CN102641744B - Catalytic oxidation active medium for removing nitrobenzene pollutant - Google Patents
Catalytic oxidation active medium for removing nitrobenzene pollutant Download PDFInfo
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 title claims abstract description 27
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 18
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 27
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010457 zeolite Substances 0.000 claims abstract description 27
- 239000010881 fly ash Substances 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 claims abstract description 18
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 18
- 239000003673 groundwater Substances 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 230000003204 osmotic effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 238000001035 drying Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 238000002791 soaking Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 18
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 description 5
- 238000005067 remediation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 230000033558 biomineral tissue development Effects 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000007857 degradation product Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003895 groundwater pollution Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 150000005181 nitrobenzenes Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 239000000015 trinitrotoluene Substances 0.000 description 2
- 229910006540 α-FeOOH Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 description 1
- 101150071746 Pbsn gene Proteins 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 229960004995 magnesium peroxide Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 231100000175 potential carcinogenicity Toxicity 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Abstract
一种用于去除地下水中硝基苯类污染物的催化氧化活性介质材料，其组成按重量百分比计为40％-50％活性粉煤灰、20-30％α-羟基氧化铁柱撑沸石、10-20％CaO2、10-20％MgO2混合而成。制备介质材料的方法为：将粉煤灰盐酸溶液中浸泡后，550-700℃烧结制成活性粉煤灰；把经Fe离子改性后的沸石置于强碱溶液中柱撑交联，分离干燥后制得α-羟基氧化铁柱撑沸石；将活性粉煤灰、α-羟基氧化铁柱撑沸石、CaO2、MgO2按照比例混合，混合物料粒径为0.1-1.5mm。A catalytic oxidation active medium material for removing nitrobenzene pollutants in groundwater, the composition of which is 40%-50% active fly ash, 20-30% α-iron oxyhydroxide pillared zeolite, 10-20% CaO 2 , 10-20% MgO 2 mixed. The method of preparing the medium material is as follows: after soaking the fly ash in hydrochloric acid solution, sintering at 550-700°C to make active fly ash; placing the zeolite modified by Fe ions in a strong alkali solution for cross-linking, separating After drying, α-oxyhydroxide pillared zeolite is obtained; active fly ash, α-oxyhydroxide pillared zeolite, CaO 2 and MgO 2 are mixed in proportion, and the particle size of the mixture is 0.1-1.5mm.
Description
技术领域 technical field
本发明属环境污染防治与修复技术领域，具体地涉及用于去除地下水中硝基苯类污染物的催化氧化活性介质及其制备方法。The invention belongs to the technical field of environmental pollution prevention and restoration, and in particular relates to a catalytic oxidation active medium for removing nitrobenzene pollutants in groundwater and a preparation method thereof.
背景技术 Background technique
有机物污染已经成为当前地下水污染的主要形式。硝基苯类污染物作为难降解有机物的一类化合物，该类污染物的防治与污染修复技术成为世界各国研究学者关注的热点。Organic pollution has become the main form of groundwater pollution. Nitrobenzene pollutants are a class of refractory organic compounds. The prevention and remediation technology of this kind of pollutants has become a hot spot for researchers all over the world.
渗透反应墙(Permeable Reactive Barrier，PRB)技术是近年来迅速发展的一种污染地下水原位修复技术，正逐步取代运行成本高昂的抽出处理技术，成为地下水修复技术的发展方向。迄今为止，在北美和欧洲已经建立安装了120座以上的PRB，其渗透介质材料主要有羟基磷酸盐、碳酸钙、沸石、颗粒活性炭、铁的氢氧化物、黏土矿物、过氧化镁、过氧化钙、零价铁、Fe(II)矿物及双金属等，针对各自适用的污染物种类均取得了良好的修复效果。硝基苯类化合物如硝基苯(NB)、2，4-二硝基甲苯(2，4-DNT)、三硝基甲苯(TNT)等多具有很强的生物毒性或潜在致癌性，对地下水中微生物生存不利，同时由于地下水特定的贫氧、低温条件，使得其生物降解效果较差。针对该类污染物的地下水生物修复技术研究主要是新型代谢硝基苯类微生物的发现与驯化。Permeable Reactive Barrier (PRB) technology is an in-situ remediation technology for contaminated groundwater that has developed rapidly in recent years. It is gradually replacing the extraction treatment technology with high operating costs and has become the development direction of groundwater remediation technology. So far, more than 120 PRBs have been established and installed in North America and Europe. The infiltration medium materials mainly include hydroxyphosphate, calcium carbonate, zeolite, granular activated carbon, iron hydroxide, clay minerals, magnesium peroxide, peroxide Calcium, zero-valent iron, Fe(II) minerals and bimetals, etc., have achieved good remediation effects for the types of pollutants they are applicable to. Nitrobenzene compounds such as nitrobenzene (NB), 2,4-dinitrotoluene (2,4-DNT), trinitrotoluene (TNT), etc. have strong biological toxicity or potential carcinogenicity. The survival of microorganisms in groundwater is unfavorable. At the same time, due to the specific oxygen-poor and low-temperature conditions of groundwater, its biodegradation effect is poor. The research on groundwater bioremediation technology for such pollutants is mainly the discovery and domestication of new microorganisms that metabolize nitrobenzene.
目前，在地下水中硝基苯类污染物修复工程实践中，普遍采用零价铁作为PRB活性反应介质材料，将硝基类物质还原为苯胺类物质，可提高污染物可生化性，但苯胺类物质仍具有一定的生物毒性，同时零价铁PRB本身无法实现硝基苯类污染物的高效矿化去除。双层PRB技术是在单层渗透反应墙基础之上发展而来，两墙体之间并非简单串联布设，通常第一层为第二层的辅助或第二层为第一层的强化，两者紧密联系，组成一个高效的双层PRB修复体系。但无论采用何种修复模式，选择适宜的、高效的、廉价易得的、绿色环保的活性渗透介质材料仍是该技术发展与应用的关键。At present, in the practice of remediation engineering of nitrobenzene pollutants in groundwater, zero-valent iron is generally used as the active reaction medium material of PRB, and the reduction of nitro substances to aniline substances can improve the biodegradability of pollutants, but aniline The substance still has certain biological toxicity, and the zero-valent iron PRB itself cannot realize the efficient mineralization and removal of nitrobenzene pollutants. The double-layer PRB technology is developed on the basis of a single-layer permeable reaction wall. The two walls are not simply arranged in series. Usually, the first layer is the auxiliary of the second layer or the second layer is the reinforcement of the first layer. They are closely connected to form an efficient double-layer PRB repair system. However, no matter what kind of restoration mode is adopted, the key to the development and application of this technology is to choose suitable, efficient, cheap and easy-to-obtain, green and environmentally friendly active permeable media materials.
发明内容 Contents of the invention
本发明的目的在于提供一种用于修复受硝基苯类物质污染地下水的催化氧化活性介质。The object of the present invention is to provide a catalytic oxidation active medium for repairing groundwater polluted by nitrobenzene substances.
本发明的又一目的在于提供一种制备上述催化氧化活性介质的方法。Another object of the present invention is to provide a method for preparing the above catalytic oxidation active medium.
为实现上述目的，本发明提供的去除地下水中硝基苯类污染物的催化氧化活性介质，用于双层渗透反应墙中的催化氧化反应墙，该催化氧化活性介质的组成按重量百分比计为40％-50％活性粉煤灰、20-30％α-羟基氧化铁柱撑沸石、10-20％CaO2和10-20％MgO2，其中α-羟基氧化铁柱撑沸石是由柱撑了α-羟基氧化铁的沸石构成。In order to achieve the above object, the catalytic oxidation active medium for removing nitrobenzene pollutants in groundwater provided by the present invention is used in the catalytic oxidation reaction wall in the double-layer permeable reaction wall, and the composition of the catalytic oxidation active medium is calculated as 40%-50% activated fly ash, 20-30% α-iron oxyhydroxide pillared zeolite, 10-20% CaO 2 and 10-20% MgO 2 , where α-iron oxyhydroxide pillared zeolite is made of pillared Zeolite composed of α-iron oxyhydroxide.
所述的催化氧化活性介质，其中，α-羟基氧化铁柱撑沸石中α-羟基氧化铁的重量百分比为20-35％。In the catalytic oxidation active medium, the weight percent of α-iron oxyhydroxide in the α-iron oxyhydroxide pillared zeolite is 20-35%.
所述的催化氧化活性介质，其中，催化氧化活性介质的粒径为0.1-1.5mm。The catalytic oxidation active medium, wherein the particle size of the catalytic oxidation active medium is 0.1-1.5mm.
本发明提供的制备上述催化氧化活性介质的方法，包括如下步骤：The method for preparing the above-mentioned catalytic oxidation active medium provided by the present invention comprises the following steps:
1)将粉煤灰在pH＝4-5的盐酸溶液中浸泡后，550-700℃烧结制成活性粉煤灰；1) After soaking the fly ash in a hydrochloric acid solution with pH=4-5, sintering at 550-700°C to make active fly ash;
2)70-80℃恒温条件下，把经Fe离子改性后的沸石置于强碱溶液中柱撑交联，分离干燥后制得α-羟基氧化铁柱撑沸石；2) Under constant temperature conditions of 70-80°C, the zeolite modified by Fe ions is placed in a strong alkali solution for pillared cross-linking, separated and dried to obtain α-iron oxyhydroxide pillared zeolite;
3)按重量百分比计，活性粉煤灰∶α-羟基氧化铁柱撑沸石∶CaO2∶MgO2＝40％-50％∶25-35％∶10-20％∶10-20％混合。3) Active fly ash: α-iron oxyhydroxide pillared zeolite: CaO 2 : MgO 2 = 40%-50%: 25-35%: 10-20%: 10-20% mixed by weight percentage.
所述的制备方法，其中，步骤1中粉煤灰在pH＝4-5的盐酸溶液中浸泡20-24小时。Said preparation method, wherein in step 1, the fly ash is soaked in the hydrochloric acid solution with pH=4-5 for 20-24 hours.
所述的制备方法，其中，盐酸浸泡的粉煤灰在550-700℃烧结15-20分钟。Said preparation method, wherein, the fly ash soaked in hydrochloric acid is sintered at 550-700° C. for 15-20 minutes.
所述的制备方法，其中，步骤2中把经Fe离子改性后的沸石置于强碱溶液中柱撑交联6-8天。The preparation method, wherein, in step 2, the zeolite modified by Fe ions is placed in a strong alkali solution for cross-linking by pillars for 6-8 days.
本发明具有以下优点：The present invention has the following advantages:
1)可以实现地下水中硝基苯类污染物的矿化降解1) It can realize the mineralization and degradation of nitrobenzene pollutants in groundwater
在双层渗透反应墙中采用催化氧化活性介质，处理后的地下水中的硝基苯类污染物彻底矿化降解为CO2和H2O，实现受硝基苯类物质污染地下水的彻底修复。The catalytic oxidation active medium is used in the double-layer permeable reaction wall, and the nitrobenzene pollutants in the treated groundwater are completely mineralized and degraded into CO 2 and H 2 O, thereby realizing the thorough restoration of the groundwater polluted by nitrobenzene substances.
2)去除效率高2) High removal efficiency
使用了催化氧化活性介质实现硝基苯类污染物彻底矿化降解，对硝基苯类污染物的去除可以达到85～95％，效率高，不产生有毒有害最终产物。The catalytic oxidation active medium is used to realize the complete mineralization and degradation of nitrobenzene pollutants, the removal of p-nitrobenzene pollutants can reach 85-95%, the efficiency is high, and no toxic and harmful final products are produced.
3)介质材料价廉无毒无害3) The medium material is cheap, non-toxic and harmless
催化氧化活性介质使用寿命长，介质材料的更换周期是传统材料的2-3倍，更换出的材料无毒无害，无需按照危险废物进行处置，同时这种介质材料来源广泛，价格低廉。The catalytic oxidation active medium has a long service life, and the replacement cycle of the medium material is 2-3 times that of the traditional material. The replaced material is non-toxic and harmless, and does not need to be disposed of as hazardous waste. At the same time, this medium material has a wide range of sources and is cheap.
具体实施方式 Detailed ways
本发明的催化氧化活性介质是应用于双层渗透反应墙中的催化氧化反应墙，由该催化氧化反应墙和还原反应墙串联构成的理化固定式渗透反应墙，还原反应墙是零价铁反应墙。该催化氧化活性介质的粒径较理想为0.1-1.5mm，其组成按重量百分比计，由40-50％粉煤灰、20-30％α-羟基氧化铁柱撑沸石(zeolite pillared byα-FeOOH，以下简称ZPF)、10-20％CaO2和10-20％MgO2。ZPF材料是由柱撑了α-羟基氧化铁的沸石构成，α-羟基氧化铁在ZPF材料中的含量在20-35％。The catalytic oxidation active medium of the present invention is a catalytic oxidation reaction wall applied to double-layer osmotic reaction walls. wall. The particle size of the catalytic oxidation active medium is preferably 0.1-1.5 mm, and its composition is by weight percentage, consisting of 40-50% fly ash, 20-30% α-iron oxyhydroxide pillared zeolite (zeolite pillared by α-FeOOH , hereinafter referred to as ZPF), 10-20% CaO 2 and 10-20% MgO 2 . The ZPF material is composed of zeolite supported by α-iron oxyhydroxide, and the content of α-iron oxyhydroxide in the ZPF material is 20-35%.
本发明的催化氧化活性介质反应材料的主要制作过程如下：将粉煤灰在pH＝4-5的盐酸溶液中浸泡20-24h，风干后，在550-700℃烧结15-20min，制成活性粉煤灰；ZPF是70-80℃恒温条件下，把经Fe离子改性后的沸石置于强碱溶液中柱撑交联6-8天，分离、干燥后制得，主要元素组成为Fe、Al、Si、Na等，其中α-FeOOH组分形态含量为20-35％。The main production process of the catalytic oxidation active medium reaction material of the present invention is as follows: soak the fly ash in the hydrochloric acid solution of pH=4-5 for 20-24h, after air-drying, sinter at 550-700°C for 15-20min to make active Fly ash; ZPF is obtained by placing the zeolite modified by Fe ions in a strong alkali solution for 6-8 days under constant temperature conditions of 70-80°C, and then separating and drying. The main element is Fe , Al, Si, Na, etc., wherein the α-FeOOH component form content is 20-35%.
本发明在第二层催化氧化反应墙中采用了上述催化氧化活性介质，该催化氧化介质可缓缓释放出一定浓度的绿色氧化剂H2O2，与ZPF材料发生催化氧化反应生成强氧化性羟基自由基。羟基自由基可以将硝基苯类物质还原产物苯胺类化合物矿化降解为CO2和H2O，进而实现地下水中的硝基苯类污染物的矿化降解，对地下水中的硝基苯类污染物具有去除效率高，降解产物无毒无害，同时介质材料价格低廉，具有十分广阔的应用前景。The present invention adopts the above-mentioned catalytic oxidation active medium in the second layer of catalytic oxidation reaction wall, and the catalytic oxidation medium can slowly release a certain concentration of green oxidant H 2 O 2 , which undergoes catalytic oxidation reaction with ZPF material to generate strong oxidative hydroxyl free radicals. Hydroxyl radicals can mineralize and degrade the aniline compounds, which are the reduction products of nitrobenzenes, into CO 2 and H 2 O, and then realize the mineralization and degradation of nitrobenzene pollutants in groundwater. The pollutants have high removal efficiency, the degradation products are non-toxic and harmless, and the dielectric material is cheap, so it has a very broad application prospect.
以下举若干实施例对本发明作进一步的描述。The present invention will be further described by citing several examples below.
实施例1Example 1
本实例采用土柱实验模拟双层渗透反应墙体系，第一层为粒径0.5-1mm零价铁，第二层为催化氧化介质材料。催化氧化介质由40％的活化粉煤灰、15％的CaO2、15％的MgO2、30％的ZPF组成，其中粉煤灰在pH＝4的盐酸溶液中浸泡20h，风干后，在600℃烧结15min；ZPF是70℃恒温条件下，经Fe离子改性后的沸石置于强碱溶液中柱撑交联7天，分离、干燥后制得。这两层介质材料构成的PRB用于处理浓度为5mg/L硝基苯地下水，运行3个月后，硝基苯平均去除率为91.5％，最终降解产物为CO2和H2O。In this example, the soil column experiment is used to simulate the double-layer permeable reaction wall system. The first layer is zero-valent iron with a particle size of 0.5-1 mm, and the second layer is a catalytic oxidation medium material. The catalytic oxidation medium is composed of 40% activated fly ash, 15% CaO 2 , 15% MgO 2 , and 30% ZPF. The fly ash is soaked in hydrochloric acid solution with pH=4 for 20 hours, and after air-drying, the Sintering at ℃ for 15 minutes; ZPF is prepared by placing the zeolite modified by Fe ions in a strong alkali solution for 7 days for pillar cross-linking at a constant temperature of 70 ℃, separating and drying. The PRB composed of these two layers of media materials was used to treat groundwater with a concentration of 5 mg/L nitrobenzene. After 3 months of operation, the average removal rate of nitrobenzene was 91.5%, and the final degradation products were CO 2 and H 2 O.
实施例2Example 2
本实施例在实验室地下水污染三维模拟装置中进行。装置中布设双层渗透反应墙，第一层为粒径0.1-1.5mm零价铁；第二层为催化氧化介质。催化氧化介质由40％的活化粉煤灰、20％的CaO2、15％的MgO2、25％的ZPF组成，其中粉煤灰在pH＝5的盐酸溶液中活化交联24h，风干后，在650℃烧结25min；ZPF是75℃恒温条件下，经Fe离子改性后的沸石置于强碱溶液中柱撑交联8天，分离、干燥后制得。由零价铁和催化氧化介质两种材料构成的双层PRB用于处理浓度为5mg/L2，4-二硝基甲苯(2，4-DNT)地下水，运行4个月后，2，4-DNT的平均去除率为92.4％，最终降解产物为CO2和H2O。This embodiment is carried out in a laboratory groundwater pollution three-dimensional simulation device. A double-layer permeable reaction wall is arranged in the device. The first layer is zero-valent iron with a particle size of 0.1-1.5mm; the second layer is a catalytic oxidation medium. The catalytic oxidation medium is composed of 40% activated fly ash, 20% CaO 2 , 15% MgO 2 , and 25% ZPF. The fly ash is activated and cross-linked in a hydrochloric acid solution with pH=5 for 24 hours. After air-drying, Sintered at 650°C for 25 minutes; ZPF is obtained by placing the zeolite modified by Fe ions in a strong alkali solution for 8 days, separated and dried at a constant temperature of 75°C. The double-layer PRB composed of zero-valent iron and catalytic oxidation medium was used to treat groundwater with a concentration of 5mg/L 2,4-dinitrotoluene (2,4-DNT). After 4 months of operation, 2,4- The average removal rate of DNT was 92.4%, and the final degradation products were CO 2 and H 2 O.
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