CN114409028A - 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 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 115
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 38
- 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 21
- 238000005470 impregnation Methods 0.000 claims abstract description 15
- 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 31
- 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
- 229910052709 silver Inorganic materials 0.000 claims description 17
- 229910052684 Cerium Inorganic materials 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 229910052718 tin Inorganic materials 0.000 claims description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 150000002823 nitrates Chemical class 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
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 2
- 229910000480 nickel oxide Inorganic materials 0.000 abstract description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001923 silver oxide Inorganic materials 0.000 abstract description 2
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 description 16
- 239000012847 fine chemical Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 210000004884 grey matter Anatomy 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011160 research 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
- 238000011161 development Methods 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
- 238000001704 evaporation Methods 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
- 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
- 239000002244 precipitate Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010944 silver (metal) Substances 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 is an AC/Sn/Ce-Ni-Ag type three-dimensional particle electrode consisting of columnar activated 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 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 the anode and OH and ClO generated in the experimental process-And active oxidizing substances such as HClO and the like directly and indirectly degrade pollutants in the wastewater. The electrocatalytic oxidation technology has the advantages of simple operation, mild reaction conditions, no secondary pollution and the like, shows excellent degradation capability in the aspect of treating refractory wastewater, and becomes a research hotspot in the field of sewage treatment. The traditional two-dimensional flat plate electrode has the defects of small surface area ratio, high power consumption, low current efficiency, low mass transfer rate and the like, so that the three-dimensional electrode is produced. Three-dimensional electrodes require that the electrodes be filled with particulate electrode material in the form of particles or swarf. During the process of energization, the particles are polarized and charged on their surfaces, which in turn causes chemical reactions on their surfaces. The particle electrodes can increase the surface area ratio of the three-dimensional electrodes, and because the distance between the particle electrodes is small, the mass transfer process of substances is greatly improved, the reaction rate is accelerated, and the electrocatalysis efficiency is further improved. Therefore, it is necessary to structurally modify a three-dimensional electrode reactor or research a particle electrode with high catalytic activity.
The active carbon has a high specific surface area, is one of the most effective adsorbents at present, and 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, and therefore, the development of a high-efficiency and stable catalytic particle electrode is urgently needed.
Disclosure of Invention
The invention aims to overcome the problems of the particle electrode and provides a three-dimensional particle electrode for wastewater treatment and a preparation method thereof, and the three-dimensional particle electrode has the characteristics of high catalytic activity, strong stability, simple preparation method and the like.
The technical scheme adopted by the invention is as follows: a preparation method of a three-dimensional particle electrode for wastewater treatment, the three-dimensional particle electrode is composed of columnar Activated Carbon (AC), tin oxide (Sn), cerium oxide (Ce), nickel oxide (Ni) and silver oxide (Ag), and the preparation method specifically comprises the following steps:
(1) pretreatment of columnar activated carbon: firstly, treating columnar activated carbon by acid and alkali to remove impurities such as gray matter, washing by deionized water and drying to obtain activated carbon particles;
(2) preparing 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 reaction product, and adding 0.1-0.5 mol/L dropwise to the white precipitate-1Dissolving the oxalic acid solution, 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 nitrates of cerium, nickel and silver into deionized water to obtain a metal salt soaking 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), shaking and dipping for 3-6 h in a shaking table, drying for 4-6 h at the temperature of 80-90 ℃, and then roasting at the temperature of 200-250 ℃ to obtain activated carbon particles loaded with intermediate layer tin;
(5) adding the activated carbon particles loaded with the middle layer tin obtained in the step (4) into the metal salt impregnation liquid obtained in the step (3), performing vibration impregnation for 3-6 hours, and drying at 80-100 ℃ for 4-6 hours to obtain activated carbon particles loaded with activated metal; and finally, carrying out temperature programming roasting under the protection of inert gas to obtain the three-dimensional particle electrode for wastewater treatment.
The invention also provides a three-dimensional particle electrode prepared by the preparation method, which is an AC/Sn/Ce-Ni-Ag type three-dimensional particle electrode taking activated carbon as a carrier and loaded with a tin intermediate layer, a cerium active layer, a nickel active layer and a silver active layer.
The three-dimensional particle electrode for wastewater treatment and the preparation method thereof provided by the invention have the advantages that the three-dimensional particle electrode for wastewater treatment is obtained by soaking, drying and evaporating moisture to escape, so that the salts of active components can be retained on the inner surface of the columnar activated carbon, the metal salts are uniformly distributed in the pores of the carrier, and thermal decomposition and activation are carried out. The preparation method has the advantages of simple operation, good stability and the like, the three-dimensional particle electrode prepared according to the provided preparation method has a good effect of removing COD in the fine chemical wastewater, and the energy consumption is low.
Detailed Description
The present invention will be described in detail with reference to specific examples, which are not intended to limit the scope of the present invention.
Examples 1 to 4 are preparations of three-dimensional particle electrodes for wastewater treatment, example 5 is a performance evaluation of the three-dimensional particle electrodes prepared in examples 1 to 4, and examples 6 to 8 are stability tests of the prepared three-dimensional particle electrodes and advantages of the prepared three-dimensional particle electrodes compared with conventional preparation methods.
Example 1
(1) Pretreatment of columnar activated carbon: firstly, the columnar activated carbon is treated by acid and alkali to remove impurities such as ash and the like. Then washing with deionized water and drying to obtain the active carbon particles.
(2) Preparing tin dioxide sol: 10.01g of tin tetrachloride and 1.0g of citric acid were dissolved in 500mL of deionized water, stirred at 40 ℃ for 30min, followed by dropwise addition of an aqueous ammonia solution to a pH of 2.03, stirred until the reaction was completed, and allowed to stand overnight. Removing the supernatant of the reaction product, and adding 0.15 mol. L dropwise to the white precipitate-1Dissolving the oxalic acid solution, stirring uniformly at 40 ℃, dropwise adding oxalic acid until the pH value is 1.01, stopping dropwise adding, and continuously stirring until the reaction is finished to obtain the tin dioxide sol.
(3) Preparation of metal salt solution: nitrate salts of cerium, nickel and silver (the molar ratio of cerium to nickel to silver is 2: 3: 5) are added into deionized water to obtain a metal salt impregnation solution.
(4) Preparation of three-dimensional particle electrode: and (3) adding the activated carbon obtained in the step (1) into the tin dioxide sol obtained in the step (2), shaking and dipping for 3h in a shaking table, drying for 5h at 83 ℃, and then roasting at 210 ℃ to obtain the activated carbon particles loaded with the intermediate layer tin.
(5) Adding the activated carbon particles loaded with the intermediate layer tin obtained in the step (4) into the metal salt impregnation liquid obtained in the step (3), vibrating and impregnating for 3 hours, and drying for 6 hours at the temperature of 80 ℃ to obtain activated carbon particles loaded with activated metal; and finally, carrying out temperature programming roasting under the protection of inert gas to obtain the three-dimensional particle electrode I for wastewater treatment.
Example 2
(1) Pretreatment of columnar activated carbon: firstly, treating columnar activated carbon by acid and alkali to remove impurities such as gray matter, washing by deionized water and drying to obtain activated carbon particles.
(2) Preparing tin dioxide sol: 13.12g of tin tetrachloride and 1.13g of citric acid were dissolved in 500mL of deionized water, stirred at 40 ℃ for 30min, followed by dropwise addition of an aqueous ammonia solution to a pH of 2.56, stirred until the reaction was completed, and allowed to stand overnight. Removing the supernatant of the reaction product, and adding 0.2 mol. L dropwise to the white precipitate-1Dissolving the oxalic acid solution, stirring uniformly at 40 ℃, dropwise adding oxalic acid until the pH value is 1.31, stopping dropwise adding, and continuously stirring until the reaction is finished to obtain the tin dioxide sol.
(3) Preparation of metal salt solution: nitrate salts of cerium, nickel and silver (molar ratio of cerium, nickel and silver is 2: 3: 7) are added into deionized water to obtain a metal salt impregnation solution.
(4) Preparation of three-dimensional particle electrode: and (3) adding the activated carbon obtained in the step (1) into the tin dioxide sol obtained in the step (2), shaking and dipping for 3h in a shaking table, drying for 6h at the temperature of 80 ℃, and then roasting at the temperature of 205 ℃ to obtain the activated carbon particles loaded with the intermediate layer tin.
(5) Adding the activated carbon particles loaded with the intermediate layer tin obtained in the step (4) into the metal salt impregnation liquid obtained in the step (3), vibrating and impregnating for 3 hours, and drying for 5 hours at the temperature of 90 ℃ to obtain activated carbon particles loaded with activated metal; and finally, carrying out temperature programming roasting under the protection of inert gas to obtain a three-dimensional particle electrode II for wastewater treatment.
Example 3
(1) Pretreatment of columnar activated carbon: firstly, treating columnar activated carbon by acid and alkali to remove impurities such as gray matter, washing by deionized water and drying to obtain activated carbon particles.
(2) Preparing tin dioxide sol: 14.98g of tin tetrachloride and 1.49g of citric acid were dissolved in 500mL of deionized water, stirred at 40 ℃ for 30min, followed by dropwise addition of an aqueous ammonia solution to a pH of 3.68, stirred until the reaction was completed, and allowed to stand overnight. Removing the supernatant of the reaction product, and adding 0.25 mol. L dropwise to the white precipitate-1Dissolving the oxalic acid solution, stirring uniformly at 40 ℃, dropwise adding oxalic acid until the pH value is 1.81, stopping dropwise adding, and continuously stirring until the reaction is finished to obtain the tin dioxide sol.
(3) Preparation of metal salt solution: nitrate salts of cerium, nickel and silver (molar ratio of cerium, nickel and silver is 2: 4: 7) are added into deionized water to obtain a metal salt impregnation solution.
(4) Preparation of three-dimensional particle electrode: and (3) adding the activated carbon obtained in the step (1) into the tin dioxide sol obtained in the step (2), shaking and dipping for 5h in a shaking table, drying for 4h at the temperature of 90 ℃, and then roasting at the temperature of 250 ℃ to obtain activated carbon particles loaded with intermediate layer tin.
(5) Adding the activated carbon particles loaded with the intermediate layer tin obtained in the step (4) into the metal salt impregnation liquid obtained in the step (3), vibrating and impregnating for 5 hours, and drying for 5 hours at the temperature of 90 ℃ to obtain activated carbon particles loaded with activated metal; and finally, carrying out temperature programming roasting under the protection of inert gas to obtain the three-dimensional particle electrode III for wastewater treatment.
Example 4
(1) Pretreatment of columnar activated carbon: firstly, treating columnar activated carbon by acid and alkali to remove impurities such as gray matter, washing by deionized water and drying to obtain activated carbon particles.
(2) DioxygenPreparing tin sol: 13.12g of tin tetrachloride and 1.48g of citric acid were dissolved in 500mL of deionized water, stirred at 40 ℃ for 30min, followed by dropwise addition of an aqueous ammonia solution to a pH of 3.96, stirred until the reaction was completed, and allowed to stand overnight. Removing the supernatant of the reaction product, and adding 0.50 mol. L dropwise to the white precipitate-1Dissolving the oxalic acid solution, stirring uniformly at 40 ℃, dropwise adding oxalic acid until the pH value is 2.0, stopping dropwise adding, and continuously stirring until the reaction is finished to obtain the tin dioxide sol.
(3) Preparation of metal salt solution: nitrate salts of cerium, nickel and silver (molar ratio of cerium, nickel and silver is 2: 4: 8) are added into deionized water to obtain a metal salt impregnation solution.
(4) Preparation of three-dimensional particle electrode: and (3) adding the activated carbon obtained in the step (1) into the tin dioxide sol obtained in the step (2), shaking and dipping for 6h in a shaking table, drying for 5h at 85 ℃, and then roasting at 250 ℃ to obtain activated carbon particles loaded with intermediate layer tin.
(5) Adding the activated carbon particles loaded with the intermediate layer tin obtained in the step (4) into the metal salt impregnation liquid obtained in the step (3), vibrating and impregnating for 5 hours, and drying for 5 hours at the temperature of 90 ℃ to obtain activated carbon particles loaded with activated metal; and finally, carrying out temperature programming roasting under the protection of inert gas to obtain the three-dimensional particle electrode IV for wastewater treatment.
Example 5
A three-dimensional electrocatalysis system is constructed by taking the fine chemical wastewater of a certain factory in Shenzhen city as a treatment object, taking the DSA electrode as a working electrode and the particle electrodes prepared in the embodiments 1 to 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 inlet water is 560 mg.L-1And the pH value is 7.23, and the ammonia nitrogen value and the COD of the wastewater are measured after 45min of electrocatalytic degradation. Which is shown in table 1.
TABLE 1 evaluation results of the Performance of three-dimensional particle electrodes
| Examples | 1 | 2 | 3 | 4 |
| COD removal Rate (%) | 85.65 | 86.34 | 91.12 | 88.23 |
A two-dimensional electrode system is constructed by taking a DSA electrode as a working electrode, an electro-catalytic degradation experiment is carried out on the fine chemical wastewater under the same condition, and the COD removal rate of the wastewater is only 18.32% after 45 min. Therefore, the three-dimensional particle electrode for wastewater treatment prepared by the invention has high catalytic efficiency.
Example 6
For comparison, the active metal loaded AC/Sn-Ce-Ni-Ag and AC/Ce-Ni-Ag particle electrodes were obtained by a one-step impregnation method. Preparing salt solutions of Sn, Ce, Ni and Ag and salt solutions of Ce, Ni and Ag respectively, and impregnating, 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 in the embodiment 6 and the AC/Ce-Ni-Ag are respectively used as particle electrodes to be applied to the electro-catalysis treatment of the fine chemical wastewater. 500mL of fine chemical wastewater is subjected to electro-catalytic treatment by taking the DSA electrode as a working electrode, and treated 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 respectively 91.12%, 60.53% and 50.29%. Therefore, the three-dimensional particle electrode for wastewater treatment prepared by the invention has higher catalytic efficiency than that of the traditional impregnation method.
Example 8
Stability test of three-dimensional particle electrodes for wastewater treatment:
a DSA electrode is used as a working electrode, a three-dimensional electro-catalysis system is constructed with the AC/Sn/Ce-Ni-Ag particle electrode prepared in the embodiment 3 of the invention, 500mL of fine chemical wastewater is subjected to electro-catalysis 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 subjected to 5 times of electro-catalysis tests repeatedly under the same condition. The measured COD removal rate of the wastewater is as follows in sequence: 91.12%, 88.13%, 86.89%, 83.11%, 82.56%. Similarly, the three-dimensional electro-catalysis system using AC/Ce-Ni-Ag as a particle electrode has five consecutive COD removal rates of the fine chemical wastewater: 50.29%, 46.92%, 42.36%, 33.18% and 20.89%. Therefore, the three-dimensional particle electrode for wastewater treatment, which is prepared by the invention, has higher stability and can be repeatedly used. And compared with the particle electrode prepared by the traditional method, the stability is better.
Claims (2)
1. A preparation method of a 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, the columnar activated carbon is treated by acid and alkali to remove impurities such as ash and the like. Then washing with deionized water and drying to obtain the active carbon particles.
(2) Preparing 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 reaction product, and adding 0.1-0.5 mol/L dropwise to the white precipitate-1Dissolving the oxalic acid solution, 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 nitrates of cerium, nickel and silver into deionized water to obtain a metal salt soaking 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), shaking and dipping for 3-6 h in a shaking table, drying for 4-6 h at the temperature of 80-90 ℃, and then roasting at the temperature of 200-250 ℃ to obtain activated carbon particles loaded with intermediate layer tin;
(5) adding the activated carbon particles loaded with the middle layer tin obtained in the step (4) into the metal salt impregnation liquid obtained in the step (3), performing vibration impregnation for 3-6 hours, and drying at 80-100 ℃ for 4-6 hours to obtain activated carbon particles loaded with activated metal; and finally, carrying out temperature programming roasting under the protection of inert gas to obtain the three-dimensional particle electrode for wastewater treatment.
2. The three-dimensional particle electrode prepared by the preparation method of claim 1, which is an AC/Sn/Ce-Ni-Ag three-dimensional particle electrode taking columnar activated carbon as a carrier and loaded with a tin intermediate layer and a cerium, nickel and silver active layer.
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