CN111495958A - Contaminated soil remediation method - Google Patents
Contaminated soil remediation method Download PDFInfo
- Publication number
- CN111495958A CN111495958A CN202010350168.0A CN202010350168A CN111495958A CN 111495958 A CN111495958 A CN 111495958A CN 202010350168 A CN202010350168 A CN 202010350168A CN 111495958 A CN111495958 A CN 111495958A
- Authority
- CN
- China
- Prior art keywords
- soil
- leaching
- transition metal
- oxidation catalyst
- macrocyclic ligand
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
Abstract
The invention relates to a method for restoring polluted soil, which comprises the following steps: and (3) treating the polluted soil by combining a transition metal tetra-amido macrocyclic ligand oxidation catalyst and an oxidant in a leaching mode or a non-leaching mode to remove pollutants in the soil. The repairing agent of the repairing method has lower integral consumption and can be degraded or recycled, and secondary pollution caused by introducing new pollutants into a reaction system can be avoided; the method can efficiently and greenly remove pollutants in soil, particularly cyanogen, has strong adaptability, wide application range and simple operation, does not need to add any filler or carrier, solves the problems of difficult operation, long reaction period, high treatment cost, large occupied area and the like in the prior art, and is easy to realize industrialized application.
Description
Technical Field
The invention belongs to the technical field of soil remediation, and particularly relates to a remediation method of contaminated soil.
Background
With the rapid development of modern society, natural environmental pollution becomes the key point of social attention, and the problem of soil pollution is highly valued by various social circles. Soil pollution can not only destroy the original soil property, but also directly affect the growth, development and reproduction of animals and plants, and finally affect human health, so that the remediation of the soil pollution becomes an important research field. The purpose of contaminated soil remediation is to remove contaminants, restore soil properties, and reuse them. The choice of soil pollution remediation technology is influenced by many factors: environmental conditions, pollutant source and toxicity, current and potential harm of pollutants, whether secondary pollution is caused, physical and chemical properties of soil, land use properties, effective period of remediation, public acceptance, cost effectiveness, and the like. Therefore, in practical application, an appropriate technical method needs to be selected according to practical situations.
At present, the soil remediation mainly adopts the following methods: firstly, soil solidification and stabilization: the stabilized material is adopted to fix the pollutants in the soil in the original soil, so that the pollutants can be in a stable state for a long time without diffusion, transfer and property change, and the surrounding environment is not influenced. The method changes the soil structure, leads to soil consolidation, loses the soil function and the production and cultivation capacity, and further destroys the soil ecological environment system. Second, chemical extraction techniques: the polluted soil is extracted by the chemical extracting agent, the main defects are high cost and easy secondary pollution, after the pollutants are extracted by the extracting agent, the highly concentrated wastewater needs to be subjected to advanced treatment, and the subsequent treatment cost is high. Third, soil mixing/dilution techniques: the method mainly adopts clean soil to replace or partially replace polluted soil, reduces the concentration of pollutants to be below the critical hazard concentration by simply covering or stirring and uniformly mixing, reduces the contact of the pollutants and plant roots by mixing and diluting, and reduces the pollutants from entering a food chain. Fourthly, chemical leaching repair technology: the pollutants are leached and concentrated into leaching water through the leaching agent, organic pollutants in the leaching agent water are treated through a chemical technology, at present, the common chemical methods include oxidation methods, such as fenton, ozone, chlorine, potassium permanganate and other chemical oxidation technologies, the degradation efficiency is low, and for example, the chlorine treatment technology has high toxicity of byproducts. Meanwhile, the Fenton technology is used for repairing polluted soil, but due to the defects of large sludge production, low efficiency, easy decomposition, high energy consumption and the like, the selectivity of the reaction is low. The use of expensive chemical leaching agents not only causes secondary pollution problems, but also leads to significant increases in engineering costs.
CN110330978A discloses a soil remediation agent and a remediation method of contaminated soil. The raw materials for preparing the soil remediation agent mainly comprise nano phosphate, modified silicon-containing minerals, industrial wastes, magnesium compounds and a pH regulator. The modified silicon-containing mineral is a modified silicon-containing mineral, and the modified substance is one of ferric salt and an amino coupling agent; the nano phosphate mainly refers to hydroxyapatite, calcium phosphate and calcium hydrophosphate; the industrial waste mainly refers to coal ash, fly ash and red mud; the pH regulator mainly refers to calcium oxide, calcium hydroxide and calcium carbonate. The raw materials in the soil remediation agent are matched with each other, so that after the soil remediation agent is applied to soil, in-situ solidification of heavy metals can be realized through various modes such as adsorption, surface complexation, ion exchange, coprecipitation and the like, the solidification efficiency is high, and the soil remediation agent is insoluble powder, and can stably act on the soil without loss after being applied to the soil, and the soil remediation agent can form stable substances with the heavy metals, so that the stability of the soil remediation agent is good.
CN110746976A discloses a soil remediation agent for passivating soil heavy metals and a preparation method thereof. The soil restoration agent with high-efficiency restoration effect on soil heavy metal is obtained by mixing biochar, bentonite and magnesium oxide together according to a specific dosage proportion, wherein the biochar is a porous carbonaceous material obtained by cracking and sieving any one of crop straws or crop seed shells at high temperature. The three components are combined together according to a specific proportion, have a synergistic passivation effect on the soil heavy metal, and particularly can efficiently reduce the effective state content of the heavy metal cadmium in the soil, and the effective state cadmium content can be reduced by 55-60% within one month. The soil remediation agent for remediating the heavy metal contaminated soil has the advantages of low remediation cost, simple operation, convenient maintenance and the like.
CN110479756A discloses a soil remediation process, which comprises the steps of mixing soil to be remediated, an anionic surfactant and water, carrying out ultrasonic dispersion, carrying out freeze pressing and thawing to obtain thawed slurry, mixing the thawed slurry, dodecyl acrylamide, polyethylene glycol phosphate, a tackifier and polyethylene oxide, carrying out high-viscosity kneading and discharging to obtain a kneaded material, treating the kneaded material under the action of an electric field for 2-4 hours, transferring the kneaded material into a mixer, introducing fast drying carbon dioxide gas under the stirring state until the water content of the material in the mixer is reduced to below 5%, carrying out cyclone separation on the material in the mixer, and removing fine particles to complete the remediation of the soil. The invention solves the problems that the conventional repair process for the heavy metal contaminated soil has poor repair effect, is difficult to destroy the heavy metal-colloid stable state in the soil and cannot improve the structure of the soil.
Although some polluted soil remediation processes are provided in the prior art, the problems that the cyanogen pollution is difficult to reach the standard in the traditional treatment technology, the running cost of the traditional technology is ultrahigh, the problem of heavy pollutant-containing environmental load caused by soil treatment is serious, the process flow is long, the construction investment is large, the stability is poor, the adaptability to external temperature is poor, the secondary pollution is caused, the new water supplement amount is large, the double waste of water resources and the cost is caused, the stability of the remediation agent is poor and the like exist. Therefore, the development of the polluted soil remediation process which is simple and convenient to operate, remarkable in economic and energy-saving performance, good in environmental adaptation, strong in stability and high in polluted soil remediation efficiency is of great significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polluted soil remediation method, which is an efficient and green polluted soil in-situ remediation or ex-situ remediation technology, can efficiently and green remove pollutants, especially cyanogen, in soil, and solves the problems of difficult operation, long reaction period, high treatment cost, large occupied area and the like in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for repairing polluted soil, which comprises the following steps: and (3) treating the polluted soil by combining a transition metal tetra-amido macrocyclic ligand oxidation catalyst and an oxidant in a leaching mode or a non-leaching mode to remove pollutants in the soil.
The invention relates to a method for restoring polluted soil, which is a high-efficiency green technology for restoring polluted soil in situ or ex situ, and establishes a brand-new method for active group conversion, multiple deep active groups and step-by-step progressive treatment according to the principles of active structures, substance affinity and the like under the guidance of the theories of heterogeneous catalysis, composite oxidation, targeted removal and the like. The transition metal tetra-amido macrocyclic ligand oxidation catalyst has the characteristics of direct oxidation and indirect oxidation, generates nonspecific hydroxyl free radicals, has strong oxidation activity, high efficiency of removing pollutants by oxidation and wide pH range, not only has high catalytic oxidation activity, but also has increased indirect oxidation efficiency when being used together with other oxidants such as hydrogen peroxide, ozone, chlorine, sodium persulfate and the like for reaction. The whole dosage is lower, the catalyst can be degraded or recycled, and secondary pollution caused by introducing new pollutants into a reaction system is avoided; the method can efficiently and greenly remove pollutants in soil, particularly cyanogen, has strong adaptability, wide application range and simple operation, does not need to add any filler or carrier, solves the problems of difficult operation, long reaction period, high treatment cost, large occupied area and the like in the prior art, and is easy to realize industrialized application.
Preferably, the contaminant comprises any one or a combination of at least two of free cyanogen, complex cyanogen, cyanogen derivatives or polycyclic aromatic hydrocarbons; the combination of at least two of the compounds, such as the combination of free cyanogen and complex cyanogen, the combination of complex cyanogen and a cyanogen derivative, the combination of a cyanogen derivative and polycyclic aromatic hydrocarbon, can be selected in any combination manner, and is not repeated herein.
The method for repairing the polluted soil has the advantages of being superior to most pollutants, particularly to double-bond and triple-bond characteristic pollutants which are difficult to eliminate, good in removing effect and good in market application prospect.
Preferably, the oxidizing agent comprises any one or a combination of at least two of hydrogen peroxide, ozone, an oxy-chloro compound, sodium persulfate, calcium peroxide or potassium permanganate; the combination of at least two of the above-mentioned compounds, such as the combination of hydrogen peroxide and ozone, the combination of sodium persulfate and calcium peroxide, the combination of sodium persulfate and hydrogen peroxide, etc., can be selected in any combination manner, and will not be described in detail herein.
When a transition metal tetraamido macrocyclic ligand oxidation catalyst is used in combination with hydrogen peroxide, the reaction mechanism is roughly: when the transition metal tetra-amido macrocyclic ligand oxidation catalyst is added into a working reaction liquid system, a water molecule is connected to the axial direction of the active center of the metal of the catalyst, when hydrogen peroxide exists in the aqueous solution, the water molecule can be replaced, then a hydrogen atom and a hydroxyl group are removed by the peroxide, an oxygen atom is left to be connected to a catalytic site atom, and the oxygen which attracts electrons is far away from the active center atom, so that the catalyst ligand is changed into a high-activity reaction intermediate, other substrates can be rapidly and almost completely degraded into nontoxic substances, and a part of the non-toxic substances is completely mineralized into CO2Inorganic form of (2), discharge system. Hydrogen peroxide has three functions: firstly, hydrogen peroxide is easily adsorbed on the surface of passivated soil, and macromolecules such as humus in a passivation film are oxidized, so that dissolubles are generated to dissolve the passivated soil; secondly, the method is beneficial to improving the permeability of soil, improving mass transfer and reducing energy consumption; the secondary hydrogen peroxide is used as indirect oxidation, generates hydroxyl free radicals in the chemical catalytic oxidation process and plays a very important role in the oxidation process.
When a transition metal tetraamido macrocyclic ligand oxidation catalyst is used in combination with sodium persulfate, the reaction mechanism is roughly: catalytic oxidation of persulfate, SO, via transition metal tetra-amido macrocyclic ligands4 -The ability to produce HO with HO in the system significantly enhances the oxidation capacity and processing efficiency, enabling rapid oxidative processing of triple bond containing compounds or refractory materials. The main oxidation reaction of DY6 and sodium persulfate system generates O2S8 2-→SO4 -The oxidation reaction chain → HO, makes effective use of the highly active free radicals, which is beneficial to the reaction of the oxidation catalyst and sodium persulfate to generate the active substance with higher activity in oxidation state, thereby greatly improving the removal of cyanogen pollutants in the soil.
In the invention, the specific method for treating the polluted soil by combining the transition metal tetra-amido macrocyclic ligand oxidation catalyst and the oxidant in a leaching manner comprises the following steps:
and leaching the polluted soil by using a leaching agent to obtain leaching waste liquid, and adding a transition metal tetra-amido macrocyclic ligand oxidation catalyst and an oxidant into the leaching waste liquid for reaction.
The leaching mode is actually an ex-situ remediation mode, pollutants in the soil are completely transferred into the leaching waste liquid in the leaching mode, and then the pollutants are removed from the leaching waste liquid.
Preferably, the eluent comprises any one or at least two of citric acid, ethylene diamine tetraacetic acid, hydroxyethyl ethylene diamine acetic acid, ammonium acetate or water; the combination of at least two of the above-mentioned compounds, such as the combination of citric acid and ethylenediamine tetraacetic acid, the combination of hydroxyethylethylenediamine tetraacetic acid and ammonium acetate, the combination of ammonium acetate and water, etc., and any other combination mode can be selected, and thus, the description thereof is omitted.
Preferably, the volume ratio of the eluting agent to the contaminated soil is (5-50):1, such as 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1 or 50:1, and preferably (20-30):1, and any specific value in the above range can be selected, and is not described in detail herein.
Preferably, the number of rinses is 1-10, such as 1,2, 3, 4, 5, 7, 10, etc.
Preferably, the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the leaching waste liquid is 1-50 μmol/L, such as 1 μmol/L, 10 μmol/L, 20 μmol/L, 30 μmol/L, 40 μmol/L or 50 μmol/L, and preferably 10-20 μmol/L, and any specific value in the above range can be selected, and is not repeated herein.
Preferably, the concentration of the oxidant in the leaching waste liquid is 5-60 g/L, such as 5 g/L, 10 g/L, 20 g/L, 30 g/L, 40 g/L, 50 g/L or 60 g/L, and preferably 20-40 g/L, and any specific value in the above range can be selected, and is not repeated herein.
The mass ratio of the transition metal tetraamido macrocyclic ligand oxidation catalyst to the oxidizing agent is preferably 1 (1000-) 3000, for example 1:1000, 1:1300, 1:1500, 1:1900, 1:2200, 1:2500, 1:2800 or 1:3000, and more preferably 1 (1300-) 2200.
Preferably, the oxidizing agent is hydrogen peroxide.
When the oxidant is hydrogen peroxide, the leaching mode is preferably selected to repair the soil, because the hydrogen peroxide is volatile, and if the non-leaching mode is adopted to repair the soil, the utilization rate of the hydrogen peroxide is not high.
Preferably, the reaction temperature is 6-40 ℃, such as 6 ℃, 10 ℃, 18 ℃, 30 ℃, 35 ℃ or 40 ℃, preferably 18-30 ℃, and any specific value in the above range can be selected, and is not repeated herein.
The reaction device is preferably a constant temperature oscillating water bath.
Preferably, the reaction time is 60-240min, such as 60min, 100min, 120min, 150min, 180min or 240min, and preferably 120-180min, and any specific value in the above range can be selected, and is not repeated herein.
Preferably, the reaction is carried out at a pH of 7 to 14, for example, pH 7, 8, 9, 10, 11, 12, 13 or 14, preferably 10 to 11, and any specific value within the above range may be selected, and will not be described herein again.
Here the spent leaching solution is treated to remove most of the contaminants and can be reused as a leaching agent for soil leaching.
As a preferred technical scheme of the invention, the specific method for treating the polluted soil by combining the transition metal tetra-amido macrocyclic ligand oxidation catalyst and the oxidant in a leaching manner comprises the following steps:
leaching the soil for 1-10 times by using a leaching agent with the volume 5-50 times that of the polluted soil to obtain leaching waste liquid, adding a transition metal tetraamido macrocyclic ligand oxidation catalyst and an oxidant into the leaching waste liquid, enabling the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the leaching waste liquid to be 1-50 mu mol/L, enabling the concentration of the oxidant in the leaching waste liquid to be 5-60 g/L, and reacting for 60-240min at the temperature of 6-40 ℃ and the pH value of 7-14.
The concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the leaching waste liquid is specially selected to be 1-50 mu mol/L, and the concentration of the oxidant in the leaching waste liquid is specially selected to be 5-60 g/L, so that the soil remediation effect is better, wherein 10-20 mu mol/L and 20-40 g/L are ranges with better effects.
In the invention, the specific method for treating the polluted soil by combining the transition metal tetra-amido macrocyclic ligand oxidation catalyst and the oxidant in a non-leaching manner comprises the following steps:
the polluted soil is mixed with the oxidation catalyst of the transition metal tetra-amido macrocyclic ligand and the oxidant, stirred and reacted.
Preferably, the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in soil is 5-50 μmol/kg, such as 5 μmol/kg, 6 μmol/kg, 10 μmol/kg, 20 μmol/kg, 30 μmol/kg, 40 μmol/kg or 50 μmol/kg, etc., preferably 6-20 μmol/kg, and any specific value within the above range can be selected, and thus, the detailed description is omitted.
Preferably, the concentration of the oxidant in the soil is 5-40g/kg, such as 5g/kg, 10g/kg, 20g/kg, 25g/kg, 30g/kg or 40g/kg, etc., preferably 10-20g/kg, and any specific value within the above range can be selected, and is not repeated herein.
Preferably, the reaction temperature is 8-38 ℃, such as 8 ℃, 10 ℃, 15 ℃, 25 ℃ or 38 ℃, preferably 10-25 ℃, and any specific value in the above range can be selected, and is not repeated herein.
Preferably, the reaction time is 12-120h, for example, 12h, 18h, 24h, 30h, 36h, 42h, 48h, 54h, 60h or 72h, and the like, and preferably 48-72h, and any specific value within the above range can be selected, and is not repeated herein.
Preferably, the reaction is carried out at a pH of 7 to 14, for example, pH 7, 8, 9, 10, 11, 12, 13 or 14, preferably 10 to 11, and any specific value within the above range may be selected, and will not be described herein again.
As a preferred technical scheme of the invention, the specific method for treating the polluted soil by combining the transition metal tetra-amido macrocyclic ligand oxidation catalyst and the oxidant in a non-leaching way comprises the following steps:
mixing the polluted soil with a transition metal tetraamido macrocyclic ligand oxidation catalyst and an oxidant, wherein the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the soil is 5-50 mu mol/kg, the concentration of the oxidant in the soil is 5-40g/kg, stirring uniformly, and reacting for 12-120h at the temperature of 8-38 ℃ and the pH value of 7-14.
The concentration of the transition metal tetra-amido macrocyclic ligand oxidation catalyst in the soil is specifically selected to be 5-50 mu mol/kg, and the concentration of the oxidant in the soil is specifically selected to be 5-40g/kg, so that the soil remediation effect is better, wherein 6-20 mu mol/L and 10-20 g/L are ranges with better effects.
The transition metal tetraamido macrocyclic ligand oxidation catalysts mentioned in the present invention may be exemplified by, but not limited to, compounds of the following structure:
wherein R is selected from any one of hydrogen, methyl, ethyl, cyclopropyl or methoxy;
r' is independently selected from any one of methyl, ethyl, cyclopropyl or methoxy;
n is selected from any integer of 0-4, and when n is more than or equal to 2, R' are the same or different;
m is selected from transition metals such as iron, copper, cobalt, nickel, zinc, manganese and the like.
The preparation method of the compound represented by formula (a) may be exemplified by, but not limited to:
(1) adding triethylamine into an ethanol solution in a round-bottom flask, dissolving a compound shown as a formula (I) in the ethanol solution dissolved with the triethylamine, heating in a water bath kettle at 60 ℃, and stirring by adopting magnetic force under reflux to obtain a mixed solution A; in another round-bottom flask, the compound represented by the formula (II) and dicycloethylcarbodiimide were mixed in an ethanol solution to obtain a mixed solution B.
(2) Dropwise adding the mixed solution B into the mixed solution A at the speed of 1 drop in 2 seconds, stirring at the speed of 800rpm for 5 hours, dropwise adding hydrochloric acid with the concentration of 10.2 mol/L into the solution while stirring at the speed of 600rpm, stirring the solution for 4 hours after the addition is finished, and standing and precipitating for 24 hours.
(3) And (3) dropwise adding deionized water into the solution until the top layer of the crystal is dissolved, filtering the solution in vacuum through a sintered funnel, and washing by using an ethanol water solution as a flushing agent until the crystal is completely changed from orange to white, namely the tetraamido macrocyclic ligand.
(4) Weighing the synthesized tetra-acylamino macrocyclic ligand, putting the tetra-acylamino macrocyclic ligand into a Schlenk bottle, simultaneously adding tetrahydrofuran subjected to water removal through distillation, stirring, introducing nitrogen as protective gas, then quickly adding n-butyl lithium, keeping an ice water bath and stirring for 15min, then removing the ice water bath, and stirring for 15min at 25 ℃.
(5) Adding a transition metal salt solution into the system, stirring for 12h at the rotating speed of 500rpm, closing the nitrogen protection, continuously stirring for 3h in the air, filtering to obtain a solid, and washing for 5 times by using dichloromethane to finally obtain the transition metal tetraamido macrocyclic ligand oxidation catalyst shown in the formula (A).
Wherein R is1、R2、R3、R4Independently selected from any one of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, alkynyl, alkoxy, phenoxy or halogen;
m is selected from transition metals such as iron, copper, cobalt, nickel, zinc, manganese and the like;
as a method for producing the compound represented by the formula (B), for example, but not by limitation, the method described in patent No. 201610147534.6 can be referred.
In addition, the tetraamido macrocyclic ligand metal complexes disclosed in patent documents CN1844128, US5298618, US6127536, US6384279, US5853428 and the like can be used as oxidation catalysts of transition metal tetraamido macrocyclic ligands in accordance with the present invention.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method for repairing the polluted soil has good adaptability, and can adapt to the dynamic changes of various pollutants of high, medium and low levels; the external environment has good adaptability and can stably run under the conditions of wider temperature and wider pH.
(2) The method has the advantages that the integral dosage of the oxidant and the oxidation catalyst is lower, the oxidant and the oxidation catalyst can be degraded or recycled, and secondary pollution caused by introducing new pollutants into a reaction system is avoided.
(3) The method can efficiently and greenly remove pollutants in soil, particularly cyanogen, is simple to operate, does not need any filler or carrier, has the highest total cyanogen removal rate of 98.0-99.4 percent, solves the problems of difficult operation, long reaction period, high treatment cost, large occupied area and the like in the prior art, and is easy to realize industrial application.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following further describes the technical solution of the present invention with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
The contaminated soil samples used in the following specific examples are provided by the heavy mechanization ltd of chemical engineering in china, and are cyanide-contaminated soil in a field, and the characteristic contaminants of the contaminated soil mainly contain cyanide, polycyclic aromatic hydrocarbon, hexachlorobenzene and other organic matters. The same contaminated soil samples were used as in examples 1-8 below, and the cyanogen contamination concentration was 8.3mg/kg as determined by spectrophotometric assay; the contaminated soil samples used in examples 9-17 were identical and were tested for cyanogen contamination at a concentration of 13.7 mg/kg.
Preparation example 1
The preparation example provides a transition metal tetra-amido macrocyclic ligand oxidation catalyst, which is prepared by the following method:
(1) in a 500m L round bottom flask, 70m L of triethylamine was added to an ethanol solution, the volume was adjusted to 300m L with the ethanol solution, 28g of 1, 2-o-phenylenediamine was dissolved in the above ethanol solution in which triethylamine was dissolved, heating was carried out in a water bath at 60 ℃ under reflux with magnetic stirring at 800rpm to obtain a mixed solution A, and in another 500m L round bottom flask, 52g of dimethylmalonic acid and 211.5g of dicycloethylcarbodiimide were mixed in a 300m L ethanol solution to obtain a mixed solution B.
(2) Dropwise adding the mixed solution B into the mixed solution A at the speed of 1 drop in 2 seconds, stirring at the speed of 800rpm for 5 hours, dropwise adding 100m of hydrochloric acid with the concentration of L being 10.2 mol/L into the solution while stirring at the speed of 600rpm, stirring the solution for 4 hours after the addition is finished, and standing and precipitating for 24 hours.
(3) Dropwise adding deionized water into the solution until the top layer of the crystal is dissolved, filtering the solution in a sintered funnel in vacuum, and cleaning the solution by using a solution of ethanol and deionized water in a ratio of 1:5 as a flushing agent until the crystal is completely changed from orange to white, namely the tetraamido macrocyclic ligand.
(4) Weighing 4.06g of the synthesized tetra-acylamino macrocyclic ligand, putting the ligand in a Schlenk bottle with the diameter of 500m L, adding tetrahydrofuran with the diameter of 160m L and distilled water, stirring at the rotation speed of 500rpm, introducing nitrogen as protective gas with the flow rate of 100m L/min, then rapidly adding 10m L n-butyllithium, keeping the ice-water bath stirring for 15min, removing the ice-water bath, and stirring at the temperature of 25 ℃ for 15 min.
(5) Adding 1.5g of anhydrous ferrous chloride into the system, stirring for 12h at the rotating speed of 500rpm, closing the nitrogen protection, continuously stirring for 3h in the air, filtering to obtain a solid, and washing for 5 times by using dichloromethane to finally obtain the oxidation catalyst of the iron tetraamido macrocyclic ligand with the following structure.
Example 1
The embodiment provides a method for repairing contaminated soil, which comprises the following steps:
restoring soil by adopting a leaching mode, leaching the soil for 3 times by using tap water, wherein the tap water with the volume 20 times that of the soil is used for leaching each time to obtain leaching waste liquid, adding the transition metal tetraamido macrocyclic ligand oxidation catalyst prepared in the preparation example 1 and hydrogen peroxide into the leaching waste liquid to ensure that the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the leaching waste liquid is 15 mu mol/L and the concentration of the hydrogen peroxide in the leaching waste liquid is 25 g/L, reacting for 150min at 25 ℃ and the pH value of 10.5, detecting the concentration of residual cyanogen in a soil sample by using a spectrophotometer after the reaction is finished, and calculating the removal rate.
Example 2
The embodiment provides a method for repairing contaminated soil, which comprises the following steps:
restoring soil by adopting a leaching mode, leaching the soil for 5 times by using tap water, wherein the tap water with the volume 20 times that of the soil is used for leaching each time to obtain leaching waste liquid, adding the transition metal tetraamido macrocyclic ligand oxidation catalyst prepared in the preparation example 1 and hydrogen peroxide into the leaching waste liquid to ensure that the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the leaching waste liquid is 10 mu mol/L and the concentration of the hydrogen peroxide in the leaching waste liquid is 40 g/L, reacting for 180min at 20 ℃ and the pH value of 8.5, detecting the concentration of residual cyanogen in a soil sample by using a spectrophotometer after the reaction is finished, and calculating the removal rate.
Example 3
The embodiment provides a method for repairing contaminated soil, which comprises the following steps:
restoring soil by adopting a leaching mode, leaching the soil for 3 times by using tap water, wherein the tap water with the volume 30 times that of the soil is used for leaching each time to obtain leaching waste liquid, adding the transition metal tetraamido macrocyclic ligand oxidation catalyst prepared in the preparation example 1 and hydrogen peroxide into the leaching waste liquid to ensure that the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the leaching waste liquid is 20 mu mol/L and the concentration of the hydrogen peroxide in the leaching waste liquid is 20 g/L, reacting for 60min at 30 ℃ and the pH value of 13, detecting the concentration of residual cyanogen in a soil sample by using a spectrophotometer after the reaction is finished, and calculating the removal rate.
Example 4
This example provides a method for remediating contaminated soil, which differs from example 1 only in that "the reaction is carried out at 25 ℃" is replaced with "the reaction is carried out at 0 ℃, and other conditions are kept unchanged. And after the reaction is finished, detecting the concentration of residual cyanogen in the soil sample by using a spectrophotometer, and calculating the removal rate.
Example 5
This example provides a method for remediating contaminated soil, which differs from example 1 only in that "the reaction is carried out at 25 ℃" is replaced with "the reaction is carried out at 60 ℃, and other conditions are kept unchanged. And after the reaction is finished, detecting the concentration of residual cyanogen in the soil sample by using a spectrophotometer, and calculating the removal rate.
Example 6
This example provides a method for remediating contaminated soil, which is different from example 1 only in that "the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the elution waste liquid is 15 μmol/L" is replaced with "the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the elution waste liquid is 1 μmol/L", and other conditions are kept unchanged.
Example 7
This example provides a method for remediating contaminated soil, which is different from example 1 only in that "the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the elution waste liquid is 15 μmol/L" is replaced with "the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the elution waste liquid is 50 μmol/L", and other conditions are kept unchanged.
Example 8
This example provides a method for remediating contaminated soil, which differs from example 1 only in that "reacting at pH 10.5" is replaced with "reacting at pH 5.5", and the other conditions are maintained. And after the reaction is finished, detecting the concentration of residual cyanogen in the soil sample by using a spectrophotometer, and calculating the removal rate.
Example 9
The embodiment provides a method for repairing contaminated soil, which comprises the following steps:
the soil was remediated by a non-leaching method, and the contaminated soil was mixed with the transition metal tetraamido macrocyclic ligand oxidation catalyst prepared in preparation example 1 and sodium persulfate so that the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the soil was 16 μmol/kg and the concentration of the oxidant in the soil was 10g/kg, and the mixture was stirred uniformly and reacted at 15 ℃ and a pH of 11 for 60 hours.
Example 10
The embodiment provides a method for repairing contaminated soil, which comprises the following steps:
the soil was remediated by a non-leaching method, and the contaminated soil was mixed with the transition metal tetraamido macrocyclic ligand oxidation catalyst prepared in preparation example 1 and sodium persulfate so that the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the soil was 6 μmol/kg and the concentration of the oxidant in the soil was 20g/kg, and the mixture was stirred uniformly and reacted at 10 ℃ and a pH of 7.5 for 72 hours.
Example 11
The embodiment provides a method for repairing contaminated soil, which comprises the following steps:
the soil was remediated by a non-leaching method, and the contaminated soil was mixed with the transition metal tetraamido macrocyclic ligand oxidation catalyst prepared in preparation example 1 and sodium persulfate so that the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the soil was 20 μmol/kg and the concentration of the oxidant in the soil was 10g/kg, and the mixture was stirred uniformly and reacted at 30 ℃ and pH 13 for 60 hours.
Example 12
This example provides a method for remediating contaminated soil, which differs from example 9 only in that "the reaction is carried out at 25 ℃" is replaced with "the reaction is carried out at 8 ℃, and other conditions are kept unchanged. And after the reaction is finished, detecting the concentration of residual cyanogen in the soil sample by using a spectrophotometer, and calculating the removal rate.
Example 13
This example provides a method for remediating contaminated soil, which differs from example 9 only in that "the reaction is carried out at 25 ℃" is replaced with "the reaction is carried out at 8 ℃, and other conditions are kept unchanged. And after the reaction is finished, detecting the concentration of residual cyanogen in the soil sample by using a spectrophotometer, and calculating the removal rate.
Example 14
This example provides a method for remediating contaminated soil, which differs from example 9 only in that "the reaction is carried out at 25 ℃" is replaced with "the reaction is carried out at 38 ℃, and other conditions are kept unchanged. And after the reaction is finished, detecting the concentration of residual cyanogen in the soil sample by using a spectrophotometer, and calculating the removal rate.
Example 15
This example provides a remediation method for contaminated soil, which differs from example 9 only in that "the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in soil is made to be 16. mu. mol/kg" is replaced with "the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in soil is made to be 5. mu. mol/kg", and the other conditions are kept unchanged. And after the reaction is finished, detecting the concentration of residual cyanogen in the soil sample by using a spectrophotometer, and calculating the removal rate.
Example 16
This example provides a remediation method for contaminated soil, which differs from example 9 only in that "the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in soil is made 16. mu. mol/kg" is replaced with "the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in soil is made 50. mu. mol/kg", and the other conditions are kept unchanged. And after the reaction is finished, detecting the concentration of residual cyanogen in the soil sample by using a spectrophotometer, and calculating the removal rate.
Example 17
This example provides a method for remediating contaminated soil, which differs from example 9 only in that "reacting at pH 10.5" is replaced with "reacting at pH 5.5", and all other conditions are maintained. And after the reaction is finished, detecting the concentration of residual cyanogen in the soil sample by using a spectrophotometer, and calculating the removal rate.
The results of the calculations for examples 1-17 are summarized in Table 1:
TABLE 1
As can be seen from the data in Table 1: the method for repairing the polluted soil can adopt a leaching mode or a non-leaching mode for treatment; can adapt to the dynamic change of various pollutants of high, medium and low levels; the adaptability of the external environment is good, and the device can stably operate under a wider temperature condition and a wider pH condition; the method has the advantages that the integral using amount of the oxidant and the oxidation catalyst is low, and the cost is reduced; the method can efficiently and greenly remove the pollutant cyanogen in the soil, is simple to operate, does not need any filler or carrier, and has a total cyanogen removal rate of 98.0-99.4% at most, wherein the removal rate can be influenced by the compounding rate of an oxidation catalyst and an oxidant, the reaction temperature, the pH environment and the like.
The applicant states that the present invention is described in the above examples as a method for remediating contaminated soil, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (10)
1. A remediation method for contaminated soil, the remediation method comprising: and (3) treating the polluted soil by combining a transition metal tetra-amido macrocyclic ligand oxidation catalyst and an oxidant in a leaching mode or a non-leaching mode to remove pollutants in the soil.
2. The method for remediating contaminated soil according to claim 1, wherein the contaminants comprise any one of free cyanogen, complex cyanogen, cyanogen derivatives, or polycyclic aromatic hydrocarbons, or a combination of at least two thereof.
3. The method for remediating contaminated soil as claimed in claim 1 or 2, wherein said oxidizing agent comprises any one of hydrogen peroxide, ozone, an oxy-chloro compound, sodium persulfate, calcium peroxide, or potassium permanganate, or a combination of at least two thereof.
4. The method for remediating contaminated soil as set forth in any one of claims 1 to 3, wherein said step of treating the contaminated soil with the transition metal tetraamido macrocyclic ligand oxidation catalyst in combination with the oxidizing agent in a leaching manner comprises:
and leaching the polluted soil by using a leaching agent to obtain leaching waste liquid, and adding a transition metal tetra-amido macrocyclic ligand oxidation catalyst and an oxidant into the leaching waste liquid for reaction.
5. The method for remediating contaminated soil according to claim 4, wherein the eluent comprises any one or a combination of at least two of citric acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediamineacetic acid, ammonium acetate, or water;
preferably, the volume ratio of the eluting agent to the polluted soil is (5-50) to 1, preferably (20-30) to 1;
preferably, the number of times of leaching is 1-10 times;
preferably, the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the spent leach liquor is from 1 to 50 μmol/L, preferably from 10 to 20 μmol/L;
preferably, the concentration of the oxidant in the leaching waste liquid is 5-60 g/L, preferably 20-40 g/L;
preferably, the oxidizing agent is hydrogen peroxide.
6. A method for remediating contaminated soil as claimed in claim 4 or 5, wherein the temperature of the reaction is 6-40 ℃, preferably 18-30 ℃;
preferably, the reaction time is 60-240min, preferably 120-180 min;
preferably, the reaction is carried out at a pH of 7 to 14, preferably 10 to 11.
7. The method for remediating contaminated soil as set forth in any one of claims 4 to 6, wherein said treating contaminated soil with a transition metal tetraamido macrocyclic ligand oxidation catalyst in combination with an oxidizing agent in a leaching manner comprises:
leaching the soil for 1-10 times by using a leaching agent with the volume 5-50 times that of the polluted soil to obtain leaching waste liquid, adding a transition metal tetraamido macrocyclic ligand oxidation catalyst and an oxidant into the leaching waste liquid, enabling the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the leaching waste liquid to be 1-50 mu mol/L, enabling the concentration of the oxidant in the leaching waste liquid to be 5-60 g/L, and reacting for 60-240min at the temperature of 6-40 ℃ and the pH value of 7-14.
8. The method of remediating contaminated soil as recited in any one of claims 1 to 3, wherein said treating contaminated soil with a transition metal tetraamido macrocyclic ligand oxidation catalyst in combination with an oxidizing agent in a non-leaching manner comprises:
the polluted soil is mixed with the oxidation catalyst of the transition metal tetra-amido macrocyclic ligand and the oxidant, stirred and reacted.
9. The method for remediating contaminated soil as claimed in claim 8, wherein the concentration of said transition metal tetraamido macrocyclic ligand oxidation catalyst in the soil is 5-50 μmol/kg, preferably 6-20 μmol/kg;
preferably, the concentration of the oxidant in the soil is 5-40g/kg, preferably 10-20 g/kg;
preferably, the oxidizing agent is sodium persulfate;
preferably, the temperature of the reaction is 8-38 ℃, preferably 10-25 ℃;
preferably, the reaction time is 12-120h, preferably 48-72 h;
preferably, the reaction is carried out at a pH of 7 to 14, preferably 10 to 11.
10. The method for remediating contaminated soil as set forth in claim 8 or 9, wherein said treating contaminated soil with a transition metal tetraamido macrocyclic ligand oxidation catalyst in combination with an oxidizing agent in a non-leaching manner comprises:
mixing the polluted soil with a transition metal tetraamido macrocyclic ligand oxidation catalyst and an oxidant, wherein the concentration of the transition metal tetraamido macrocyclic ligand oxidation catalyst in the soil is 5-50 mu mol/kg, the concentration of the oxidant in the soil is 5-40g/kg, stirring uniformly, and reacting for 12-120h at the temperature of 8-38 ℃ and the pH value of 7-14.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010350168.0A CN111495958A (en) | 2020-04-28 | 2020-04-28 | Contaminated soil remediation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010350168.0A CN111495958A (en) | 2020-04-28 | 2020-04-28 | Contaminated soil remediation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111495958A true CN111495958A (en) | 2020-08-07 |
Family
ID=71878145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010350168.0A Pending CN111495958A (en) | 2020-04-28 | 2020-04-28 | Contaminated soil remediation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111495958A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112157120A (en) * | 2020-08-25 | 2021-01-01 | 中国科学院烟台海岸带研究所 | Method and device for repairing soil by solubilizing and increasing drainage mode |
| CN113652221A (en) * | 2021-08-23 | 2021-11-16 | 南京工业大学 | Fracturing fluid for enhancing treatment efficiency of polycyclic aromatic hydrocarbon in low-permeability soil and preparation method thereof |
| CN114907856A (en) * | 2022-05-13 | 2022-08-16 | 中国科学院南京土壤研究所 | Green and efficient polycyclic aromatic hydrocarbon contaminated soil remediation eluent and application method thereof |
| CN115318791A (en) * | 2022-08-16 | 2022-11-11 | 河南理工大学 | Red mud dealkalization method realized through phase state control |
| TWI829594B (en) * | 2023-05-24 | 2024-01-11 | 國立高雄科技大學 | Mean of treating soil volatile organic pollutants and its related device |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105537254A (en) * | 2016-01-27 | 2016-05-04 | 南京农业大学 | Wastewater chemical leaching purification treatment method for repairing heavy metal contaminated soil |
| CN105689000A (en) * | 2015-12-04 | 2016-06-22 | 魏东初 | Novel tetra-amido macrocyclic ligand catalyst and preparing method thereof |
| CN106623389A (en) * | 2016-12-06 | 2017-05-10 | 天津华勘环保科技有限公司 | Remediation method for cyanide contaminated soil |
| CN108290848A (en) * | 2015-09-25 | 2018-07-17 | 卡内基美浓大学 | Super excellent oxidative catalyst based on macrocyclic compound |
| CN108380663A (en) * | 2018-04-25 | 2018-08-10 | 上海化工研究院有限公司 | The method that class Fenton oxidation method removes half volatile organic contaminant in soil |
| CN208743348U (en) * | 2018-07-30 | 2019-04-16 | 天津华勘环保科技有限公司 | Dump leaching-ozone cooperative decyanation processing system |
| WO2019083452A1 (en) * | 2017-10-25 | 2019-05-02 | National University Of Singapore | An oxidant activator |
| CN110180879A (en) * | 2019-07-02 | 2019-08-30 | 天津生态城环保有限公司 | A kind of method of cyanide polluted soil leaching reparation |
| WO2019168635A2 (en) * | 2018-03-01 | 2019-09-06 | Arkema Inc. | Soil treatment using peroxide |
-
2020
- 2020-04-28 CN CN202010350168.0A patent/CN111495958A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108290848A (en) * | 2015-09-25 | 2018-07-17 | 卡内基美浓大学 | Super excellent oxidative catalyst based on macrocyclic compound |
| CN105689000A (en) * | 2015-12-04 | 2016-06-22 | 魏东初 | Novel tetra-amido macrocyclic ligand catalyst and preparing method thereof |
| CN105537254A (en) * | 2016-01-27 | 2016-05-04 | 南京农业大学 | Wastewater chemical leaching purification treatment method for repairing heavy metal contaminated soil |
| CN106623389A (en) * | 2016-12-06 | 2017-05-10 | 天津华勘环保科技有限公司 | Remediation method for cyanide contaminated soil |
| WO2019083452A1 (en) * | 2017-10-25 | 2019-05-02 | National University Of Singapore | An oxidant activator |
| WO2019168635A2 (en) * | 2018-03-01 | 2019-09-06 | Arkema Inc. | Soil treatment using peroxide |
| CN108380663A (en) * | 2018-04-25 | 2018-08-10 | 上海化工研究院有限公司 | The method that class Fenton oxidation method removes half volatile organic contaminant in soil |
| CN208743348U (en) * | 2018-07-30 | 2019-04-16 | 天津华勘环保科技有限公司 | Dump leaching-ozone cooperative decyanation processing system |
| CN110180879A (en) * | 2019-07-02 | 2019-08-30 | 天津生态城环保有限公司 | A kind of method of cyanide polluted soil leaching reparation |
Non-Patent Citations (2)
| Title |
|---|
| 曲胜利: "《黄金冶金新技术》", 31 July 2018, 冶金工业出版社 * |
| 赵海楠 等: "锰氧化物催化氧化挥发性有机物( VOCs) 研究进展", 《环境工程》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112157120A (en) * | 2020-08-25 | 2021-01-01 | 中国科学院烟台海岸带研究所 | Method and device for repairing soil by solubilizing and increasing drainage mode |
| CN113652221A (en) * | 2021-08-23 | 2021-11-16 | 南京工业大学 | Fracturing fluid for enhancing treatment efficiency of polycyclic aromatic hydrocarbon in low-permeability soil and preparation method thereof |
| CN113652221B (en) * | 2021-08-23 | 2023-05-05 | 南京工业大学 | Fracturing fluid for enhancing treatment efficiency of polycyclic aromatic hydrocarbon in hypotonic soil and preparation method thereof |
| CN114907856A (en) * | 2022-05-13 | 2022-08-16 | 中国科学院南京土壤研究所 | Green and efficient polycyclic aromatic hydrocarbon contaminated soil remediation eluent and application method thereof |
| CN115318791A (en) * | 2022-08-16 | 2022-11-11 | 河南理工大学 | Red mud dealkalization method realized through phase state control |
| CN115318791B (en) * | 2022-08-16 | 2023-06-16 | 河南理工大学 | Red mud dealkalization method realized through phase state control |
| TWI829594B (en) * | 2023-05-24 | 2024-01-11 | 國立高雄科技大學 | Mean of treating soil volatile organic pollutants and its related device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111495958A (en) | Contaminated soil remediation method | |
| CN104628200B (en) | A kind of method utilizing photoelectric combination technical finesse organic wastewater | |
| Fu et al. | Co-oxidative removal of arsenite and tetracycline based on a heterogeneous Fenton-like reaction using iron nanoparticles-impregnated biochar | |
| CN107413835B (en) | Method for restoring petroleum polluted soil | |
| CN108993475B (en) | Ternary composite material heterogeneous light Fenton catalyst and preparation and application thereof | |
| CN110759319A (en) | Slow-release nano calcium peroxide material, preparation method thereof and method for removing chlorohydrocarbon and/or benzene series in underground water by using slow-release nano calcium peroxide material | |
| CN108380214B (en) | A kind of preparation of modified meerschaum and method applied to wastewater treatment | |
| Fan et al. | Multi-targeted removal of coexisted antibiotics in water by the synergies of radical and non-radical pathways in PMS activation | |
| CN111871374A (en) | Preparation method and application of magnetic biochar | |
| CN112939187A (en) | Method for treating sewage by combining nitrogen-doped sludge biochar and peroxydisulfate | |
| CN109012565A (en) | A kind of method of the magnetic carbon material Adsorption heavy metal ions in wastewater of nitrating | |
| CN105148831A (en) | Hangjin 2# soil loaded nano-zero valent iron adsorption material, preparation method and application | |
| CN109608021A (en) | Deep dehydration method for sludge | |
| CN110841654A (en) | Zero-valent iron-loaded iron-manganese oxide composite material, and preparation method and application thereof | |
| CN114890528B (en) | Biochar-loaded iron-based nano modified material as well as preparation method and application thereof | |
| CN101708886B (en) | Method for treating organic waste water | |
| CN113600166A (en) | Biomass-based catalyst for advanced oxidation and preparation method and application thereof | |
| CN115231680A (en) | Preparation method and application of biochar loaded nano zero-valent iron material | |
| CN105253962A (en) | Preparation method and application of arsenic removal agent | |
| CN106744952A (en) | The method that sewage sludge prepares modified active coke | |
| CN113979527A (en) | Method for synchronously and efficiently removing hexavalent chromium and trichloroethylene combined pollution | |
| CN105060454A (en) | Method for removing pollutants in water through magnetic field reinforced Hangjin 2# clay supported nanometer zero-valent iron | |
| JP6042237B2 (en) | Purification method | |
| CN115722251A (en) | Preparation method and application of hetero-atom-doped algae-based biochar loaded nano zero-valent metal catalyst | |
| CN102764637A (en) | Method for preparing load type zero valent iron for water processing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200807 |