WO2023151437A1 - 一种三维粒子电极及其制备方法和应用 - Google Patents

一种三维粒子电极及其制备方法和应用 Download PDF

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WO2023151437A1
WO2023151437A1 PCT/CN2023/071228 CN2023071228W WO2023151437A1 WO 2023151437 A1 WO2023151437 A1 WO 2023151437A1 CN 2023071228 W CN2023071228 W CN 2023071228W WO 2023151437 A1 WO2023151437 A1 WO 2023151437A1
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activated carbon
dimensional particle
particle electrode
preparation
tin
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PCT/CN2023/071228
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English (en)
French (fr)
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张程蕾
谢陈鑫
滕厚开
雷太平
钱光磊
赵慧
任春燕
李旗
周立山
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中海油天津化工研究设计院有限公司
中海油能源发展股份有限公司
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Publication of WO2023151437A1 publication Critical patent/WO2023151437A1/zh

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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
    • C02F1/46—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

Definitions

  • the invention relates to the technical field of electrocatalysis, in particular to a three-dimensional particle electrode and its preparation method and application.
  • Electrocatalytic technology has been widely used in the field of wastewater treatment.
  • This technology uses the oxidation reaction of the anode and the active oxidizing substances such as OH, ClO - and HClO produced during the experiment to directly and indirectly degrade the pollutants in the wastewater.
  • Electrocatalytic oxidation technology has the advantages of simple operation, mild reaction conditions, and no secondary pollution. It has shown excellent degradation ability in the treatment of refractory wastewater, and has become a research hotspot in the field of sewage treatment. Due to the disadvantages of traditional two-dimensional plate electrodes such as small surface-to-body ratio, high power consumption, low current efficiency, and slow mass transfer rate, three-dimensional electrodes emerged as the times require.
  • Three-dimensional electrodes require granular or waste particle electrode materials to be filled between the electrodes. Particles are polarized during the electrification process, charging their surfaces and causing chemical reactions to take place on their surfaces.
  • the particle electrode can increase the surface-to-body ratio of the three-dimensional electrode, and because the distance between the particle electrodes is small, the mass transfer process of the substance is greatly improved, and the electrocatalytic efficiency is further improved while accelerating the reaction rate. Therefore, it is very necessary to modify the structure of the three-dimensional electrode reactor or study the particle electrode with higher catalytic activity.
  • Activated carbon has a high specific surface area and is currently one of the most effective adsorbents. The adsorbed organic matter will be oxidized and degraded under the action of an electric field.
  • pure activated carbon is directly used as a particle electrode, there are disadvantages such as low catalytic activity, poor stability, and low current utilization efficiency. Therefore, an efficient and stable catalytic particle electrode is urgently needed to be developed.
  • the object of the present invention is to overcome the problems existing in the above-mentioned particle electrodes, and provide a three-dimensional particle electrode and its preparation method and application.
  • the three-dimensional particle electrode can be used to remove organic pollutants in wastewater, and has high catalytic activity, strong stability, and preparation
  • the method is simple and so on.
  • the present invention provides a method for preparing a three-dimensional particle electrode, which is realized by adopting the following technical solutions.
  • a method for preparing a three-dimensional particle electrode comprising the steps of:
  • the concentrations of cerium, nickel and silver nitrates are 20mmol/L, 20-50mmol/L, and 50-80mmol/L, respectively.
  • the present invention provides a three-dimensional particle electrode, which is realized by adopting the following technical solutions.
  • a three-dimensional particle electrode prepared by the above preparation method is an AC/Sn/Ce-Ni-Ag type three-dimensional particle electrode with activated carbon as a carrier, a tin intermediate layer, and an active layer of cerium, nickel and silver.
  • the present invention provides a use of a three-dimensional particle electrode, which is realized by adopting the following technical solutions.
  • the application has the following beneficial effects.
  • the method of the present invention is dried after impregnating, and the water evaporates and escapes, so that the salts of the active components can be retained on the inner surface of the columnar activated carbon.
  • These metal salts are evenly distributed in the pores of the carrier, and after thermal decomposition and After activation, a three-dimensional particle electrode is obtained. It has the advantages of simple operation, good stability, etc., and the three-dimensional particle electrode prepared according to the provided preparation method has a good removal effect on COD in fine chemical wastewater, and has low energy consumption.
  • Examples 1-4 are the preparation of a three-dimensional particle electrode for wastewater treatment
  • Example 5 is the performance evaluation of the three-dimensional particle electrode prepared in Examples 1-4
  • Examples 6-8 are the stability of the prepared three-dimensional particle electrode. Sex test and advantages over traditional preparation methods.
  • Pretreatment of columnar activated carbon first, the columnar activated carbon is treated with acid and alkali to remove impurities such as ash. Then washed with deionized water and dried to obtain activated carbon particles.
  • step (4) Add the activated carbon particles loaded with tin in the middle layer obtained in step (4) into the metal salt impregnation solution obtained in step (3), oscillate and impregnate for 3 hours, and dry at 80°C for 6 hours to obtain activated carbon particles loaded with active metals ; Finally, the three-dimensional particle electrode I for wastewater treatment was obtained by temperature-programmed roasting under the protection of inert gas.
  • Pretreatment of columnar activated carbon first, the columnar activated carbon is treated with acid and alkali to remove impurities such as ash, and then washed with deionized water and dried to obtain activated carbon particles.
  • step (4) Add the activated carbon particles loaded with tin in the middle layer obtained in step (4) into the metal salt impregnation solution obtained in step (3), oscillate and impregnate for 3 hours, and dry at 90°C for 5 hours to obtain activated carbon particles loaded with active metals ; Finally, the three-dimensional particle electrode II for wastewater treatment was obtained by temperature-programmed roasting under the protection of inert gas.
  • Pretreatment of columnar activated carbon first, the columnar activated carbon is treated with acid and alkali to remove impurities such as ash, and then washed with deionized water and dried to obtain activated carbon particles.
  • step (4) Add the activated carbon particles loaded with tin in the middle layer obtained in step (4) into the metal salt impregnation solution obtained in step (3), oscillate and impregnate for 5 hours, and dry at 90°C for 5 hours to obtain activated carbon particles loaded with active metals ; Finally, the three-dimensional particle electrode III for wastewater treatment was obtained by temperature-programmed roasting under the protection of inert gas.
  • Pretreatment of columnar activated carbon first, the columnar activated carbon is treated with acid and alkali to remove impurities such as ash, and then washed with deionized water and dried to obtain activated carbon particles.
  • step (4) Add the activated carbon particles loaded with tin in the middle layer obtained in step (4) into the metal salt impregnation solution obtained in step (3), oscillate and impregnate for 5 hours, and dry at 90°C for 5 hours to obtain activated carbon particles loaded with active metals ; Finally, the three-dimensional particle electrode IV for wastewater treatment was obtained by temperature-programmed roasting under the protection of inert gas.
  • DSA electrode as the working electrode, and the particle electrodes prepared in Examples 1-4 of the present invention were used to construct a three-dimensional electrocatalytic system, and an evaluation test was performed in a plexiglass electrolytic cell.
  • the wastewater volume is 500mL
  • the current value is 5A
  • the voltage value is 2.9V
  • the influent COD is 560mg ⁇ L -1
  • the pH is 7.23
  • the ammonia nitrogen value and COD of the wastewater are measured after electrocatalytic degradation for 45min. It is shown in Table 1.
  • AC/Sn-Ce-Ni-Ag and AC/Ce-Ni-Ag particle electrodes loaded with active metals were obtained by one-step impregnation method.
  • the salt solution of Sn, Ce, Ni, Ag and the salt solution of Ce, Ni, Ag were prepared respectively, and two particle electrodes were obtained by impregnating, drying and roasting.
  • AC/Sn/Ce-Ni-Ag and AC/Ce-Ni-Ag in Example 6 of the present invention as particle electrodes for electrocatalytic treatment of fine chemical industry in wastewater.
  • DSA electrode As the working electrode, 500mL of fine chemical wastewater was electrocatalytically treated at a current value of 5A for 45min. It is measured that under the three systems, the COD removal rates of fine chemical wastewater are 91.12%, 60.53% and 50.29%, respectively. It can be seen that the catalytic efficiency of a three-dimensional particle electrode for wastewater treatment prepared by the present invention is higher than that of the traditional impregnation method.
  • Example 3 of the present invention Using the DSA electrode as the working electrode, construct a three-dimensional electrocatalytic system with the AC/Sn/Ce-Ni-Ag particle electrode prepared in Example 3 of the present invention, and perform electrocatalytic treatment on 500mL of fine chemical wastewater, under the condition that the current value is 5A After 45 minutes of treatment, the waste water was filtered, the obtained precipitate was washed and dried, and the electrocatalytic test was repeated 5 times under the same conditions.
  • the measured COD removal rates of wastewater are: 91.12%, 88.13%, 86.89%, 83.11%, 82.56%.
  • the three-dimensional electrocatalytic system using AC/Ce-Ni-Ag as the particle electrode the COD removal rates of fine chemical wastewater for five consecutive times are: 50.29%, 46.92%, 42.36%, 33.18% and 20.89%. It can be seen that the three-dimensional particle electrode for wastewater treatment prepared by the present invention has high stability and can be used repeatedly. And compared with the particle electrode prepared by the traditional method, the stability is better.
  • a method for preparing a three-dimensional particle electrode comprising the following steps:
  • Pretreatment of columnar activated carbon first, the columnar activated carbon is treated with acid and alkali to remove impurities such as ash, and then washed with deionized water and dried to obtain activated carbon particles.
  • metal salt solution 0.04 mol, 0.06 mol and 0.10 mol of cerium, nickel and silver nitrates were respectively added into 200 mL of deionized water to obtain a metal salt impregnation solution.
  • step (4) Add the activated carbon particles loaded with tin in the middle layer obtained in step (4) into the metal salt impregnation solution obtained in step (3), oscillate and impregnate for 3 hours, and dry at 80°C for 6 hours to obtain activated carbon particles loaded with active metals ; Finally, the three-dimensional particle electrode I for wastewater treatment was obtained by temperature-programmed roasting under the protection of inert gas.
  • a method for preparing a three-dimensional particle electrode comprising the following steps:
  • Pretreatment of columnar activated carbon first, the columnar activated carbon is treated with acid and alkali to remove impurities such as ash, and then washed with deionized water and dried to obtain activated carbon particles.
  • metal salt solution 0.04 mol, 0.06 mol and 0.14 mol of nitrates of cerium, nickel and silver were respectively added into 200 mL of deionized water to obtain a metal salt impregnation solution.
  • step (4) Add the activated carbon particles loaded with tin in the middle layer obtained in step (4) into the metal salt impregnation solution obtained in step (3), oscillate and impregnate for 3 hours, and dry at 90°C for 5 hours to obtain activated carbon particles loaded with active metals ; Finally, the three-dimensional particle electrode II for wastewater treatment was obtained by temperature-programmed roasting under the protection of inert gas.
  • a method for preparing a three-dimensional particle electrode comprising the following steps:
  • Pretreatment of columnar activated carbon first, the columnar activated carbon is treated with acid and alkali to remove impurities such as ash, and then washed with deionized water and dried to obtain activated carbon particles.
  • metal salt solution 0.04 mol, 0.08 mol, 0.14 mol of cerium, nickel and silver nitrates were added to 200 mL of deionized water respectively to obtain a metal salt impregnation solution.
  • step (4) Add the activated carbon particles loaded with tin in the middle layer obtained in step (4) into the metal salt impregnation solution obtained in step (3), oscillate and impregnate for 5 hours, and dry at 90°C for 5 hours to obtain activated carbon particles loaded with active metals ; Finally, the three-dimensional particle electrode III for wastewater treatment was obtained by temperature-programmed roasting under the protection of inert gas.
  • a method for preparing a three-dimensional particle electrode comprising the following steps:
  • Pretreatment of columnar activated carbon first, the columnar activated carbon is treated with acid and alkali to remove impurities such as ash, and then washed with deionized water and dried to obtain activated carbon particles.
  • metal salt solution 0.04 mol, 0.08 mol and 0.16 mol of nitrates of cerium, nickel and silver were respectively added into 200 mL of deionized water to obtain a metal salt impregnation solution.
  • step (4) Add the activated carbon particles loaded with tin in the middle layer obtained in step (4) into the metal salt impregnation solution obtained in step (3), oscillate and impregnate for 5 hours, and dry at 90°C for 5 hours to obtain activated carbon particles loaded with active metals ; Finally, the three-dimensional particle electrode IV for wastewater treatment was obtained by temperature-programmed roasting under the protection of inert gas.
  • the AC/Sn-Ce-Ni-Ag particle electrode was prepared by a one-step impregnation method, including the following steps:
  • the AC/Ce-Ni-Ag particle electrode was prepared by a one-step impregnation method, including the following steps:
  • Example 11 of the present invention Using the DSA electrode as the working electrode, construct a three-dimensional electrocatalytic system with the AC/Sn/Ce-Ni-Ag particle electrode prepared in Example 11 of the present invention, and perform electrocatalytic treatment on 500mL of fine chemical wastewater with a pH value of 6.5. After 45 minutes of treatment under the condition of 5A, the wastewater was filtered, and the obtained precipitate was washed and dried, and the electrocatalytic test was repeated 5 times under the same conditions.
  • the measured COD removal rates of wastewater were: 91.12%, 88.13%, 86.89%, 83.11%, 82.56%, and ammonia nitrogen removal rates were 98.57%, 98.02%, 97.85%, 97.82%, 96.95%.
  • the COD removal rates of fine chemical wastewater for five consecutive times were: 50.29%, 46.92%, 42.36%, 33.18% and 20.89%.
  • the removal rates of ammonia nitrogen were 82.48%, 78.96%, 70.36%, 68.45%, and 25.59%, respectively. It can be seen that the three-dimensional particle electrode prepared by the present invention for wastewater treatment has high stability and can be used repeatedly. And compared with the particle electrode prepared by the traditional method, the stability is better.

Abstract

本发明公开了一种三维粒子电极及其制备方法和应用。该三维粒子电极是以活性炭为载体，负载了锡中间层，铈、镍和银活性层的AC/Sn/Ce-Ni-Ag型三维粒子电极。所述制备方法包括：柱状活性炭的预处理、二氧化锡溶胶的制备、金属盐溶液的制备、浸渍、烘干和焙烧，即可得到三维粒子电极。本发明制备的三维粒子电极可用于去除废水中的有机污染物，具有性质稳定、催化活性高、寿命长等特点，且工艺简单，易于推广使用。

Description

一种三维粒子电极及其制备方法和应用 技术领域
本发明涉及电催化技术领域，特别涉及一种三维粒子电极及其制备方法和应用。
背景技术
近年来，电催化技术在废水处理领域得到了广泛的应用。该技术是利用阳极的氧化反应和实验过程中产生的·OH、ClO -和HClO等活性氧化物质直接和间接的降解废水中的污染物。电催化氧化技术具有操作简单、反应条件温和以及无二次污染等优点，在处理难降解废水方面展现出了优异的降解能力，成为污水处理领域的研究热点。由于传统的二维平板电极，具有面体比小、电耗高、电流效率低和传质速率慢等缺点，因此三维电极应运而生。三维电极要求在电极间填充颗粒状或废屑状的粒子电极材料。在通电过程中粒子发生极化，并使其表面带电，进而在其表面上发生化学反应。粒子电极能够增加三维电极的面体比，并且由于粒子电极之间的间距较小，极大的改善了物质的传质过程，在加快反应速率的同时进一步提高了电催化效率。因此，对三维电极反应器进行结构改造或研究具有较高催化活性的粒子电极显得十分必要。
活性炭(AC)具有较高的比表面积，是目前最有效的吸附剂之一，吸附的有机物会在电场的作用下被氧化降解。纯活性炭直接作为粒子电极时，存在催化活性不高、稳定性差、电流利用效率低等缺点，因此，一种高效稳定的催化粒子电极亟待开发。
发明内容
本发明的目的在于克服上述粒子电极存在的问题，提供一种三维粒子电极及其制备方法和应用，该三维粒子电极可用于去除废水中的有机污染物，具有催化活性高、稳定性强、制备方法简单等特点。
第一方面，本发明提供了一种三维粒子电极的制备方法，是采用以下技术方案得以实现的。
一种三维粒子电极的制备方法，包括如下步骤：
(1)柱状活性炭的预处理：将柱状活性炭经酸和碱处理去除杂质，再用去离子 水洗涤并干燥得到活性炭颗粒；
(2)二氧化锡溶胶的制备：将四氯化锡和柠檬酸以摩尔比为(3～6)∶1的比例溶解在去离子水中，并在40～60℃下搅拌20～40min，随后滴加氨水溶液至pH为2～4，搅拌至反应结束，静置过夜；除去反应物的上清液，向白色沉淀中滴加0.1～0.5mol·L -1的草酸溶液，使其溶解，在35～45℃下搅拌均匀后，滴加草酸至pH为1.0～2.0时停止滴加，继续搅拌至反应结束，得到二氧化锡溶胶；
(3)金属盐浸渍溶液的制备：将铈、镍和银的硝酸盐加入到去离子水中，得到金属盐浸渍溶液；所述铈、镍和银的摩尔比为2∶(2～5)∶(5～8)；
(4)三维粒子电极的制备：将活性炭颗粒加入到二氧化锡溶胶中，震荡浸渍3～6h，在80～90℃的条件下干燥4～6h，然后在200～250℃在焙烧，得到负载中间层锡的活性炭颗粒；
(5)将负载中间层锡的活性炭颗粒加入到金属盐浸渍溶液中，震荡浸渍3～6h，在80～100℃的条件下干燥4～6h，得到负载活性金属的活性炭颗粒；最后至于惰性气体保护下程序升温焙烧得到三维粒子电极。
进一步的，每100mL二氧化锡溶胶中加入80-130g活性炭。
进一步的，所述金属盐浸渍溶液中，铈、镍和银的硝酸盐的浓度分别为20mmol/L、20-50mmol/L、50-80mmol/L。
第二方面，本发明提供了一种三维粒子电极，是采用以下技术方案得以实现的。
一种上述制备方法制得的三维粒子电极，所述电极是以活性炭为载体，负载了锡中间层，铈、镍和银活性层的AC/Sn/Ce-Ni-Ag型三维粒子电极。
第三方面，本发明提供了一种三维粒子电极的用途，是采用以下技术方案得以实现的。
一种上述三维粒子电极在废水处理中的用途。
本申请具有以下有益效果。
本发明方法通过浸渍后经干燥，将水分蒸发逸出，可使活性组分的盐类保留在柱状活性炭的内表面上，这些金属盐类均匀的分布在载体的细孔中，经热分解及活化后，即得到一种三维粒子电极。其具有操作简单，稳定性好等优点，依照所提供的制备方法制备得到的三维粒子电极对精细化工废水中的COD具有良好的去除效果，且能耗较低。
具体实施方式
下面结合实施例对本发明进行进一步的说明。如无特殊说明，本发明实施例中采用的原料、试剂均为市售商品。
实施例1～4为一种用于废水处理的三维粒子电极的制备，实施例5为实施例1～4所制备三维粒子电极的性能评价，实施例6～8为所制备三维粒子电极的稳定性试验及较传统制备方法的优势。
实施例1
(1)柱状活性炭的预处理：首先将柱状活性炭经酸和碱处理，去除灰质等杂质。再用去离子水洗涤并干燥得到活性炭颗粒。
(2)二氧化锡溶胶的制备：将10.01g四氯化锡和1.0g柠檬酸加入到500mL去离子水中溶解，在40℃下搅拌30min，随后随后滴加氨水溶液至pH为2.03时，搅拌至反应结束，静置过夜。除去反应物的上清液，向白色沉淀滴加0.15mol·L -1的草酸溶液，使其溶解，在40℃下搅拌均匀后，滴加草酸至pH为1.01时停止滴加，继续搅拌至反应结束，得到二氧化锡溶胶。
(3)金属盐溶液的制备：将铈、镍和银的硝酸盐(铈、镍和银的摩尔比为2∶3∶5)加入到去离子水中，得到金属盐浸渍溶液。
(4)三维粒子电极的制备：将(1)得到的活性炭加入到步骤(2)得到的二氧化锡溶胶中，在摇床震荡浸渍3h，在83℃的条件下干燥5h，然后在210℃在焙烧，得到负载中间层锡的活性炭颗粒。
(5)将步骤(4)所得负载中间层锡的活性炭颗粒加入到步骤(3)得到的金属盐浸渍液中，震荡浸渍3h，在80℃的条件下干燥6h，得到负载活性金属的活性炭颗粒；最后至于惰性气体保护下程序升温焙烧得到用于废水处理的三维粒子电极I。
实施例2
(1)柱状活性炭的预处理：首先将柱状活性炭经酸和碱处理，去除灰质等杂质，再用去离子水洗涤并干燥得到活性炭颗粒。
(2)二氧化锡溶胶的制备：将13.12g四氯化锡和1.13g柠檬酸加入到500mL去离子水中溶解，在40℃下搅拌30min，随后随后滴加氨水溶液至pH为pH为2.56时，搅拌至反应结束，静置过夜。除去反应物的上清液，向白色沉淀滴加0.2mol·L -1 的草酸溶液，使其溶解，在40℃下搅拌均匀后，滴加草酸至pH为1.31时停止滴加，继续搅拌至反应结束，得到二氧化锡溶胶。
(3)金属盐溶液的制备：将铈、镍和银的硝酸盐(铈、镍和银的摩尔比为2∶3∶7)加入到去离子水中，得到金属盐浸渍溶液。
(4)三维粒子电极的制备：将(1)得到的活性炭加入到步骤(2)得到的二氧化锡溶胶中，在摇床震荡浸渍3h，在80℃的条件下干燥6h，然后在205℃在焙烧，得到负载中间层锡的活性炭颗粒。
(5)将步骤(4)所得负载中间层锡的活性炭颗粒加入到步骤(3)得到的金属盐浸渍液中，震荡浸渍3h，在90℃的条件下干燥5h，得到负载活性金属的活性炭颗粒；最后至于惰性气体保护下程序升温焙烧得到用于废水处理的三维粒子电极II。
实施例3
(1)柱状活性炭的预处理：首先将柱状活性炭经酸和碱处理，去除灰质等杂质，再用去离子水洗涤并干燥得到活性炭颗粒。
(2)二氧化锡溶胶的制备：将14.98g四氯化锡和1.49g柠檬酸加入到500mL去离子水中溶解，在40℃下搅拌30min，随后随后滴加氨水溶液至pH为pH为3.68时，搅拌至反应结束，静置过夜。除去反应物的上清液，向白色沉淀滴加0.25mol·L -1的草酸溶液，使其溶解，在40℃下搅拌均匀后，滴加草酸至pH为1.81时停止滴加，继续搅拌至反应结束，得到二氧化锡溶胶。
(3)金属盐溶液的制备：将铈、镍和银的硝酸盐(铈、镍和银的摩尔比为2∶4∶7)加入到去离子水中，得到金属盐浸渍溶液。
(4)三维粒子电极的制备：将(1)得到的活性炭加入到步骤(2)得到的二氧化锡溶胶中，在摇床震荡浸渍5h，在90℃的条件下干燥4h，然后在250℃在焙烧，得到负载中间层锡的活性炭颗粒。
(5)将步骤(4)所得负载中间层锡的活性炭颗粒加入到步骤(3)得到的金属盐浸渍液中，震荡浸渍5h，在90℃的条件下干燥5h，得到负载活性金属的活性炭颗粒；最后至于惰性气体保护下程序升温焙烧得到用于废水处理的三维粒子电极III。
实施例4
(1)柱状活性炭的预处理：首先将柱状活性炭经酸和碱处理，去除灰质等杂质，再用去离子水洗涤并干燥得到活性炭颗粒。
(2)二氧化锡溶胶的制备：将13.12g四氯化锡和1.48g柠檬酸加入到500mL去离子水中溶解，在40℃下搅拌30min，随后随后滴加氨水溶液至pH为pH为3.96时，搅拌至反应结束，静置过夜。除去反应物的上清液，向白色沉淀滴加0.50mol·L -1的草酸溶液，使其溶解，在40℃下搅拌均匀后，滴加草酸至pH为2.0时停止滴加，继续搅拌至反应结束，得到二氧化锡溶胶。
(3)金属盐溶液的制备：将铈、镍和银的硝酸盐(铈、镍和银的摩尔比为2∶4∶8)加入到去离子水中，得到金属盐浸渍溶液。
(4)三维粒子电极的制备：将(1)得到的活性炭加入到步骤(2)得到的二氧化锡溶胶中，在摇床震荡浸渍6h，在85℃的条件下干燥5h，然后在250℃在焙烧，得到负载中间层锡的活性炭颗粒。
(5)将步骤(4)所得负载中间层锡的活性炭颗粒加入到步骤(3)得到的金属盐浸渍液中，震荡浸渍5h，在90℃的条件下干燥5h，得到负载活性金属的活性炭颗粒；最后至于惰性气体保护下程序升温焙烧得到用于废水处理的三维粒子电极IV。
实施例5
以深圳市某厂精细化工废水为处理对象，以DSA电极为工作电极，与本发明实施例1-4制备的粒子电极构建三维电催化体系，在有机玻璃电解槽内做评价试验。其中废水体积为500mL，电流值为5A，电压值为2.9V，进水COD为560mg·L -1，pH为7.23，电催化降解45min后测定废水的氨氮值和COD。其如表1所示。
表1三维粒子电极的性能评价结果
Figure PCTCN2023071228-appb-000001
以DSA电极为工作电极，构建二维电极体系，在相同的条件下对精细化工废水进行电催化降解实验，45min后废水的COD去除率仅为18.32％。由此可见，本发明制备的一种用于废水处理的三维粒子电极催化效率较高。
实施例6
作为对比，采用一步浸渍法，得到负载活性金属的AC/Sn-Ce-Ni-Ag和AC/Ce-Ni-Ag粒子电极。分别配制Sn、Ce、Ni、Ag的盐溶液和Ce、Ni、Ag的盐溶液，经浸渍、干燥和焙烧得到两种粒子电极。
实施例7
以本发明实施例3中的AC/Sn/Ce-Ni-Ag、实施例6中AC/Sn-Ce-Ni-Ag和AC/Ce-Ni-Ag分别作为粒子电极应用于电催化处理精细化工废水中。以DSA电极为工作电极，对500mL精细化工废水进行电催化处理，在电流值为5A的条件下处理45min。测得在三种体系下，对精细化工废水的COD去除率分别为91.12％、60.53％和50.29％。由此可见，本发明制备的一种用于废水处理的三维粒子电极较传统的浸渍法催化效率高。
实施例8
用于废水处理的三维粒子电极的稳定性试验：
以DSA电极为工作电极，与本发明实施例3制备的AC/Sn/Ce-Ni-Ag粒子电极构建三维电催化体系，对500mL精细化工废水进行电催化处理，在电流值为5A的条件下处理45min后，将废水进行过滤，所得沉淀物洗涤、烘干，在相同的条件下重复进行5次电催化试验。测得废水的COD去除率依次为：91.12％、88.13％、86.89％、83.11％、82.56％。类似的，以AC/Ce-Ni-Ag为粒子电极的三维电催化体系，连续五次对精细化工废水的COD去除率分别为：50.29％、46.92％、42.36％、33.18％和20.89％。由此可见，本发明制备的一种用于废水处理的三维粒子电极稳定性较高，可重复使用。且与传统的方法制备的粒子电极相比，稳定性更好。
实施例9
一种三维粒子电极的制备方法，包括以下步骤：
(1)柱状活性炭的预处理：首先将柱状活性炭经酸和碱处理去除灰质等杂质，再用去离子水洗涤并干燥得到活性炭颗粒。
(2)二氧化锡溶胶的制备：将10.01g四氯化锡和1.0g柠檬酸加入到500mL去离子水中溶解，在40℃下搅拌30min，随后滴加氨水溶液至pH为2.03时，搅拌至反应结束，静置过夜。除去反应物的上清液，向白色沉淀滴加0.15mol·L -1的草酸溶液，使其溶解，在40℃下搅拌均匀后，滴加草酸至pH为1.01时停止滴加，继续搅拌至反应结束，得到二氧化锡溶胶。
(3)金属盐溶液的制备：分别将0.04mol、0.06mol和0.10mol铈、镍和银的硝酸盐加入到200mL去离子水中，得到金属盐浸渍溶液。
(4)三维粒子电极的制备：将(1)得到的活性炭200g加入到步骤(2)得到的二氧化锡溶胶中，在摇床震荡浸渍3h，在83℃的条件下干燥5h，然后在210℃在焙烧，得到负载中间层锡的活性炭颗粒。
(5)将步骤(4)所得负载中间层锡的活性炭颗粒加入到步骤(3)得到的金属盐浸渍液中，震荡浸渍3h，在80℃的条件下干燥6h，得到负载活性金属的活性炭颗粒；最后至于惰性气体保护下程序升温焙烧得到用于废水处理的三维粒子电极I。
实施例10
一种三维粒子电极的制备方法，包括以下步骤：
(1)柱状活性炭的预处理：首先将柱状活性炭经酸和碱处理去除灰质等杂质，再用去离子水洗涤并干燥得到活性炭颗粒。
(2)二氧化锡溶胶的制备：将13.12g四氯化锡和1.13g柠檬酸加入到500mL去离子水中溶解，在40℃下搅拌30min，随后滴加氨水溶液至pH为2.56时，搅拌至反应结束，静置过夜。除去反应物的上清液，向白色沉淀滴加0.2mol·L -1的草酸溶液，使其溶解，在40℃下搅拌均匀后，滴加草酸至pH为1.31时停止滴加，继续搅拌至反应结束，得到二氧化锡溶胶。
(3)金属盐溶液的制备：分别将0.04mol、0.06mol和0.14mol铈、镍和银的硝酸盐加入到200mL去离子水中，得到金属盐浸渍溶液。
(4)三维粒子电极的制备：将(1)得到的活性炭200g加入到步骤(2)得到的二氧化锡溶胶中，在摇床震荡浸渍3h，在80℃的条件下干燥6h，然后在205℃在焙烧，得到负载中间层锡的活性炭颗粒。
(5)将步骤(4)所得负载中间层锡的活性炭颗粒加入到步骤(3)得到的金属盐浸渍液中，震荡浸渍3h，在90℃的条件下干燥5h，得到负载活性金属的活性炭颗粒；最后至于惰性气体保护下程序升温焙烧得到用于废水处理的三维粒子电极II。
实施例11
一种三维粒子电极的制备方法，包括以下步骤：
(1)柱状活性炭的预处理：首先将柱状活性炭经酸和碱处理去除灰质等杂质，再用去离子水洗涤并干燥得到活性炭颗粒。
(2)二氧化锡溶胶的制备：将14.98g四氯化锡和1.49g柠檬酸加入到500mL去离子水中溶解，在40℃下搅拌30min，随后滴加氨水溶液至pH为3.68时，搅拌 至反应结束，静置过夜。除去反应物的上清液，向白色沉淀滴加0.25mol·L -1的草酸溶液，使其溶解，在40℃下搅拌均匀后，滴加草酸至pH为1.81时停止滴加，继续搅拌至反应结束，得到二氧化锡溶胶。
(3)金属盐溶液的制备：分别将0.04mol、0.08mol、0.14mol铈、镍和银的硝酸盐加入到去200mL离子水中，得到金属盐浸渍溶液。
(4)三维粒子电极的制备：将(1)得到的200g活性炭加入到步骤(2)得到的二氧化锡溶胶中，在摇床震荡浸渍5h，在90℃的条件下干燥4h，然后在250℃在焙烧，得到负载中间层锡的活性炭颗粒。
(5)将步骤(4)所得负载中间层锡的活性炭颗粒加入到步骤(3)得到的金属盐浸渍液中，震荡浸渍5h，在90℃的条件下干燥5h，得到负载活性金属的活性炭颗粒；最后至于惰性气体保护下程序升温焙烧得到用于废水处理的三维粒子电极III。
实施例12
一种三维粒子电极的制备方法，包括以下步骤：
(1)柱状活性炭的预处理：首先将柱状活性炭经酸和碱处理去除灰质等杂质，再用去离子水洗涤并干燥得到活性炭颗粒。
(2)二氧化锡溶胶的制备：将13.12g四氯化锡和1.48g柠檬酸加入到500mL去离子水中溶解，在40℃下搅拌30min，随后滴加氨水溶液至pH为3.96时，搅拌至反应结束，静置过夜。除去反应物的上清液，向白色沉淀滴加0.50mol·L -1的草酸溶液，使其溶解，在40℃下搅拌均匀后，滴加草酸至pH为2.0时停止滴加，继续搅拌至反应结束，得到二氧化锡溶胶。
(3)金属盐溶液的制备：分别将0.04mol、0.08mol和0.16mol铈、镍和银的硝酸盐加入到200mL去离子水中，得到金属盐浸渍溶液。
(4)三维粒子电极的制备：将(1)得到的200g活性炭加入到步骤(2)得到的二氧化锡溶胶中，在摇床震荡浸渍6h，在85℃的条件下干燥5h，然后在250℃在焙烧，得到负载中间层锡的活性炭颗粒。
(5)将步骤(4)所得负载中间层锡的活性炭颗粒加入到步骤(3)得到的金属盐浸渍液中，震荡浸渍5h，在90℃的条件下干燥5h，得到负载活性金属的活性炭颗粒；最后至于惰性气体保护下程序升温焙烧得到用于废水处理的三维粒子电极IV。
对比例1
采用一步浸渍法制备AC/Sn-Ce-Ni-Ag粒子电极，包括以下步骤：
配制200mL含Sn、Ce、Ni、Ag的盐溶液，Sn、Ce、Ni、Ag的用量分别为0.04mol、0.04mol、0.08mol、0.14mol，将200g活性炭加入到Sn、Ce、Ni、Ag的盐溶液中，震荡浸渍5h，在90℃的条件下干燥5h，得到负载活性金属的活性炭颗粒；最后至于惰性气体保护下程序升温焙烧得到AC/Sn-Ce-Ni-Ag粒子电极。
对比例2
采用一步浸渍法制备AC/Ce-Ni-Ag粒子电极，包括以下步骤：
配制含Ce、Ni、Ag的盐溶液，Ce、Ni、Ag的用量分别为0.04mol、0.08mol、0.14mol，将200g活性炭加入到Ce、Ni、Ag的盐溶液中，震荡浸渍5h，在90℃的条件下干燥5h，得到负载活性金属的活性炭颗粒；最后至于惰性气体保护下程序升温焙烧得到AC/Ce-Ni-Ag粒子电极。
性能检测
1、以深圳市某厂精细化工废水为处理对象，以DSA电极为工作电极，与本发明实施例9-12制备的粒子电极构建三维电催化体系，在有机玻璃电解槽内做评价试验。其中废水体积为500mL，电流值为5A，电压值为2.9V，进水COD为560mg·L -1，pH为7.23，电催化降解45min后测定废水的氨氮值和COD。其如表2所示。
表2三维粒子电极的性能评价结果
  氨氮值 COD去除率(％)
实施例9 97.61 85.65
实施例10 97.69 86.34
实施例11 98.57 91.12
实施例12 98.01 88.23
以DSA电极为工作电极，构建二维电极体系，在相同的条件下对精细化工废水进行电催化降解实验，45min后废水的COD去除率仅为18.32％，对氨氮的去除率为72.23％。由此可见，本发明制备的一种用于废水处理的三维粒子电极催化效率较高。
2、以本发明实施例11中的AC/Sn/Ce-Ni-Ag、对比例1中的AC/Sn-Ce-Ni-Ag和对比例2中的AC/Ce-Ni-Ag分别作为粒子电极应用于电催化处理精细化工废水 中。以DSA电极为工作电极，对500mL pH值为6.5的精细化工废水进行电催化处理，在电流值为5A，电压为3V的条件下处理45min。测得在三种体系下，对精细化工废水的COD去除率分别为91.12％、60.53％和50.29％。氨氮去除率分别为98.51％、88.25％、82.48％。由此可见，本发明制备的一种用于废水处理的三维粒子电极较传统的浸渍法催化效率高。
3、三维粒子电极的稳定性试验
以DSA电极为工作电极，与本发明实施例11制备的AC/Sn/Ce-Ni-Ag粒子电极构建三维电催化体系，对500mL pH值为6.5的精细化工废水进行电催化处理，在电流值为5A的条件下处理45min后，将废水进行过滤，所得沉淀物洗涤、烘干，在相同的条件下重复进行5次电催化试验。测得废水的COD去除率依次为：91.12％、88.13％、86.89％、83.11％、82.56％，氨氮去除率分别为98.57％、98.02％、97.85％、97.82％、96.95％。
采用相同的方法，以对比例2制备的AC/Ce-Ni-Ag为粒子电极的三维电催化体系，连续五次对精细化工废水的COD去除率分别为：50.29％、46.92％、42.36％、33.18％和20.89％。氨氮去除率分别为82.48％、78.96％、70.36％、68.45％、25.59％。由此可见，本发明制备的一种用于废水处理的三维粒子电极稳定性较高，可重复使用。且与传统的方法制备的粒子电极相比，稳定性更好。
本具体实施方式的实施例均为本发明的较佳实施例，并非依此限制本发明的保护范围，故：凡依本发明的结构、形状、原理所做的等效变化，均应涵盖于本发明的保护范围之内。

Claims (5)

  1. 一种三维粒子电极的制备方法，其特征在于，包括如下步骤：
    (1)柱状活性炭的预处理：将柱状活性炭经酸和碱处理去除杂质，再用去离子水洗涤并干燥得到活性炭颗粒；
    (2)二氧化锡溶胶的制备：将四氯化锡和柠檬酸以摩尔比为(3～6):1的比例溶解在去离子水中，并在40～60℃下搅拌20～40min，随后滴加氨水溶液至pH为2～4，搅拌至反应结束，静置过夜；除去反应物的上清液，向沉淀中滴加0.1～0.5mol·L -1的草酸溶液，使其溶解，在35～45℃下搅拌均匀后，滴加草酸至pH为1.0～2.0时停止滴加，继续搅拌至反应结束，得到二氧化锡溶胶；
    (3)金属盐浸渍溶液的制备：将铈、镍和银的硝酸盐加入到去离子水中，得到金属盐浸渍溶液；所述铈、镍和银的摩尔比为2:(2～5):(5～8)；
    (4)三维粒子电极的制备：将活性炭颗粒加入到二氧化锡溶胶中，震荡浸渍3～6h，在80～90℃的条件下干燥4～6h，然后在200～250℃在焙烧，得到负载中间层锡的活性炭颗粒；
    (5)将负载中间层锡的活性炭颗粒加入到金属盐浸渍溶液中，震荡浸渍3～6h，在80～100℃的条件下干燥4～6h，得到负载活性金属的活性炭颗粒；最后至于惰性气体保护下程序升温焙烧得到三维粒子电极。
  2. 根据权利要求1所述的一种三维粒子电极的制备方法，其特征在于：每100mL二氧化锡溶胶中加入80-130g活性炭。
  3. 根据权利要求1所述的一种三维粒子电极的制备方法，其特征在于：所述金属盐浸渍溶液中，铈、镍和银的硝酸盐的浓度分别为20mmol/L、20-50mmol/L、50-80mmol/L。
  4. 一种权利要求1-3任一所述制备方法制得的三维粒子电极，其特征在于，所述电极是以活性炭为载体，负载了锡中间层，铈、镍和银活性层的AC/Sn/Ce-Ni-Ag型三维粒子电极。
  5. 一种权利要求4所述三维粒子电极在废水处理中的用途。
PCT/CN2023/071228 2022-02-11 2023-01-09 一种三维粒子电极及其制备方法和应用 WO2023151437A1 (zh)

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