WO2022116495A1 - 电动-曝气-注液联合修复重金属有机复合污染土的方法 - Google Patents

电动-曝气-注液联合修复重金属有机复合污染土的方法 Download PDF

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WO2022116495A1
WO2022116495A1 PCT/CN2021/097041 CN2021097041W WO2022116495A1 WO 2022116495 A1 WO2022116495 A1 WO 2022116495A1 CN 2021097041 W CN2021097041 W CN 2021097041W WO 2022116495 A1 WO2022116495 A1 WO 2022116495A1
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aeration
liquid injection
electric
repair
soil
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PCT/CN2021/097041
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English (en)
French (fr)
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谢新宇
葛尚奇
郑凌逶
章旬立
王韵超
刘春阳
孙旻洋
戴朴修
张康
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浙江大学
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Priority to US17/553,672 priority Critical patent/US11759836B2/en
Publication of WO2022116495A1 publication Critical patent/WO2022116495A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
    • B09C1/085—Reclamation of contaminated soil chemically electrochemically, e.g. by electrokinetics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/005—Extraction of vapours or gases using vacuum or venting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C2101/00—In situ

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  • the invention belongs to the field of polluted soil remediation, and particularly relates to a method for combined electromechanical-aeration-liquid injection restoration of heavy metal organic composite polluted soil.
  • Common contaminated soil remediation methods such as electric remediation, aeration method, solidification/stabilization remediation methods, etc., often only have a good remediation effect on soil of a single type of pollution.
  • a soil remediation method that can A good balance between heavy metal contaminated soil remediation and organic contaminated soil remediation.
  • the aeration method has a good effect on the remediation of volatile organic compounds in groundwater;
  • the electrokinetic remediation method has a better effect on the removal of heavy metal ions in the soil;
  • the curing/stabilization method of treating polluted soil can realize the sequestration of pollutants,
  • the depth of treatment is often limited; thermal desorption is more suitable for the treatment of organic contaminated soil. Facing the restoration of composite polluted soil, it is often necessary to combine a variety of restoration methods in order to achieve a good restoration effect on composite polluted soil of heavy metals and organic compounds.
  • the present invention proposes a method for the combined repairing of heavy metal organic compound polluted soil by electrodynamics-aeration-liquid injection.
  • a method for electric-aeration-liquid injection combined repairing heavy metal organic composite polluted soil comprises the following steps:
  • a double-channel porous EKG electrode is laid at the bottom of the heavy metal-organic composite polluted soil.
  • the electrode has a liquid injection transmission channel and a bubble transmission channel.
  • the upper surface of the electrode has a number of liquid injection holes that communicate with the liquid injection transmission channel and communicate with the bubble transmission channel.
  • Several bubble emission holes lay conventional EKG electrodes and isolation layers in sequence on the top of the polluted soil, and bury the pumping wells;
  • the bottom double-channel porous EKG electrode is connected to the anode of the power supply, and the top EKG electrode is connected to the cathode of the power supply, and the electric repair starts when the power is turned on;
  • the bottom dual-channel porous EKG electrode injects bubbles through the bubble emission hole to start the aeration process, and the top air extraction well is opened to collect toxic gases; the bottom dual-channel porous EKG electrode injects electrolyte through the liquid injection hole to start the liquid injection process; Collect the discharged liquid at the cathode;
  • in-situ or ex-situ treatment is performed on the soil enriched with surface pollutants by leaching or solidification/stabilization methods.
  • the electrolyte injected into the bottom double-channel porous EKG electrode through the liquid injection hole adopts natural surfactant, glycerol, sodium bicarbonate or mixed liquid, etc., to repair heavy metals and organic pollutants in polluted soil.
  • the bubbles injected by the bottom double-channel porous EKG electrode through the bubble emission holes are micro-nano bubbles, which are small in volume, slow in movement, and in a curve-rising state.
  • the gas-liquid mass transfer rate is high, and the repair effect is better.
  • the whole remediation process is carried out from bottom to top, so that heavy metals and organic pollutants are enriched in the topsoil, and finally the topsoil only needs to be treated by step (4).
  • the dual-channel porous EKG electrode can be used as an electrode material for electrokinetic repair, can also be used to transport air bubbles by aeration method, and can also inject electrolyte into polluted soil.
  • the water in the soil moves from the bottom to the top, and the pollutants are enriched to the top, especially for heavy metals, which has a better treatment effect. channel and drive.
  • the aeration method is used to generate bubbles, and a large number of hydroxyl radicals are generated instantly when the bubbles burst, and the existing redox potential can oxidize and reduce pollutants that are difficult to remove in the polluted soil, especially for organic pollutants.
  • the repair effect of the electric repair method can be enhanced.
  • electrolyte can alleviate the excessive acidity near the anode and maintain the pH stability of the soil; the higher temperature near the anode causes the gas generated by the decomposition of the electrolyte (for example, the electrolyte contains The carbon dioxide produced by sodium bicarbonate) can promote the bubbles generated by the aeration method to expand further during the process of moving from the bottom to the top, and the contact force with the soil increases, taking away more pollutants.
  • the poisonous gas collected at the top gas extraction well is purified by the gas purification device; and the discharged liquid collected at the cathode is purified.
  • the isolation layer adopts a water-impermeable and air-impermeable geomembrane, which is used to prevent the toxic substance-carrying gas produced by the aeration method and the toxic substance-carrying liquid produced in the repair process from being discharged into the external environment.
  • the electric remediation method drives the accumulation of heavy metals in the polluted soil to the top; the micro-nano bubbles generated by the aeration method drive the volatile organic compounds to diffuse to the top soil.
  • the electrokinetic repair flow generates more diffusion channels and diffusion driving force for aeration, and the aeration process accelerates the desorption of pollutants on the surface of soil particles and dissolves them into pore water;
  • the natural surfactant in the injection liquid is more conducive to the separation of heavy metals and organic pollutants from soil particles, and enhances the repair effect of electric repair method and aeration method;
  • FIG. 1 is a schematic structural diagram of a dual-channel porous EKG electrode provided in an embodiment of the present invention
  • Fig. 2 is a schematic diagram of a method for combined repairing heavy metal organic composite polluted soil provided by an embodiment of the present invention
  • a dual-channel porous EKG electrode 13 is first prepared. As shown in FIG. 1 , the electrode 13 has a liquid injection transmission channel 5 and a bubble transmission channel 6 inside. Liquid injection holes 3, several bubble emission holes 4 communicated with the bubble transmission channel 6.
  • the double-channel porous EKG electrode 13 can be used as the electrode material for electric repair, and can also transmit air bubbles for the aeration method, and also has a liquid injection channel.
  • Both the dual-channel porous EKG electrode 13 and the conventional EKG electrode 11 have a main body material 1 and a conductive material 2 .
  • the main body material 1 is made of polyethylene or polyvinyl chloride material
  • the conductive material 2 is made of carbon fiber or stainless steel.
  • the heavy metal-organic composite polluted soil is repaired through a combination of electrokinetic-aeration-liquid injection.
  • the repair method includes the following steps:
  • Double-channel porous EKG electrodes 13 are laid on the bottom of heavy metal organic composite polluted soil 19, conventional EKG electrodes 11 and isolation layers 18 are laid on the top in sequence, and a gas extraction well 9 is buried, and a micro-nano bubble generator 7 and a liquid supply are also arranged. Room 8.
  • the isolation layer 18 adopts an impermeable and airtight geomembrane, which is used to prevent the gas carrying toxic substances produced by the aeration method and the liquid carrying toxic substances produced in the repair process from being discharged into the external environment; the micro-nano bubble generators 7 and The micro-nano bubbles and liquid generated in the liquid supply chamber 8 are transferred to the dual-channel porous EKG electrode 13 at the bottom of the contaminated soil 19 through the delivery pipeline 12 .
  • the bottom double-channel porous EKG electrode 13 is connected to the anode of the power supply, and the top EKG electrode 11 is connected to the cathode of the power supply, and the electric repair starts when the power is turned on.
  • micro-nano bubble generator 7 manufactures micro-nano bubbles
  • bottom double-channel porous EKG electrode 13 injects bubbles through bubble emission holes 4, starts aeration process, opens top air extraction well 9, collects toxic gas, and passes through gas purification device 10 Purify.
  • the liquid supply chamber 8 supplies electrolyte intermittently, and the bottom double-channel porous EKG electrode 13 injects the electrolyte through the liquid injection hole 3 to start the liquid injection process; the discharged liquid is collected at the cathode, and the discharged liquid is purified.
  • the electrolyte can use natural surfactants, glycerol, sodium bicarbonate or mixed solution, etc., to repair heavy metals and organic pollutants in polluted soil; the micro-nano bubbles injected through the bubble emission holes are small in size and slow in movement. , showing a curve rising state, the gas-liquid mass transfer rate is high, and the repair effect is better.
  • the electric remediation flow direction 14 In the process of remediating polluted soil, the electric remediation flow direction 14 , micro-nano bubble diffusion 15 , liquid diffusion 16 , and bubble movement direction 17 are shown in FIG. 2 .

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  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

一种电动-曝气-注液联合修复重金属有机复合污染土的方法，属于污染土修复领域。该方法采用电动修复法联合曝气法，并通过底部注液加强修复效果。联合修复方法自下而上进行，电动修复法使土体中的水分由底部向顶部运移，带动重金属、有机物向顶部富集；曝气法产生的气泡由底部向顶部扩散，带动挥发性有机物向顶部土体移动，在顶部进行集中收集处理，气液传质率高，修复效果好；注液法通过底部间歇注入电解液，借助电动修复流的作用自下而上移动修复污染土体，同时维持土体pH稳定。电动修复法、曝气法和注液过程采用设计的双通道多孔EKG电极同时完成，高效、便捷。

Description

电动-曝气-注液联合修复重金属有机复合污染土的方法 技术领域
本发明属于污染土修复领域，具体涉及一种电动-曝气-注液联合修复重金属有机复合污染土的方法。
背景技术
随着工业化进程加速，工业生产、农业生产和城市生活对土壤的污染逐渐加重，污染场地的类型逐渐从单一污染源向多污染源发展，越来越多的土壤出现重金属和有机物的复合物污染情况，严重危害人类、动植物健康，已经成为目前亟待解决的环境问题之一。
常见的污染土修复方法，如电动修复、曝气法、固化/稳定化修复方法等，往往只对某单一污染类型的土壤具有很好的修复效果，目前，尚缺少一种土壤修复方法，能够很好的兼顾重金属污染土修复和有机污染土修复。例如，曝气法对修复地下水中挥发性的有机物具有很好的效果；电动修复法对土壤中的重金属离子的去除效果更佳；固化/稳定化方法处理污染土可以实现对污染物的封存，但是往往处理深度会受到限制；热脱附法更适用于处理有机污染土。面对复合污染土的修复，往往需要多种修复方法的结合，才能达到对重金属和有机物复合污染土的良好修复效果。
发明内容
为解决上述电动修复过程中存在的单一修复方法无法修复重金属和有机物复合污染土等问题，本发明提出了一种电动-曝气-注液联合修复重金属有机复合污染土的方法。
本发明的目的是通过以下技术方案实现的：一种电动-曝气-注液联合修复重金属有机复合污染土的方法，该方法包括以下步骤：
(1)在重金属有机复合污染土底部铺设双通道多孔EKG电极，电极内部具有注液传输通道和气泡传输通道，电极上表面具有与注液传输通道连通的若干注液孔，与气泡传输通道连通的若干气泡发射孔；在污染土顶部依次铺设常规EKG电极和隔离层，并埋设抽气井；
(2)底部双通道多孔EKG电极接电源阳极，顶部EKG电极接电源阴极，通电开始电动修复；
(3)底部双通道多孔EKG电极通过气泡发射孔注入气泡，开始曝气过程，打开顶部抽气井，收集有毒气体；底部双通道多孔EKG电极通过注液孔注入电解液，开始注液过程；在阴极处收集排出液体；
(4)结束电动修复和曝气注液过程后，通过淋洗或者固化/稳定化方法对表层污染物富 集的土壤进行原位或异位处理。
进一步地，底部双通道多孔EKG电极通过注液孔注入的电解液采用天然表面活性剂、甘油、碳酸氢钠或混合液等，用于修复污染土中的重金属和有机污染物。
进一步地，底部双通道多孔EKG电极通过气泡发射孔注入的气泡为微纳米气泡，气泡体积小，移动缓慢，呈曲线上升状态，气液传质率高，修复效果更好。
进一步地，整个修复过程自下而上进行，使重金属和有机污染物在表层土富集，最终仅需采用步骤(4)对表层污染土进行处理即可。
进一步地，所述双通道多孔EKG电极既可以作为电动修复的电极材料，又可以为曝气法传输气泡，还可以向污染土中注入电解液。
进一步地，利用电动修复法，使土体中的水分由底部向顶部运移，带动污染物向顶部富集，尤其对重金属有更好的处理效果，同时利用电渗流为气泡产生更多扩散的通道和驱动力。
进一步地，利用曝气法产生气泡，气泡破裂瞬间产生大量的羟基自由基，其存在的氧化还原电位可氧化还原污染土中难以去除的污染物，尤其对有机污染物有更好的处理效果，同时能够增强电动修复法的修复效果。
进一步地，电动修复过程中在阳极附近产生偏酸性环境，利用电解液能够缓解阳极附近酸性过强，维持土体pH稳定；阳极附近较高的温度导致电解液分解产生的气体(如电解液含有碳酸氢钠时产生的二氧化碳)，能够促进曝气法产生的气泡在从底部往顶部运移的过程中进一步膨胀，与土体接触力增大，带走更多污染物。
进一步地，在顶部抽气井收集的有毒气体通过气体净化装置进行净化处理；对阴极处收集的排出液体进行净化处理。
进一步地，所述隔离层采用不透水不透气土工膜，用于防止曝气法产生的携带有毒物质的气体和修复过程中产生的携带有毒物质的液体排放到外界环境中。
本发明的优点和效果在于：
1.充分发挥电动修复法和曝气法优势，电动修复法带动污染土中的重金属向顶部富集；曝气法产生的微纳米气泡带动挥发性有机物向顶部土体扩散。电动修复流为曝气产生更多扩散的通道和扩散驱动力，曝气过程加速了土颗粒表面的污染物解吸附并溶解到孔隙水中；
2.电动修复过程中间歇注液法，通过底部间歇注入含有采用天然表面活性剂、甘油、碳酸氢钠等的电解液，借助电动修复流的作用，驱动液体自下而上移动；
3.利用电动修复法在土体底部(阳极附近)产生的偏酸性环境、较高温度，导致碳酸氢钠等成分分解产生的二氧化碳，能够使曝气法产生的微纳米气泡在从底部往顶部运移的过程中继续膨大、与土体接触力增大，带走更多污染物；碳酸氢钠成分也能避免阳极附近酸性过 强，维持电渗过程中土体的pH稳定；
4.注液中的天然表面活性剂更有利于重金属和有机污染物成分从土颗粒上脱离，加强电动修复法和曝气法修复效果；
5.电动修复法、曝气法和注液过程采用本发明设计的双通道多孔EKG电极同时完成，高效、便捷。
附图说明
图1是本发明实施例提供的双通道多孔EKG电极结构示意图；
图2是本发明实施例提供的电动-曝气-注液联合修复重金属有机复合污染土方法示意图；
图中：1-主体材料；2-导电材料；3-注液孔；4-气泡发射孔；5-注液传输通道；6-气泡传输通道；7-微纳米气泡发生器；8-供液室；9-抽气井；10-气体净化装置；11-常规EKG电极；12-输送管路；13-双通道多孔EKG电极；14-电动修复流方向；15-微纳米气泡扩散；16-液体扩散；17-气泡运动方向；18-隔离层；19-污染土。
具体实施方式
下面结合具体实施例对本发明做进一步说明，但本发明不受实施例的限制。
本发明实施例首先制备一种双通道多孔EKG电极13，如图1所示，电极13内部具有注液传输通道5和气泡传输通道6，电极13上表面具有与注液传输通道5连通的若干注液孔3，与气泡传输通道6连通的若干气泡发射孔4。双通道多孔EKG电极13可同时作为电动修复的电极材料，又可以为曝气法传送气泡，同时还有注液通道。
双通道多孔EKG电极13和常规EKG电极11均具有主体材料1和导电材料2，主体材料1采用聚乙烯或聚氯乙烯材料，导电材料2采用碳纤维或不锈钢。
本实施例中，双通道多孔EKG电极13制备好后，通过电动-曝气-注液联合修复重金属-有机复合污染土，修复方法包括以下步骤：
(1)在重金属有机复合污染土19底部铺设双通道多孔EKG电极13，顶部依次铺设常规EKG电极11和隔离层18，并埋设抽气井9，此外还布置有微纳米气泡发生器7和供液室8。其中，隔离层18采用不透水不透气土工膜，用于防止曝气法产生的携带有毒物质的气体和修复过程中产生的携带有毒物质的液体排放到外界环境中；微纳米气泡发生器7和供液室8产生的微纳米气泡和液体通过输送管路12传送到污染土19底部的双通道多孔EKG电极13。
(2)底部双通道多孔EKG电极13接电源阳极，顶部EKG电极11接电源阴极，通电开始电动修复。
(3)微纳米气泡发生器7制造微纳米气泡，底部双通道多孔EKG电极13通过气泡发射孔4注入气泡，开始曝气过程，打开顶部抽气井9，收集有毒气体，并通过气体净化装置10 进行净化。供液室8间歇提供电解液，底部双通道多孔EKG电极13通过注液孔3注入电解液，开始注液过程；在阴极处收集排出液体，对排出液体进行净化处理。
其中，电解液可以采用天然表面活性剂、甘油、碳酸氢钠或混合液等，用于修复污染土中的重金属和有机污染物；通过气泡发射孔注入的微纳米气泡，气泡体积小，移动缓慢，呈曲线上升状态，气液传质率高，修复效果更好。
(4)结束电动修复和曝气注液过程后，通过淋洗或者固化/稳定化方法对表层污染物富集的土壤进行原位或异位处理。
在修复污染土过程中，电动修复流方向14、微纳米气泡扩散15、液体扩散16、气泡运动方向17如图2所示。
通过上述步骤，通电后在电动修复流的作用下，污染土19中的水分和注入的液体从底部向顶部移动，伴随着污染土19中的重金属和有机污染物解吸附到孔隙水中，并随着电动修复流向顶部土体富集；同时，微纳米气泡向上不断扩散，溶解挥发性有机物，并最终被抽气井收集。利用微纳米气泡破裂瞬间产生大量的羟基自由基，其存在的氧化还原电位可氧化污染土19中难以解吸附的有机和重金属污染，不仅有利于曝气法对有机物的去除，还有利于增强电动修复法的修复效果。
以上所述仅为本发明示意性具体实施方案，并非用以限制本发明的范围。任何本领域的技术人员，在不脱离本发明的构思和原则的前提下所作出的等同变化与修改，均应属于本发明保护的范围。

Claims (3)

  1. 一种电动-曝气-注液联合修复重金属有机复合污染土的方法，其特征在于，该方法包括以下步骤：
    (1)在重金属有机复合污染土底部铺设双通道多孔EKG电极，电极内部具有注液传输通道和气泡传输通道，电极上表面具有与注液传输通道连通的若干注液孔，与气泡传输通道连通的若干气泡发射孔；在污染土顶部依次铺设常规EKG电极和隔离层，并埋设抽气井；
    (2)底部双通道多孔EKG电极接电源阳极，顶部EKG电极接电源阴极，通电开始电动修复；
    (3)底部双通道多孔EKG电极通过气泡发射孔注入微纳米气泡，开始曝气过程，打开顶部抽气井，收集有毒气体；
    底部双通道多孔EKG电极通过注液孔注入电解液，开始注液过程；在阴极处收集排出液体；所述电解液采用天然表面活性剂、甘油、碳酸氢钠或混合液，用于修复污染土中的重金属和有机污染物；
    整个修复过程自下而上进行，使重金属和有机污染物在表层土富集；
    (4)结束电动修复和曝气注液过程后，通过淋洗或者固化/稳定化方法对表层污染物富集的土壤进行原位或异位处理；
    利用电动修复法，使土体中的水分由底部向顶部运移，带动污染物向顶部富集，对重金属有更好的处理效果，同时利用电渗流为气泡产生更多扩散的通道和驱动力；
    利用曝气法产生气泡，气泡破裂瞬间产生大量的羟基自由基，其存在的氧化还原电位可氧化还原污染土中难以去除的污染物，对有机污染物有更好的处理效果，同时能够增强电动修复法的修复效果；
    电动修复过程中在阳极附近产生偏酸性环境，利用电解液能够缓解阳极附近酸性过强，维持土体pH稳定；阳极附近较高的温度导致电解液分解产生的气体，能够促进曝气法产生的气泡在从底部往顶部运移的过程中进一步膨胀，与土体接触力增大，带走更多污染物；
    所述隔离层采用不透水不透气土工膜，用于防止曝气法产生的携带有毒物质的气体和修复过程中产生的携带有毒物质的液体排放到外界环境中。
  2. 根据权利要求1所述的方法，其特征在于，所述双通道多孔EKG电极既可以作为电动修复的电极材料，又可以为曝气法传输气泡，还可以向污染土中注入电解液。
  3. 根据权利要求1所述的方法，其特征在于，在顶部抽气井收集的有毒气体通过气体净化装置进行净化处理；对阴极处收集的排出液体进行净化处理。
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