CN111889109A - Preparation and application of ferro-manganese modified biochar for cooperative control of water and soil pollution - Google Patents
Preparation and application of ferro-manganese modified biochar for cooperative control of water and soil pollution Download PDFInfo
- Publication number
- CN111889109A CN111889109A CN202010706659.4A CN202010706659A CN111889109A CN 111889109 A CN111889109 A CN 111889109A CN 202010706659 A CN202010706659 A CN 202010706659A CN 111889109 A CN111889109 A CN 111889109A
- Authority
- CN
- China
- Prior art keywords
- biochar
- water
- soil
- ferro
- manganese
- 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.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Catalysts (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a ferro-manganese modified biochar catalytic material for cooperative control of water and soil pollution, which comprises biochar and Fe loaded on the surface of the biochar3O4Particles and MnO2Particles; wherein, the Fe3O4The particles are prepared from ferric iron and ferrous iron by a homovalence method, MnO2The particles are prepared from heptavalent manganese and divalent manganese by a homovalent method. In addition, the invention discloses a preparation method of the ferro-manganese modified biochar catalytic material, which comprises the following steps: step A: MnO of2The particles are loaded on the biochar; and B: mixing Fe3O4The particles are loaded on the biochar; and C: and D, washing and drying the biochar treated in the steps A and B to obtain the ferro-manganese modified biochar catalytic material. In addition, the invention also discloses an application of the ferro-manganese modified biochar catalytic material. The ferro-manganese modified biochar catalytic material has the advantages of high efficiency, low consumption, stability, environmental protection and simple operation.
Description
Technical Field
The invention relates to the field of environmental protection, relates to a preparation method and application of manganese-iron modified biochar, in particular to a method for integrally repairing soil and underground water polluted by organic matters in a field by using manganese-iron modified biochar, and more particularly relates to catalytic Fe3O4Particles and MnO2The biological carbon modified by the particles realizes the degradation of benzene series and polycyclic aromatic hydrocarbon in soil and underground water in the presence of a decomposition promoter and a surfactant.
Background
The organic pollution of soil caused by the accelerated industrialization process is increasingly and widely concerned, and the organic pollutants are migrated and transformed in the soil and underground water, so that the double pollution of the soil and the underground water is easily caused. Benzene series and polycyclic aromatic hydrocarbon are typical organic pollutants in polluted soil and underground water, and because the two pollutants have fluidity and certain volatility, the two pollutants can be diffused into the soil, the underground water and the atmosphere, so that a series of environmental problems are caused. The existing treatment strategies for benzene series and polycyclic aromatic hydrocarbon pollution in soil and underground water mostly adopt independent remediation of the soil and the underground water, and neglect cross contamination formed by interaction of the soil and the underground water, so that pollution remediation can not be continued.
The biochar has the characteristics of low cost, rich raw material sources, environmental friendliness and the like. Patent CN201610540865.6 discloses a method for degrading organic pollutants in water by using sludge biochar to catalyze persulfate, however, the traditional biochar catalytic performance is related to biochar surface groups and adsorption capacity, and after reaction substrates or intermediate products react with the biochar surface groups and block biochar free pores, the biochar catalytic activity is obviously reduced. Therefore, a biological carbon-based compound is developed and applied, for example, biological carbon loaded with ferro-manganese, which is a common element in soil, iron oxide and manganese oxide both have the function of a catalytic decomposition promoter, and when the ferro-manganese oxide and the manganese oxide are combined, electron transfer can be accelerated, and catalytic efficiency is improved.
For example: chinese patent publication No. CN108176362A, published as 2018, 6, month, and 19, entitled "a stable iron-manganese oxide preparation method" discloses a stable iron-manganese oxide preparation method. In the solution disclosed in this patent document, FeCl is used for the preparation of the iron-manganese oxide2Mixing the solution with KMnO4The solution is mixed and electrified to prepare the product, and the form of the iron-manganese oxide prepared by the electrochemical method is not fixed, so that the effect cannot be evaluated quantitatively.
Another example is: chinese patent publication No. CN107551998A, published as 2018, 10, month and 9, entitled "preparation method and application of biochar-stabilized iron-manganese oxide", discloses a preparation method of biochar-stabilized iron-manganese oxide. In the solution disclosed in this patent document, FeCl is used for the preparation of the iron-manganese oxide2Mixing the solution with KMnO4The solution is prepared by mixing, the valence states of iron and manganese are not easy to control, and a mixture with multiple valence states can be obtained.
For another example: chinese patent publication No. CN108251118A, published as 7/6/2018, entitled "biochar, soil heavy metal stabilizing agent and preparation method thereof", discloses a biochar, soil heavy metal stabilizing agent and preparation method thereof. However, the technical solution disclosed in this patent document is obtained by directly impregnating metal oxide with biochar and then drying, and the metal oxide is easily exfoliated.
Based on this, it is desirable to prepare a ferro-manganese modified biochar with a fixed valence state and easy mass production, which can synergistically repair benzene series and polycyclic aromatic hydrocarbons in soil and underground water in situ to overcome the above disadvantages.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a ferro-manganese modified biochar catalytic material, a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
according to the first scheme, the invention provides a ferro-manganese modified biochar catalytic material for cooperative control of water and soil pollution, wherein the ferro-manganese modified biochar catalytic material comprises biochar and Fe loaded on the surface of the biochar3O4Particles and MnO2Particles;
wherein, the Fe3O4The particles are prepared from ferric iron and ferrous iron by a homovalence method, MnO2The particles are prepared from heptavalent manganese and divalent manganese by a homovalent method.
In the ferro-manganese modified biocarbon catalytic material, manganese dioxide and ferroferric oxide are loaded on the surface of the biocarbon, so that electron transfer can be accelerated, and the catalytic efficiency can be accelerated.
Preferably, the biochar is one or more of coconut shell biochar, rice hull biochar, bamboo sawdust biochar, biogas residue biochar and straw biochar. If the biochar is coconut shell biochar, the size of the biochar is 5-10 mu m; if the biochar is rice hull biochar, the biochar is 1-4 mu m in size; if the biochar is bamboo dust biochar, the size of the biochar is 0.1-2 mu m; if the biochar is straw biochar, the size of the biochar is 1-8 mu m; and if the biochar is biogas residue biochar, the size of the biochar is 1-3 mu m.
Preferably, the Fe3O4The particle size is 10 nm-1000 nm, and the magnetic iron-based composite material has magnetism, firm adhesion, high chemical stability and adsorption effect on benzene series substances and the like.
Preferably, the MnO2The particle size is 10 nm-1000 nm, and the crystal form is alpha or beta.
Preferably, MnO2Particle loading (i.e., MnO)2The mass percentage of the particles in the ferromanganese modified organism) is between 3 and 5 weight percent.
Preferably, Fe3O4Particle loading (i.e., Fe)3O4The mass percentage of the particles in the ferro-manganese modified organism) is between 3 and 5 weight percent。
In a second scheme, the invention provides a preparation method of ferro-manganese modified biochar, which comprises the following steps:
step A: MnO of2The particles are loaded on the biochar;
and B: mixing Fe3O4Loading particles on the biochar obtained in the step A;
and C: and C, carrying out thermal cracking on the biochar treated in the step B to obtain the ferro-manganese modified biochar catalytic material.
Preferably, in the preparation method according to the present invention, in step a, the biochar material is soaked in MnSO4After a period of time in solution, KMnO is added4The solution is stirred in water bath at a certain temperature to obtain MnO loaded2Granular biochar.
Preferably, in the preparation method of the ferro-manganese modified biochar, in the step A, the biochar is soaked in MnSO4The solution time is 20-60min, the water bath temperature is 70-90 ℃, and the time is 30-60 min.
Preferably, the MnSO4And KMnO4The ratio is 1: 2-1: 1.6, the volume is equal, the concentration of the solution is 0.1-0.4 mol/L, the temperature of the water bath is 70-90 ℃, and the stirring speed is 120-240 rpm.
Preferably, the MnO2And (3) drying the particles after loading the particles on the surface of the biochar, wherein the drying condition is 70-90 ℃ for 12-24 h.
Preferably, in the preparation method of the present invention, in step B, the biochar material is soaked in FeCl3After a period of time in the solution, FeSO is added under the condition of introducing nitrogen at normal temperature4Stirring the solution and ammonia water to obtain the Fe-loaded solution3O4Granular biochar.
Preferably, the preparation method of the ferro-manganese modified biochar provided by the invention comprises the step of soaking the biochar in FeCl3Adding FeSO into the solution for 20-60min4The solution and ammonia water are stirred for 30-60 min, and the nitrogen flow is 100-200 mL/min.
Preferably, the method of the present inventionIn the preparation method, in the step B, the biochar material is soaked in FeCl3Adding FeSO into the solution under the condition of introducing nitrogen at normal temperature4Stirring the solution and ammonia water to obtain the Fe-loaded solution3O4Granular biochar.
Preferably, in the preparation method of the invention, the material is soaked in FeCl3Adding FeSO into the solution for 20-60min4The solution and ammonia water are stirred for 30-60 min, and the nitrogen flow is 100-200 mL/min.
Preferably, the FeCl3With FeSO4The concentration ratio is 1: 1-1: 2, the volume is equal, the concentration of the solution is 0.1-0.4 mol/L, the nitrogen flow is 100-200 mL/min, the content of the added ammonia water is 25-28%, the volume of the added ammonia water and the FeCl are3The volume ratio is 1: 6-1: 2, and the pH value of the reaction solution is 9-13.
Preferably, the Fe3O4And (3) drying the particles after loading the particles on the surface of the biochar, wherein the drying condition is 50-60 ℃ for 12-24 h.
In a third aspect, the invention provides an application of the iron-manganese modified biochar catalytic material in integrated remediation of soil and underground water in a petroleum-polluted site, which is characterized by comprising the following steps: the iron-manganese modified biochar catalytic material is paved on the surface layer of soil, a water distribution pipeline is paved above the iron-manganese modified biochar catalytic material, the polluted underground water is pumped into the water distribution pipeline, a decomposition accelerator and a surfactant are added, the polluted underground water containing the decomposition accelerator and the surfactant is uniformly irrigated on the modified biochar layer above the soil by the water distribution pipeline to carry out catalytic degradation reaction, organic pollutants in the underground water are degraded, when the reaction solution penetrates into the underground through the soil, the organic pollutants in the soil are degraded, and the organic pollutants in the underground water and the soil are continuously degraded through continuous intermittent circulation.
Preferably, the degradation accelerator is one or more of hydrogen peroxide, calcium peroxide, urea peroxide and sodium persulfate.
Preferably, the surfactant is one or more of SDS, LAS and SDBS.
Preferably, the organic pollutants are common organic pollutants in petroleum-polluted soil and underground water, and particularly 5 benzene series and 16 polycyclic aromatic hydrocarbons.
The benzene series comprises benzene, toluene, ethylbenzene, paraxylene and meta/para-xylene.
The polycyclic aromatic hydrocarbon comprises naphthalene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, indene benzene (1,2,3-cd) pyrene, dibenzo (a, n) anthracene and benzo (ghi) north.
The specific embodiment of the iron-manganese modified biochar catalytic material for synergistically degrading organic pollutants in soil and underground water comprises the following steps: laying a layer of iron-manganese modified biochar catalytic material above the soil, laying a water distribution pipeline, and intermittently scouring pumped underground water with a decomposition accelerator and a surfactant.
The concrete operation is that before construction, firstly a certain thickness of iron-manganese modified charcoal layer is laid above the soil, a water distribution pipeline covering the whole polluted site is laid, then the groundwater is filtered by a water pump and enters the water distribution pipeline, and simultaneously a proper amount of degradation accelerator and surfactant are added.
The iron-manganese modified biochar catalytic material prepared by the invention has stable catalytic performance, and after being recycled for 7 times, the 3-hour degradation efficiency of 5 benzene series in soil can still reach 50%, and the 3-hour degradation rate of polycyclic aromatic hydrocarbon can still reach 25%.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention adopts a biochar post-modification method to prepare green nontoxic iron-manganese modified biochar, and realizes effective degradation of benzene series and polycyclic aromatic hydrocarbon in a polluted site by the catalytic degradation promoter;
2. the invention adopts the ferro-manganese modified biochar catalytic material to overcome the dependence of the traditional Fenton advanced oxidation on pH and the secondary pollution of a large amount of iron mud;
3. the ferro-manganese modified biochar catalytic material prepared by the invention has higher stability, can be recycled, and realizes recycling.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 schematically shows the application of the ferro-manganese modified biochar catalytic material for integrally repairing soil and underground water polluted by organic matters.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
In this example, the preparation of the ferrimanganic modified biochar catalytic material for the synergistic control of water and soil pollution comprises the following steps:
(1) the load carries MnO2The biochar is prepared as follows:
10g of coconut shell biochar material is soaked in 100mL of 0.1mol/L MnSO4Adding 100ml of 0.16mol/L KMnO into the charcoal soaking solution for 30min4The solution is stirred at 2000rpm for 60min under the condition of 80 ℃ water bath, then centrifuged at 2000rpm for 20min, and dried at 80 ℃ for 24h to obtain the product.
(2) The carrier Fe3O4-MnO2The preparation of the biochar (i.e. the ferrimanganic modified biochar catalytic material of the present case) is as follows:
load 10g into MnO2The coconut shell is soaked in 100ml of 0.2mol/L FeCl3Adding 100ml of 0.1mol/L FeSO into the material soaking solution for 30min under the condition of 100ml/min of nitrogen gas4Adjusting pH to 10 with 15ml 28% ammonia water, reacting for 30min, centrifuging at 2000rpm for 20min, and drying at 50 deg.C for 24 h.
The treated objects are underground water and soil of a polluted site, and a site (including soil) 5m below the groundSoil and moisture) was 287mg/kg, the concentration of 16 polycyclic aromatic hydrocarbons was 2346mg/kg, the embodiment: before application, 10000m are firstly put on the soil surface2The area of the charcoal is paved with ferro-manganese modified biochar with the thickness of 10cm, and the thickness is 10000m2The area of the underground water pump is paved with a water distribution pipeline, and then the underground water is pumped and filtered by a water pump to be 1m3The underground water is irrigated on the ferro-manganese modified biochar layer through a water distribution pipeline at the speed of 0.5m3Adding 1% hydrogen peroxide solution at a speed of 0.1 m/s3Adding 1% SDS solution at a speed of/s, stopping extracting the underground water when the construction area is saturated with water and about to overflow, recovering to extract the underground water after the water completely permeates into the soil, intermittently circulating in the way, taking the soil and water 5m below the pool after a certain time, and detecting the concentrations of 5 benzene series and 16 polycyclic aromatic hydrocarbons in the soil and water according to gas chromatography-mass spectrometry specified in HJ605 and HJ 805.
The flow of this example is shown in FIG. 1. Wherein, the test conditions are as follows: the degradation rate of 5 benzene series/16 polycyclic aromatic hydrocarbons is 52 percent and 36 percent after 3 hours at the temperature of between 5 and 15 ℃, the degradation rate of 5 benzene series/16 polycyclic aromatic hydrocarbons is 90 percent and 56 percent after 24 hours, and no iron mud or other secondary pollution is generated.
Examples2
Example 2 is a variation of example 1, varying only: in step (1), FeCl3The concentration of the solution is 0.4mol/L, FeSO4The concentration of the solution is 0.2mol/L, and in the step (2), MnSO4The concentration of the solution is 0.2mol/L, KMnO4The concentration of the solution was 0.32 mol/L.
The specific embodiment of the iron-manganese modified biochar repair material comprises the following steps: firstly 10000m on the soil surface2The area of the charcoal is paved with ferro-manganese modified biochar with the thickness of 10cm, and the thickness is 10000m2The area of the underground water pump is paved with a water distribution pipeline, and then the underground water is pumped and filtered by a water pump to be 1m3The underground water is irrigated on the ferro-manganese modified biochar layer through a water distribution pipeline at the speed of 0.5m3Adding 1% hydrogen peroxide solution at a speed of 0.1 m/s3Adding 1% SDS solution at the speed of/s, stopping extracting underground when the construction area is saturated with water and about to overflowAnd recovering to extract underground water after the water and water completely permeate into the soil, performing intermittent circulation in the way, taking the soil and water 5m below the pool after a certain time, and detecting the concentrations of the 5 benzene series and the 16 polycyclic aromatic hydrocarbons in the soil and the water according to gas chromatography-mass spectrometry specified in HJ605 and HJ 805.
The flow of this example is shown in FIG. 1. Wherein, the test conditions are as follows: the degradation rate of 5 benzene series/16 polycyclic aromatic hydrocarbons is 72 percent and 56 percent after 3 hours at the temperature of between 5 and 15 ℃, the degradation rate of 5 benzene series/16 polycyclic aromatic hydrocarbons is 96 percent and 65 percent after 24 hours, and no iron mud or other secondary pollution is generated.
Examples3
Example 3 is a variation of example 1, varying only: the laying thickness of the ferro-manganese modified biochar in the embodiment is 15 cm.
Firstly 10000m on the soil surface2The area of the carbon is paved with ferro-manganese modified biochar with the thickness of 12cm, and the thickness is 10000m2The area of the underground water pump is paved with a water distribution pipeline, and then the underground water is pumped and filtered by a water pump to be 1m3The underground water is irrigated on the ferro-manganese modified biochar layer through a water distribution pipeline at the speed of 0.5m3Adding 1% hydrogen peroxide solution at a speed of 0.1 m/s3Adding 1% SDS solution at a speed of/s, stopping extracting the underground water when the construction area is saturated with water and about to overflow, recovering to extract the underground water after the water completely permeates into the soil, intermittently circulating in the way, taking the soil and water 5m below the pool after a certain time, and detecting the concentrations of 5 benzene series and 16 polycyclic aromatic hydrocarbons in the soil and water according to gas chromatography-mass spectrometry specified in HJ605 and HJ 805.
The flow of this example is shown in FIG. 1. Wherein, the test conditions are as follows: the degradation rate of 5 benzene series/16 polycyclic aromatic hydrocarbons after 3 hours is 74 percent and 59 percent at the temperature of 5-15 ℃, the degradation rate of 5 benzene series/16 polycyclic aromatic hydrocarbons after 24 hours is 99 percent and 53 percent, and no iron mud or other secondary pollution is generated.
Example 4
Example 4 is a variation of example 1, varying only: in the step (1), the biochar material is rice hull biochar.
The specific implementation scheme of the ferro-manganese modified charcoal comprises the following steps: firstly 10000m on the soil surface2The area of the carbon is paved with ferro-manganese modified biochar with the thickness of 12cm, and the thickness is 10000m2The area of the underground water pump is paved with a water distribution pipeline, and then the underground water is pumped and filtered by a water pump to be 1m3The underground water is irrigated on the ferro-manganese modified biochar layer through a water distribution pipeline at the speed of 0.5m3Adding 1% hydrogen peroxide solution at a speed of 0.1 m/s3Adding 1% SDS solution at a speed of/s, stopping extracting the underground water when the construction area is saturated with water and about to overflow, recovering to extract the underground water after the water completely permeates into the soil, intermittently circulating in the way, taking the soil and water 5m below the pool after a certain time, and detecting the concentrations of 5 benzene series and 16 polycyclic aromatic hydrocarbons in the soil and water according to gas chromatography-mass spectrometry specified in HJ605 and HJ 805.
The flow of this example is shown in FIG. 1. Wherein, the test conditions are as follows: the degradation rate of 5 benzene series/16 polycyclic aromatic hydrocarbons after 3 hours is 36 percent and 24 percent at the temperature of 5-15 ℃, the degradation rate of 5 benzene series/16 polycyclic aromatic hydrocarbons after 24 hours is 87 percent and 47 percent, and no iron mud or other secondary pollution is generated.
Example 5
Example 5 is a variation of example 1, varying only: in the step (1), the biochar material is bamboo dust biochar.
The specific implementation scheme of the ferro-manganese modified charcoal comprises the following steps: firstly 10000m on the soil surface2The area of the carbon is paved with ferro-manganese modified biochar with the thickness of 12cm, and the thickness is 10000m2The area of the underground water pump is paved with a water distribution pipeline, and then the underground water is pumped and filtered by a water pump to be 1m3The underground water is irrigated on the ferro-manganese modified biochar layer through a water distribution pipeline at the speed of 0.5m3Adding 1% hydrogen peroxide solution at a speed of 0.1 m/s3Adding 1% SDS solution at a speed of/s, stopping extracting the underground water when the construction area is saturated with water and about to overflow, recovering to extract the underground water after the water completely permeates into the soil, intermittently circulating in such a way, taking the soil and water 5m below the pool after a certain time, and detecting the concentrations of 5 benzene series and 16 polycyclic aromatic hydrocarbons in the soil and the underground water according to gas chromatography-mass spectrometry specified in HJ605 and HJ805Concentration in soil and water.
The flow of this example is shown in FIG. 1. Wherein, the test conditions are as follows: the degradation rate of 5 benzene series/16 polycyclic aromatic hydrocarbons after 3 hours is 39 percent and 31 percent at the temperature of 5-15 ℃, the degradation rate of 5 benzene series/16 polycyclic aromatic hydrocarbons after 24 hours is 88 percent and 53 percent, and no iron mud or other secondary pollution is generated.
Example 6
Example 6 is a variation of example 1, varying only: in the step (1), the biochar material is biogas residue biochar.
The specific implementation scheme of the ferro-manganese modified charcoal comprises the following steps: before application, 10000m are firstly put on the soil surface2The area of the carbon is paved with ferro-manganese modified biochar with the thickness of 12cm, and the thickness is 10000m2The area of the underground water pump is paved with a water distribution pipeline, and then the underground water is pumped and filtered by a water pump to be 1m3The underground water is irrigated on the ferro-manganese modified biochar layer through a water distribution pipeline at the speed of 0.5m3Adding 1% hydrogen peroxide solution at a speed of 0.1 m/s3Adding 1% SDS solution at a speed of/s, stopping extracting the underground water when the construction area is saturated with water and about to overflow, recovering to extract the underground water after the water completely permeates into the soil, intermittently circulating in the way, taking the soil and water 5m below the pool after a certain time, and detecting the concentrations of 5 benzene series and 16 polycyclic aromatic hydrocarbons in the soil and water according to gas chromatography-mass spectrometry specified in HJ605 and HJ 805.
The flow of this example is shown in FIG. 1. Wherein, the test conditions are as follows: 53 percent and 39 percent of 5 benzene series/16 polycyclic aromatic hydrocarbons after 3 hours at the temperature of between 5 and 15 ℃, and the degradation rate of the 5 benzene series/16 polycyclic aromatic hydrocarbons after 24 hours is 93 percent and 67 percent, and no iron mud or other secondary pollution is generated.
Example 7
Example 7 is a variation of example 1, varying only: in the step (1), the biochar material is straw biochar.
The specific implementation scheme of the ferro-manganese modified charcoal comprises the following steps: firstly 10000m on the soil surface2The area of the carbon is paved with ferro-manganese modified biochar with the thickness of 12cm, and the thickness is 10000m2Is laid onWater distribution pipeline, then pumping and filtering the underground water by 1m through a water pump3The underground water is irrigated on the ferro-manganese modified biochar layer through a water distribution pipeline at the speed of 0.5m3Adding 1% hydrogen peroxide solution at a speed of 0.1 m/s3Adding 1% SDS solution at a speed of/s, stopping extracting the underground water when the construction area is saturated with water and about to overflow, recovering to extract the underground water after the water completely permeates into the soil, intermittently circulating in the way, taking the soil and water 5m below the pool after a certain time, and detecting the concentrations of 5 benzene series and 16 polycyclic aromatic hydrocarbons in the soil and water according to gas chromatography-mass spectrometry specified in HJ605 and HJ 805.
The flow of this example is shown in FIG. 1. Wherein, the test conditions are as follows: the degradation rate of 5 benzene series/16 polycyclic aromatic hydrocarbons is 33 percent and 19 percent after 3 hours at the temperature of between 5 and 15 ℃, the degradation rate of 5 benzene series/16 polycyclic aromatic hydrocarbons is 76 percent and 64 percent after 24 hours, and no iron mud or other secondary pollution is generated.
Example 8
Example 8 is a variation of example 1, varying only: in the step (1), Fe is carried out3O4Loading of (1), MnO in step 22Loading.
(1) The carrier Fe3O4The biochar is prepared as follows:
soaking 10g of coconut shell biochar material in 100ml of 0.2mol/L FeCl3Adding 0,1mol/L FeSO 100ml into the material soaking solution under nitrogen 100ml/min for 30min4Adjusting pH of the solution and 15ml of 28% ammonia water to 10, reacting for 30min, centrifuging at 2000rpm for 20min, and drying at 50 ℃ for 24h to obtain the product.
(2) The carrier Fe3O4-MnO2The biochar is prepared as follows:
10g of Fe was loaded3O4The coconut shell biochar composite material is soaked in 100mL of 0.1mol/L MnSO4Adding 100ml of 0.16mol/L KMnO into the charcoal soaking solution for 30min4The solution is stirred at 200rpm for 60min under the condition of 80 ℃ water bath, then centrifuged at 2000rpm for 20min, and dried at 80 ℃ for 24h to obtain the product.
The specific implementation scheme of the ferro-manganese modified biochar catalytic material is as follows: firstly 10000m on the soil surface2The area of the carbon is paved with ferro-manganese modified biochar with the thickness of 12cm, and the thickness is 10000m2The area of the underground water pump is paved with a water distribution pipeline, and then the underground water is pumped and filtered by a water pump to be 1m3The underground water is irrigated on the ferro-manganese modified biochar layer through a water distribution pipeline at the speed of 0.5m3Adding 1% hydrogen peroxide solution at a speed of 0.1 m/s3Adding 1% SDS solution at a speed of/s, stopping extracting the underground water when the construction area is saturated with water and about to overflow, recovering to extract the underground water after the water completely permeates into the soil, intermittently circulating in the way, taking the soil and water 5m below the pool after a certain time, and detecting the concentrations of 5 benzene series and 16 polycyclic aromatic hydrocarbons in the soil and water according to gas chromatography-mass spectrometry specified in HJ605 and HJ 805.
The flow of this example is shown in FIG. 1. Wherein, the test conditions are as follows: the degradation rate of 5 benzene series/16 polycyclic aromatic hydrocarbons/petroleum ether is 61 percent and 47 percent after 3 hours at the temperature of between 5 and 15 ℃, the degradation rate of 5 benzene series/16 polycyclic aromatic hydrocarbons is 97 percent and 66 percent after 24 hours, and no iron mud or other secondary pollution is generated.
Example 9
Example 9 is a variation of example 1, varying only: in a particular embodiment, the disintegration promoting agent is calcium peroxide.
The specific implementation scheme of the ferro-manganese modified biochar catalytic material is as follows: firstly 10000m on the soil surface2The area of the carbon is paved with ferro-manganese modified biochar with the thickness of 12cm, and the thickness is 10000m2The area of the underground water pump is paved with a water distribution pipeline, and then the underground water is pumped and filtered by a water pump to be 1m3The underground water is irrigated on the ferro-manganese modified biochar layer through a water distribution pipeline at the speed of 0.5m31% calcium peroxide solution, 0.1m, was added at a rate of/s3Adding 1% SDS solution at a speed of/s, stopping extracting the underground water when the construction area is saturated with water and about to overflow, recovering to extract the underground water after the water completely permeates into the soil, intermittently circulating in such a way, taking the soil and water 5m below the pool after a certain time, and detecting 5 according to gas chromatography-mass spectrometry specified in HJ605 and HJ805The concentrations of the benzene series and 16 polycyclic aromatic hydrocarbons in soil and water.
The flow of this example is shown in FIG. 1. Wherein, the test conditions are as follows: the degradation rate of 5 benzene series/16 polycyclic aromatic hydrocarbons is 44 percent and 33 percent after 3 hours at the temperature of between 5 and 15 ℃, the degradation rate of 5 benzene series/16 polycyclic aromatic hydrocarbons is 94 percent and 62 percent after 24 hours, and no iron mud or other secondary pollution is generated.
Example 10
Example 10 is a variation of example 1, and the comparison and comparative results are shown in Table 1:
TABLE 1
Example 11
Example 11 is a variation of example 1, and the comparison and comparative results are shown in Table 2:
TABLE 2
Examples 12 to 15
Examples 12 to 17 are modifications of example 1, and the comparative points and effects of the above examples are shown in Table 3:
table 3.
Example 16
Example 16 is a variation of example 1, and the comparison and comparative results are shown in Table 4:
TABLE 4
Example 17
Example 17 is a comparative example to example 1, and the comparative points and effects are shown in Table 5:
TABLE 5
Comparative examples 1 and 2
Comparative examples 1 and 2 are comparative examples of example 1, which are different from comparative example 1 in that:
comparative example 1 the biochar material was loaded with only ferroferric oxide particles when biochar was prepared, whereas comparative example 2 the biochar material was loaded with only manganese dioxide when biochar was prepared, and a comparison of the final implementation results can be seen in table 6.
Table 6 shows the comparison of example 1 with comparative examples 1 and 2 and the effect of the comparison.
TABLE 6
In summary, the invention provides a ferro-manganese modified biochar and a preparation method and application thereof, and particularly provides a method for controlling petroleum site pollution based on the ferro-manganese modified biochar, which is characterized in that Fe is used3O4And MnO2The catalyst is loaded on the surface of the biochar, can improve the transfer efficiency of electrons, and accelerates the catalysis of hydrogen peroxide and other decomposition promoters, thereby achieving the purpose of degrading benzene series and polycyclic aromatic hydrocarbon in a field, and has the outstanding characteristics of low requirement on the pH value of the environment, high efficiency, environmental protection, simple operation and the like.
In addition, the ferro-manganese modified biochar catalytic material disclosed by the invention is used for cooperative control of water and soil pollution, organic pollutants in soil and underground water can be simultaneously degraded by applying the ferro-manganese modified biochar catalytic material, a good degradation effect is finally realized, and the cooperative control efficiency is good.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. The ferro-manganese modified biochar catalytic material for cooperative control of water and soil pollution is characterized by comprising biochar and Fe loaded on the surface of the biochar3O4Particles and MnO2Particles;
wherein, the Fe3O4The particles are prepared from ferric iron and ferrous iron by a homovalence method, MnO2The particles are prepared from heptavalent manganese and divalent manganese by a homovalent method.
2. The preparation method of the ferro-manganese modified biochar catalytic material as claimed in claim 1, characterized by comprising the following steps:
step A: MnO of2The particles are loaded on the biochar;
and B: mixing Fe3O4Loading particles on the biochar obtained in the step A;
and C: and D, washing and drying the biochar treated in the step B to obtain the ferro-manganese modified biochar catalytic material.
3. The method according to claim 2, wherein in step a, the biochar material is soaked in MnSO4After a period of time in solution, KMnO is added4The solution is stirred in water bath at a certain temperature to obtain MnO loaded2Granular biochar.
4. The method according to claim 3, wherein the step A comprises immersing the substrate in MnSO4The solution time is 20-60min, the water bath temperature is 70-90 ℃, and the time is 30-60 min.
5. The method of claim 2, wherein in step B, the biochar material is soaked in FeCl3After a period of time in the solution, FeSO is added under the condition of introducing nitrogen at normal temperature4Stirring the solution and ammonia water to obtain the Fe-loaded solution3O4Granular biochar.
6. The method of claim 5, wherein the coating is immersed in FeCl3Adding FeSO into the solution for 20-60min4The solution and ammonia water are stirred for 30-60 min, and the nitrogen flow is 100-200 mL/min.
7. The application of the ferro-manganese modified biochar catalytic material as claimed in claim 1 to the integrated remediation of soil and groundwater in petroleum contaminated sites, characterized by comprising: the iron-manganese modified biochar catalytic material is paved on the surface layer of soil, a water distribution pipeline is paved above the iron-manganese modified biochar catalytic material, the polluted underground water is extracted to enter the water distribution pipeline, a decomposition accelerator and a surfactant are added, the polluted underground water containing the decomposition accelerator and the surfactant is uniformly irrigated on the modified biochar layer above the soil through the water distribution pipeline to carry out catalytic degradation reaction, organic pollutants in the underground water are degraded, when the reaction solution penetrates into the underground through the surface layer soil, the organic pollutants in the soil are degraded and eluted, and the organic pollutants in the underground water and the soil are continuously degraded through continuous intermittent circulation.
8. The use of claim 7, wherein the degradation promoter comprises one or more of hydrogen peroxide, calcium peroxide, urea peroxide, and sodium persulfate.
9. The use of claim 7, wherein the surfactant comprises one or more of SDS, LAS, SDBS.
10. The use of claim 7, wherein the organic contaminants comprise benzene-based compounds and polycyclic aromatic hydrocarbons.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010706659.4A CN111889109B (en) | 2020-07-21 | 2020-07-21 | Preparation and application of ferro-manganese modified biochar for cooperative control of water and soil pollution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010706659.4A CN111889109B (en) | 2020-07-21 | 2020-07-21 | Preparation and application of ferro-manganese modified biochar for cooperative control of water and soil pollution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111889109A true CN111889109A (en) | 2020-11-06 |
| CN111889109B CN111889109B (en) | 2023-04-07 |
Family
ID=73190317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010706659.4A Active CN111889109B (en) | 2020-07-21 | 2020-07-21 | Preparation and application of ferro-manganese modified biochar for cooperative control of water and soil pollution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111889109B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109628498A (en) * | 2018-12-25 | 2019-04-16 | 江苏久力环境科技股份有限公司 | A kind of technique of organic waste anaerobism-electrical charcoal of pyrolysis coupling coproduction |
| CN113134360A (en) * | 2021-03-31 | 2021-07-20 | 南京市生态环境保护科学研究院 | Preparation method of iron-manganese active particles for dye wastewater treatment |
| CN113185367A (en) * | 2021-05-14 | 2021-07-30 | 上海交通大学 | Biogas residue modified biochar with pollution control and efficiency enhancement functions as well as preparation and application thereof |
| CN113293157A (en) * | 2021-06-18 | 2021-08-24 | 华东理工大学 | Ferroferric oxide modified charcoal immobilized polycyclic aromatic hydrocarbon degrading microbial inoculum and preparation and application thereof |
| CN113856698A (en) * | 2021-11-12 | 2021-12-31 | 中国矿业大学 | Preparation method and application of high-efficiency self-driven catalyst based on Fenton-like reaction and PMS (permanent magnet synchronous motor) activation |
| CN114164004A (en) * | 2021-11-26 | 2022-03-11 | 北京市生态环境保护科学研究院 | Soil zero-valent mercury composite oxidant and method for repairing soil by using same |
| CN114749186A (en) * | 2022-05-07 | 2022-07-15 | 江苏第二师范学院 | Preparation method and application of hydrothermal supported sludge carbon-based catalyst |
| CN115739105A (en) * | 2021-09-03 | 2023-03-07 | 中国矿业大学(北京) | Heterogeneous Fenton catalyst and preparation method and application thereof |
| CN115785957A (en) * | 2022-12-19 | 2023-03-14 | 中国地质科学院水文地质环境地质研究所 | Preparation method and application of nano manganese dioxide modified biochar passivator |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010060840A (en) * | 1999-12-28 | 2001-07-07 | 박경주 | The ceramic chacoals and their preparation methods |
| CN101250000A (en) * | 2007-12-18 | 2008-08-27 | 同济大学 | Advanced treatment method for removing iron-manganese in water |
| US20100034729A1 (en) * | 2007-01-29 | 2010-02-11 | George Mason Intellectual Properties, Inc. | Iron Composition Based Water Filtration System for the Removal of Chemical Species Containing Arsenic and other Metal Cations and Anions |
| JP2012091162A (en) * | 2010-10-01 | 2012-05-17 | Omuta Denshi Kogyo Kk | Method for purifying organic colored waste water containing suspended substance |
| CN103007882A (en) * | 2012-12-13 | 2013-04-03 | 同济大学 | Preparation method of Fe3O4@MnO2/active carbon magnetic compound adsorption material |
| CN103949212A (en) * | 2014-04-11 | 2014-07-30 | 上海交通大学 | Preparation method of biomass-based magnetic biochar |
| CN106861615A (en) * | 2015-12-10 | 2017-06-20 | 上海交通大学 | A kind of charcoal magnetic Fe3S4Composite nano adsorbent and preparation method and application |
| CN108480383A (en) * | 2018-02-08 | 2018-09-04 | 青岛农业大学 | Utilize the method for charcoal based titanium dioxide degradation PAHs in soil |
| CN109396172A (en) * | 2018-09-17 | 2019-03-01 | 上海交通大学 | A kind of pollution control synergisting method of in-situ immobilization farmland organic polluted soil |
| CN110052248A (en) * | 2019-05-08 | 2019-07-26 | 中国科学院城市环境研究所 | A kind of humic acid modified charcoal of ferrimanganic and the preparation method and application thereof |
| CN110272167A (en) * | 2019-06-28 | 2019-09-24 | 武汉环天禹生物环保科技有限公司 | A kind of mine wastewater processing system and underground water decontamination process based on carbon fiber |
| CN110665512A (en) * | 2019-09-27 | 2020-01-10 | 浙江大学 | Manganese dioxide-magnetic biochar composite catalyst and preparation method and application thereof |
-
2020
- 2020-07-21 CN CN202010706659.4A patent/CN111889109B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010060840A (en) * | 1999-12-28 | 2001-07-07 | 박경주 | The ceramic chacoals and their preparation methods |
| US20100034729A1 (en) * | 2007-01-29 | 2010-02-11 | George Mason Intellectual Properties, Inc. | Iron Composition Based Water Filtration System for the Removal of Chemical Species Containing Arsenic and other Metal Cations and Anions |
| CN101250000A (en) * | 2007-12-18 | 2008-08-27 | 同济大学 | Advanced treatment method for removing iron-manganese in water |
| JP2012091162A (en) * | 2010-10-01 | 2012-05-17 | Omuta Denshi Kogyo Kk | Method for purifying organic colored waste water containing suspended substance |
| CN103007882A (en) * | 2012-12-13 | 2013-04-03 | 同济大学 | Preparation method of Fe3O4@MnO2/active carbon magnetic compound adsorption material |
| CN103949212A (en) * | 2014-04-11 | 2014-07-30 | 上海交通大学 | Preparation method of biomass-based magnetic biochar |
| CN106861615A (en) * | 2015-12-10 | 2017-06-20 | 上海交通大学 | A kind of charcoal magnetic Fe3S4Composite nano adsorbent and preparation method and application |
| CN108480383A (en) * | 2018-02-08 | 2018-09-04 | 青岛农业大学 | Utilize the method for charcoal based titanium dioxide degradation PAHs in soil |
| CN109396172A (en) * | 2018-09-17 | 2019-03-01 | 上海交通大学 | A kind of pollution control synergisting method of in-situ immobilization farmland organic polluted soil |
| CN110052248A (en) * | 2019-05-08 | 2019-07-26 | 中国科学院城市环境研究所 | A kind of humic acid modified charcoal of ferrimanganic and the preparation method and application thereof |
| CN110272167A (en) * | 2019-06-28 | 2019-09-24 | 武汉环天禹生物环保科技有限公司 | A kind of mine wastewater processing system and underground water decontamination process based on carbon fiber |
| CN110665512A (en) * | 2019-09-27 | 2020-01-10 | 浙江大学 | Manganese dioxide-magnetic biochar composite catalyst and preparation method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| SUN, P ET AL.: ""Degradation of BTEXS with stable and pH-insensitive iron-manganese modified biochar from post pyrolysis"", 《CHEMOSPHERE》 * |
| ZHOU, H ET AL.: ""Magnetic biochar supported α-MnO2 nanorod for adsorption enhanced degradation of 4-chlorophenol via activation of peroxydisulfate"", 《SCIENCE OF THE TOTAL ENVIRONMENT》 * |
| 冯尚彩: "《综合化学实验》", 31 August 2012, 济南：山东人民出版社 * |
| 刘嘉媚等: ""生物炭负载铁锰氧化物对环丙沙星的去除研究"", 《环境科学与技术》 * |
| 温泉等: "《水土修复技术》", 31 October 2017, 吉林大学出版社 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109628498A (en) * | 2018-12-25 | 2019-04-16 | 江苏久力环境科技股份有限公司 | A kind of technique of organic waste anaerobism-electrical charcoal of pyrolysis coupling coproduction |
| CN113134360A (en) * | 2021-03-31 | 2021-07-20 | 南京市生态环境保护科学研究院 | Preparation method of iron-manganese active particles for dye wastewater treatment |
| CN113134360B (en) * | 2021-03-31 | 2023-04-25 | 南京市生态环境保护科学研究院 | Preparation method of iron-manganese active particles for dye wastewater treatment |
| CN113185367A (en) * | 2021-05-14 | 2021-07-30 | 上海交通大学 | Biogas residue modified biochar with pollution control and efficiency enhancement functions as well as preparation and application thereof |
| CN113293157A (en) * | 2021-06-18 | 2021-08-24 | 华东理工大学 | Ferroferric oxide modified charcoal immobilized polycyclic aromatic hydrocarbon degrading microbial inoculum and preparation and application thereof |
| CN115739105A (en) * | 2021-09-03 | 2023-03-07 | 中国矿业大学(北京) | Heterogeneous Fenton catalyst and preparation method and application thereof |
| CN113856698A (en) * | 2021-11-12 | 2021-12-31 | 中国矿业大学 | Preparation method and application of high-efficiency self-driven catalyst based on Fenton-like reaction and PMS (permanent magnet synchronous motor) activation |
| CN114164004A (en) * | 2021-11-26 | 2022-03-11 | 北京市生态环境保护科学研究院 | Soil zero-valent mercury composite oxidant and method for repairing soil by using same |
| CN114164004B (en) * | 2021-11-26 | 2023-06-13 | 北京市生态环境保护科学研究院 | Soil zero-valent mercury composite oxidant and method for restoring soil by using same |
| CN114749186A (en) * | 2022-05-07 | 2022-07-15 | 江苏第二师范学院 | Preparation method and application of hydrothermal supported sludge carbon-based catalyst |
| CN114749186B (en) * | 2022-05-07 | 2023-09-29 | 江苏第二师范学院 | Preparation method and application of hydrothermal supported sludge carbon-based catalyst |
| CN115785957A (en) * | 2022-12-19 | 2023-03-14 | 中国地质科学院水文地质环境地质研究所 | Preparation method and application of nano manganese dioxide modified biochar passivator |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111889109B (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111889109B (en) | Preparation and application of ferro-manganese modified biochar for cooperative control of water and soil pollution | |
| Wang et al. | Carboxyl and hydroxyl groups enhance ammonium adsorption capacity of iron (III) chloride and hydrochloric acid modified biochars | |
| Fagbohungbe et al. | The challenges of anaerobic digestion and the role of biochar in optimizing anaerobic digestion | |
| Shi et al. | A novel enhanced anaerobic biodegradation method using biochar and Fe (OH) 3@ biochar for the removal of nitrogen heterocyclic compounds from coal gasification wastewater | |
| Pereira et al. | Thermal modification of activated carbon surface chemistry improves its capacity as redox mediator for azo dye reduction | |
| CN110665512B (en) | Manganese dioxide-magnetic biochar composite catalyst and preparation method and application thereof | |
| Li et al. | Oxygen-rich biochar from torrefaction: A versatile adsorbent for water pollution control | |
| Chen et al. | Biodegradability enhancement of coking wastewater by catalytic wet air oxidation using aminated activated carbon as catalyst | |
| CN107413835B (en) | Method for restoring petroleum polluted soil | |
| Gao et al. | A pilot study on the regeneration of ferrous chelate complex in NOx scrubber solution by a biofilm electrode reactor | |
| CN105268425A (en) | Modified active carbon catalyst, and preparation and application thereof | |
| CN110314651B (en) | Magnetic sulfur-iron-carbon composite porous environment-friendly material and green preparation method and application thereof | |
| CN112939187A (en) | Method for treating sewage by combining nitrogen-doped sludge biochar and peroxydisulfate | |
| Haijia et al. | Biosorption of Ni2+ by the surface molecular imprinting adsorbent | |
| CN114832838B (en) | Metal/sulfur-persulfate loaded biochar composite material and preparation and application thereof | |
| Li et al. | Efficient oriented interfacial oxidation of petroleum hydrocarbons by functionalized Fe/N co-doped biochar-mediated heterogeneous Fenton for heavily contaminated soil remediation | |
| Shen et al. | Intensive removal of PAHs in constructed wetland filled with copper biochar | |
| CN115340168A (en) | Method for treating soil leaching waste liquid by using surface polymerization modified activated carbon | |
| Wang et al. | Review of biochar as a novel carrier for anammox process: Material, performance and mechanisms | |
| CN114917871A (en) | Photocatalytic regenerated active carbon and preparation method thereof | |
| Kang et al. | Effect of electron shuttles on typical perfluoroalkyl substance removal via iron oxide reduction in wetland sediment | |
| Sha et al. | Removal of abamectin and conventional pollutants in vertical flow constructed wetlands with Fe-modified biochar | |
| CN114308036A (en) | Method for oxidizing and repairing polluted soil by activated carbon-based monatomic iron catalyst | |
| WO2023193419A1 (en) | Oil-containing sludge treatment method, soil remediation method | |
| CN108128839B (en) | Water treatment method for strengthening and catalyzing persulfate by carbon-based auxiliary agent |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |