and finally, placing the electrode under the protection of inert gas, and performing temperature programming roasting to obtain the three-dimensional particle electrode for wastewater treatment.
2. The three-dimensional particle electrode prepared by the preparation method of claim 1, wherein the three-dimensional particle electrode is an AC/Sn/Ce-Ni-Ag three-dimensional particle electrode taking columnar active carbon as a carrier and carrying a tin interlayer, cerium, nickel and silver active layers.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210116199.9A CN114409028B (en) | 2022-02-11 | 2022-02-11 | Three-dimensional particle electrode for wastewater treatment and preparation method thereof |
| PCT/CN2023/071228 WO2023151437A1 (en) | 2022-02-11 | 2023-01-09 | Three-dimensional particle electrode, preparation method therefor, and use thereof |
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| KR20100027454A (en) * | 2008-09-02 | 2010-03-11 | 한양대학교 산학협력단 | Method for fabricating tin dioxide nano sol and porous composite using the same |
| CN105198048A (en) * | 2015-10-27 | 2015-12-30 | 雅本化学股份有限公司 | Three-dimensional electrode filling material and preparation method thereof |
| CN108726640A (en) * | 2017-04-20 | 2018-11-02 | 华中科技大学 | A kind of method of electrochemistry collaboration persulfate removal Organic Pollutants in Wastewater |
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| US9012073B2 (en) * | 2008-11-11 | 2015-04-21 | Envia Systems, Inc. | Composite compositions, negative electrodes with composite compositions and corresponding batteries |
| DE202011106025U1 (en) * | 2011-08-14 | 2012-08-17 | BLüCHER GMBH | Activated carbon with metal-based component |
| CN103539226B (en) * | 2013-10-30 | 2015-03-11 | 北京师范大学 | Multi-dimensional electrode electrocatalysis device for removing various persistent organic pollutants |
| CN103539225B (en) * | 2013-10-30 | 2014-12-10 | 北京师范大学 | Internal-circulating fluidized bed electro-catalytic reactor for treating chemical organic wastewater and operation conditions of reactor |
| CN103539229B (en) * | 2013-10-30 | 2015-01-28 | 北京师范大学 | Particle electrode for efficiently removing various organic compounds and preparation method thereof |
| CN104925913B (en) * | 2015-06-18 | 2017-12-08 | 北京林业大学 | For removing catalyst particle electrode of hardly degraded organic substance and ammonia nitrogen and its preparation method and application in decontamination sewage |
| CN107188273A (en) * | 2017-04-27 | 2017-09-22 | 华中科技大学 | A kind of preparation method of three-dimensional carbon metal oxides electro catalytic electrode |
| CN109775813B (en) * | 2019-03-13 | 2021-10-26 | 西安建筑科技大学 | Composite intermediate layer for titanium-based oxide electrode, titanium-based oxide electrode and preparation method thereof |
| CN114409028B (en) * | 2022-02-11 | 2024-04-16 | 中海油天津化工研究设计院有限公司 | Three-dimensional particle electrode for wastewater treatment and preparation method thereof |
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| CN105198048A (en) * | 2015-10-27 | 2015-12-30 | 雅本化学股份有限公司 | Three-dimensional electrode filling material and preparation method thereof |
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