CN102950149A - Restoration method for organic contaminated soil - Google Patents
Restoration method for organic contaminated soil Download PDFInfo
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- CN102950149A CN102950149A CN2012101504177A CN201210150417A CN102950149A CN 102950149 A CN102950149 A CN 102950149A CN 2012101504177 A CN2012101504177 A CN 2012101504177A CN 201210150417 A CN201210150417 A CN 201210150417A CN 102950149 A CN102950149 A CN 102950149A
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- carboxylic acid
- polluted soil
- amino carboxylic
- organic
- organic polluted
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- 239000002689 soil Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 44
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000008139 complexing agent Substances 0.000 claims abstract description 21
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 claims abstract description 13
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 8
- 239000000356 contaminant Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- 238000010668 complexation reaction Methods 0.000 claims description 3
- 230000004992 fission Effects 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- WKVMOQXBMPYPGK-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].OC(=O)CN(CC(O)=O)CC(O)=O WKVMOQXBMPYPGK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- 238000005067 remediation Methods 0.000 description 4
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- JWBOIMRXGHLCPP-UHFFFAOYSA-N Chloditan Chemical compound C=1C=CC=C(Cl)C=1C(C(Cl)Cl)C1=CC=C(Cl)C=C1 JWBOIMRXGHLCPP-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000011953 bioanalysis Methods 0.000 description 2
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- -1 NTA etc.) Chemical compound 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000021962 pH elevation Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the technical field of associated contained soil restoration of environment protection and relates to a novel restoration method for organic contaminated soil. The method comprises the following steps of: using an oxidation reaction system consisting of amino carboxylic acid substances (ethylene diamine tetraacetic acid (EDTA), ethylenediaminedisuccinic acid (EDDS), sodium triglycollamate(NTA) and the like), zero-valent iron (ZVI) and air (AIR) to complex dissolved oxygen through a series of reactions between amino carboxylic acid complexing agent and Fe<2+>; and finally, enabling O-O bond to brake and activate for in-situ generating H2O2, reacting the generated H2O2 with Fenton formed by Fe<2+> to quickly degrade organic pollutant in the soil, and simultaneously degrading the amino carboxylic acid complexing agent. Compared with the traditional Fenton and ZVI/H2O2 type Fenton, the novel oxidation system also can react under neutral and alkaline conditions without additionally adding acid to adjust the acidity; the H2O2 can be generated in situ without being additionally added. The restoration method has the advantages of high degradation rate, environmental friendliness, simplicity in operation and low cost, and is an effective method for quickly and effectively restoring high-concentration organic contaminated site soil.
Description
Technical field
The invention belongs to the soil remediation technology, be specifically related to a kind of restorative procedure of organic polluted soil.
Background technology
In recent years, fast development along with Urbanization in China, " move back the city and enter the garden ", the enforcement of policy and the fulfiling " about the Convention of Stockholm of persistence organic pollutant (POPs) " such as " industry transfer ", enterprises removes such as large quantities of fine chemistry industries of old town, nearly all big and medium-sized cities, petrochemical industry, Coal Chemical Industry, electronics or close have been left over a large amount of chemical pollutions place in the city and outskirts zone.All there is the Organic Pollution of high concentration mostly in these contaminated sites, if any document certain insecticide factory's soil is carried out monitoring and surveying, the concentration of finding BHC (HCHs) in the soil is 1 ~ 440mg/kg, and the change in concentration scope of DDT (DDTs) is 5 ~ 966mg/kg.
The restorative procedure of organic polluted soil mainly is bioanalysis, Physical and chemical method at present.To the soil remediation in the chemical pollution place of high toxicity, high contamination levels, bioanalysis is inapplicable, and Physical can only shift pollutant, and thorough degradation of contaminant.The chemistry recovery technique has fast and efficiently technical advantage.In all kinds of chemical recovery techniques, Fenton (Fenton) is more with the research of Fenton-like system.
Traditional Fenton passes through Fe
2+Catalyzing and decomposing H under acid condition
2O
2Produce strong oxidizer-hydroxyl radical free radical, thus degradation of contaminant.When being applied to soil remediation, need constantly to add Fe
2+And hydrogen peroxide.With the Fe among Zero-valent Iron (ZVI) the replacement traditional F enton
2+Form heterogeneous Fenton-like reaction, need not to add Fe
2+, organic matter is also had certain oxidation effectiveness.But traditional F enton and ZVI/H
2O
2The Fenton-like that forms all only has acid condition could produce good oxidation effectiveness.The pH of most soil generally approaches neutral, adopts traditional F enton and ZVI/H
2O
2Fenton-like needs to use a large amount of acid, and soil is had acidization, need add a large amount of H simultaneously
2O
2, and H
2O
2Storage and the transportation also very inconvenient.
Summary of the invention
The restorative procedure that the purpose of this invention is to provide a kind of organic polluted soil, the method have reaction fast, and be simple to operate, with low cost, advantages of environment protection.
The restorative procedure of a kind of organic polluted soil provided by the invention is characterized in that, the oxidation reaction system that the method utilizes amino carboxylic acid complexing agent, Zero-valent Iron and air to form is by amino carboxylic acid complexing agent and and Fe
2+A series of complexation reaction complexing dissolved oxygen, and finally make O-O bond fission activation, original position produces H
2O
2, with Fe
2+Form the Fenton reaction, the organic pollution in the organic polluted soil is degraded.
As the optimization of technique scheme, the method specifically comprises the steps:
The 1st step Zero-valent Iron and amino carboxylic acid enveloping agent solution join in the organic polluted soil, stir and form mud; Wherein, the mass ratio of Zero-valent Iron and organic polluted soil is 1:4 ~ 1:50, and organic polluted soil quality g is 1:5 ~ 1:40 with the ratio of amino carboxylic acid enveloping agent solution volume mL; The concentration range of amino carboxylic acid complexing agent is 0.01 ~ 2mmol/L in the amino carboxylic acid enveloping agent solution;
The 2nd step pumped into air in mud, mud is fully contacted with air, opened reaction, and collected the organic gas that may volatilize;
After the reaction beginning of the 3rd step, monitor respectively the concentration of water and organic contaminants in soil and amino carboxylic acid complexing agent, estimate the repairing effect of organic polluted soil, until repairing effect meets the demands.
Remarkable advantage of the present invention is:
1) new method provided by the invention has good oxidation effectiveness to the organic pollution of contaminated soil middle and high concentration.The present invention is applicable to the soil of various different organic contamination levels, and reaction fast, good degrading effect.Organic polluted soil can be sandy soil or the sandy loam of good penetrability, also can be the clay of poor permeability; Organic pollution can be water-soluble organic pollutant or the hydrophobic organic pollutant of variable concentrations level.
2) new method provided by the invention can be reacted under normal temperature and pressure, condition of different pH, and organic pollution in the contaminated soil is had good oxidation effectiveness.Under acid and neutral reaction condition, can obtain faster repairing effect.Reaction condition is simple, need not outer acid adding/alkali, can obtain good repairing effect, and to soil without acidifying/alkalinization.
3) new method provided by the invention, H
2O
2Produce at the course of reaction situ.Need not to add H
2O
2, saved cost, and solved traditional F enton and ZVI/H
2O
2The H that Fenton-like exists
2O
2Store the problem with transportation inconvenience.
4) new method provided by the invention, but Simultaneous Oxidation amino carboxylic acid complexing agent, non-secondary pollution produces, environmental friendliness.
The specific embodiment
Know-why of the present invention is the oxidation reaction system of utilizing amino carboxylic acid complexing agent (such as EDTA, EDDS, NTA etc.), Zero-valent Iron (ZVI) and air (AIR) to form, by amino carboxylic acid complexing agent and Fe
2+A series of complexation reaction complexing dissolved oxygen, and finally make O-O bond fission activation, original position produces H
2O
2, with Fe
2+Form the Fenton reaction, under normal temperature, normal pressure, condition of different pH, organic pollution is all had good degradation effect.
The specific embodiment of soil remediation method provided by the invention is:
1) Zero-valent Iron (ZVI) joins in the organic polluted soil with the amino carboxylic acid enveloping agent solution, stirs to form mud;
Zero-valent Iron (ZVI) can be the iron powder of size from the nanometer to the micron level.
The amino carboxylic acid complexing agent can be the complexing agent that ethylenediamine tetra-acetic acid (EDTA), EDDS (EDDS) or nitrilotriacetic acid sodium (NTA) etc. contain amino and carboxylic acid.
Organic polluted soil for variable concentrations, ZVI(g) and the proportion of organic polluted soil quality (g) be generally 1:4 ~ 1:50, the proportion of organic polluted soil quality (g) and amino carboxylic acid enveloping agent solution volume (mL) is generally 1:5 ~ 1:40.The concentration range of amino carboxylic acid complexing agent is 0.01 ~ 2mmol/L in the amino carboxylic acid enveloping agent solution, and solvent can be water.
2) utilize device for absorbing tail gas to absorb the organic gas that may volatilize;
3) in mud, pump into air, mud is fully contacted with air, open reaction;
4) after the reaction beginning, monitor respectively the concentration of water and organic contaminants in soil and amino carboxylic acid complexing agent, estimate the repairing effect of organic polluted soil.
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is described in more detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
Embodiment one:
For water-soluble preferably organic pollution, 2,4-Dichlorophenol is prepared in employing voluntarily, and (2, simulating pollution kaolin 4-DCP) is the oxidative degradation experiment that experimental subjects is carried out the ZVI/EDTA/Air system.The pH of simulating pollution soil is that the concentration of 5.68,2,4-DCP is 488mg/kg.The mass ratio of ZVI and organic polluted soil is 1:4 in the reaction system, and organic polluted soil quality (g) is 1:40 with the ratio of amino carboxylic acid enveloping agent solution volume (mL).Get the 10g contaminated soil, 2.5g the zeroth order iron powder is the EDTA solution of 2mmol/L in 400mL concentration, place reaction vessel, adopt magnetic stirring apparatus that mud stirring is even, rotating speed is 1000rpm, use air pump to pump into air and pass through the flowmeter adjust flux to be 1L/min, (30 ℃ start reaction under condition 1atm) at normal temperature and pressure.The result shows, reaction 30min, and the degradation rate of DCP and EDTA has reached respectively 97% and 49%; When reaction extends to 2h, the EDTA degradation rate reaches 90%.
Embodiment two:
For water miscible 2, and the 4-Dichlorophenol (2,4-DCP) POLLUTION SIMULATION kaolin, (EDDS EDDS), carries out the oxidative degradation experiment of ZVI/EDDS/Air system to use different amino carboxylic acid complexing agents.In the contaminated soil 2, the concentration of 4-DCP is 233mg/kg.The mass ratio of ZVI and organic polluted soil is 1:50 in the reaction system, and organic polluted soil quality (g) is 1:5 with the ratio of amino carboxylic acid enveloping agent solution volume (mL).Adding 100g simulating pollution soil and 500ml concentration are the EDDS aqueous solution of 0.01mmol/L in mud reactor, add simultaneously the 2g iron powder, the air speed that exposes to the sun is 1L/min, use magnetic stirring apparatus that mud is stirred, rotating speed is 900rpm, (30 ℃, startup is reacted under condition 1atm) at normal temperature and pressure.Behind the reaction 3h, the degradation rate of DCP is that the degradation rate of 93.4%, EDDS is 91.4% in the soil; DCP behind the reaction 3.5h in the system is degraded fully, and this moment, the degradation rate of EDDS was 95.9%.
Embodiment three:
For hydrophobic organic polluted soil, the organic agricultural chemicals contaminated soil that picks up from Wujiang, Jiangsu Province, China insecticide factory old site is experimental subjects.This soil belongs to silty clay loam, pH is 6.38, the content of organic matter is 0.85%, Chlordene, 4,4 '-DDE, 2,4 '-DDD, 4,4 '-DDD, 4, the concentration of 4 '-DDT and total DDT is respectively 64.2mg/kg, 4.58mg/kg, 82.4mg/kg, 295mg/kg, 987mg/kg and 1369mg/kg.The mass ratio of ZVI and organic polluted soil is 1:20 in the reaction system, and organic polluted soil quality (g) is 1:8 with the ratio of amino carboxylic acid enveloping agent solution volume (mL).In mud reactor, add 50g contaminated soil and the 400ml aqueous solution, EDTA concentration is 0.2mmol/L in the aqueous solution, add simultaneously the 2.5g iron powder, use magnetic stirring apparatus that mud is stirred, rotating speed is 800rpm, uses air pump to pump into air, is 1L/min by the flowmeter coutroi velocity, (30 ℃, startup is reacted under condition 1atm) at normal temperature and pressure.Behind the reaction 8h, Chlordene, 4 in the soil, 4 '-DDE, 2,4 '-DDD, 4,4 '-DDD, 4, the clearance of 4 '-DDT and total DDTs is respectively 95.4%, 27.5%, 64.5%, 56.4%, 53.9% and 55.6%, and EDTA is degradable simultaneously.
Those skilled in the art will readily understand; the above only is preferred embodiment of the present invention; not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. the restorative procedure of an organic polluted soil is characterized in that, the oxidation reaction system that the method utilizes amino carboxylic acid complexing agent, Zero-valent Iron and air to form is by amino carboxylic acid complexing agent and and Fe
2+A series of complexation reaction complexing dissolved oxygen, and finally make O-O bond fission activation, original position produces H
2O
2, with Fe
2+Form the Fenton reaction, the organic pollution in the organic polluted soil is degraded.
2. the restorative procedure of described organic polluted soil according to claim 1 is characterized in that, the method specifically comprises the steps:
The 1st step Zero-valent Iron and amino carboxylic acid enveloping agent solution join in the organic polluted soil, stir and form mud; Wherein, the mass ratio of Zero-valent Iron and organic polluted soil is 1:4 ~ 1:50, and organic polluted soil quality g is 1:5 ~ 1:40 with the ratio of amino carboxylic acid enveloping agent solution volume mL; The concentration range of amino carboxylic acid complexing agent is 0.01 ~ 2 mmol/L in the amino carboxylic acid enveloping agent solution;
The 2nd step pumped into air in mud, mud is fully contacted with air, opened reaction, and collected the organic gas that may volatilize;
After the reaction beginning of the 3rd step, monitor respectively the concentration of water and organic contaminants in soil and amino carboxylic acid complexing agent, estimate the repairing effect of organic polluted soil, until repairing effect meets the demands.
3. the restorative procedure of described organic polluted soil according to claim 1 and 2 is characterized in that, Zero-valent Iron is the iron powder of size from the nanometer to the micron level.
4. the restorative procedure of described organic polluted soil according to claim 1 and 2 is characterized in that, the amino carboxylic acid complexing agent is the complexing agent that contains amino and carboxylic acid.
5. the restorative procedure of described organic polluted soil according to claim 4 is characterized in that, the amino carboxylic acid complexing agent comprises edta edta, EDDS EDDS or nitrilotriacetic acid sodium NTA etc.
6. the restorative procedure of described organic polluted soil according to claim 1 and 2 is characterized in that, organic polluted soil is sandy soil, sandy loam or clay.
7. the restorative procedure of described organic polluted soil according to claim 1 and 2 is characterized in that, described organic pollution is water-soluble organic pollutant or hydrophobic organic pollutant.
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|---|---|---|---|
| CN2012101504177A CN102950149A (en) | 2012-05-15 | 2012-05-15 | Restoration method for organic contaminated soil |
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|---|---|---|---|
| CN2012101504177A CN102950149A (en) | 2012-05-15 | 2012-05-15 | Restoration method for organic contaminated soil |
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| CN103240267A (en) * | 2013-04-28 | 2013-08-14 | 华中师范大学 | Soil restoration method based on oxygen activation of iron powder and polyphosphoric acid molecules |
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| CN105855286A (en) * | 2016-04-05 | 2016-08-17 | 南京农业大学 | Oxidation removing method for polycyclic aromatic hydrocarbon in soil through Fenton reagent bag |
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| CN109675562A (en) * | 2018-12-26 | 2019-04-26 | 浙江益壤环保科技有限公司 | The preparation method and applications of one type Fenton catalysis material |
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| CN103240267B (en) * | 2013-04-28 | 2014-07-23 | 华中师范大学 | Soil restoration method based on oxygen activation of iron powder and polyphosphoric acid molecules |
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| CN103706630B (en) * | 2013-12-26 | 2015-07-22 | 江苏盖亚环境工程有限公司 | Method for remediation of organic pollutants in soil by using mineral nanocomposite material |
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| CN104310566B (en) * | 2014-11-03 | 2016-03-02 | 济南大学 | A kind of method based on polyaniline-coated type nano zero valence iron process organic waste water |
| CN105855286A (en) * | 2016-04-05 | 2016-08-17 | 南京农业大学 | Oxidation removing method for polycyclic aromatic hydrocarbon in soil through Fenton reagent bag |
| CN105860988A (en) * | 2016-06-06 | 2016-08-17 | 佛山市聚成生化技术研发有限公司 | Method for preparing degradable soil improvement chelating agent and prepared degradable soil improvement chelating agent |
| CN106830622A (en) * | 2017-03-03 | 2017-06-13 | 中山朗清膜业有限公司 | A kind of sludge conditioner and dehydration method based on zero-valent iron-silicate system |
| CN106903158A (en) * | 2017-03-03 | 2017-06-30 | 武汉大学 | A kind of Soil oxidation solidification and stabilization repairs medicament and its application method |
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| CN109675562A (en) * | 2018-12-26 | 2019-04-26 | 浙江益壤环保科技有限公司 | The preparation method and applications of one type Fenton catalysis material |
| CN112429829A (en) * | 2020-10-28 | 2021-03-02 | 暨南大学 | Reactivation stabilized layered ferric hydroxide and preparation method and application thereof |
| CN118926294A (en) * | 2023-05-09 | 2024-11-12 | 哈尔滨工业大学（深圳） | A method for enhancing the degradation of pollutants by active oxygen from soil microorganisms |
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