CN113477217A - Preparation and application of poplar sawdust biochar loaded nano zero-valent iron composite material - Google Patents
Preparation and application of poplar sawdust biochar loaded nano zero-valent iron composite material Download PDFInfo
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- 241000219000 Populus Species 0.000 title claims abstract description 55
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- 239000002131 composite material Substances 0.000 title claims abstract description 29
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
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- 238000006243 chemical reaction Methods 0.000 claims description 5
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- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
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- 238000001179 sorption measurement Methods 0.000 abstract description 10
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004098 Tetracycline Substances 0.000 abstract description 7
- 229960002180 tetracycline Drugs 0.000 abstract description 7
- 229930101283 tetracycline Natural products 0.000 abstract description 7
- 235000019364 tetracycline Nutrition 0.000 abstract description 7
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 abstract description 6
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- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 abstract 4
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 7
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
Abstract
The invention relates to a preparation method of poplar sawdust biochar loaded nano zero-valent iron and a method for repairing Tetracycline (TC) pollution in water by using an adsorption degradation system formed by the poplar sawdust biochar and sodium persulfate. The composite material activated sodium persulfate system formed by the invention can efficiently adsorb TC in water and activate sodium persulfate to generate active substances such as sulfate radicals, hydroxyl radicals and the like, so that the oxidation removal of TC is realized. The composite material has no requirements on the concentration of water and pollutants, and the pH application range is wide; the large specific surface area of the poplar biochar is utilized, TC can be adsorbed and nano zero-valent iron can be dispersed more favorably, and the degradation repair efficiency of subsequent materials is improved; the raw materials for preparing the composite material are low in cost, environment-friendly, simple and convenient in preparation process, and suitable for repairing water body antibiotic pollution.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method for repairing TC pollution in water by using poplar sawdust biochar loaded with zero-valent iron.
Background
The long-term existence of antibiotics in water seriously affects the balance of the environmental ecosystem, and the generation of drug-resistant bacteria reduces the drug effect of the antibiotics, resulting in ecosystem disorder, wherein tetracycline is a typical antibiotic, and the use amount thereof is in the front of the antibiotics for a long time, so that the removal of tetracycline in water has become an environmental problem generally concerned by the public.
In recent years, based on sulfate radicals (SO)4 •-）（E0Advanced Oxidation Processes (AOPs) = 2.5-3.1V) are considered to be effective methods for degrading antibiotics in municipal sewage and groundwater. The cheap and nontoxic transition metal iron is widely applied to the activation of persulfate because of environmental friendliness and high reaction rate. In recent years, zero-valent iron (ZVI), particularly nano ZVI, has been used to maintain Fe through continuous electron transfer2+To increase the activation efficiency of PS. This is because ZVI (particularly, nano ZVI) has advantages of small particle size, large specific surface area, strong reactivity, and the like. However, the nano zero-valent iron is easy to agglomerate, and the continuity of the reaction is influenced.
Therefore, in order to solve the problems, biochar is mostly adopted as a carrier to load nano zero-valent iron. Biochar (BC) is an abundant and inexpensive material with high specific surface area and porous structure, used to support and improve nanomaterials. The biochar surface also contains abundant oxygen-containing functional groups, including hydroxyl (-OH) and carboxyl (-COOH). These functional groups can activate persulfates and nano zero valent iron. In addition, BC has larger specific surface area and good ion exchange capacity, and can adsorb various heavy metal ions and organic pollutants. At present, more straw biochar is used, and less wood biochar is used. Compared with straw biochar, the poplar sawdust biochar used by the invention has the advantages of high yield, large specific surface area, large micropore area and the like, thereby realizing the purpose of efficiently removing TC pollution in water.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the problems that the nano zero-valent iron is easily oxidized in the air and easily agglomerated, the specific surface area, the reaction activity and the continuity of the material are reduced. The invention provides a preparation method and application of a poplar sawdust biochar loaded zero-valent iron composite material. Meanwhile, the adsorption performance of the biochar on organic pollutants is favorable for improving the degradation efficiency. The application has the advantages of high TC removal rate, wide pH application range, low composite material cost, simple preparation and good application prospect.
The technical scheme is as follows: a preparation method of a poplar sawdust biochar loaded nano zero-valent iron composite material comprises the following steps:
(1) material pretreatment: cleaning, drying and crushing poplar sawdust, and then placing the poplar sawdust in a pyrolysis reaction container;
(2) preparing poplar sawdust biochar: setting the interior of the muffle furnace to be in an oxygen-limited environment, carrying out high-temperature carbonization for a period of time, cooling to room temperature, and grinding and sieving to obtain poplar sawdust biochar;
(3) the biological charcoal of poplar sawdust loads nano zero-valent iron: weighing a certain amount of ferric salt, dissolving in a certain volume of deionized water, transferring to a 1000 ml three-neck flask after the ferric salt is dissolved, adding the poplar sawdust biochar prepared in the step (2) into the solution, continuously introducing nitrogen, stirring for 1 h through a stirrer, and uniformly mixing the biochar with the solution while discharging oxygen. Under stirring, newly prepared NaBH is added dropwise into the mixed solution at a rate of 5 ml/min4And (3) aging the solution for 1 h after the dropwise addition is finished, filtering in vacuum to separate out black particles, and washing for three times and drying by using deoxidized deionized water and absolute ethyl alcohol respectively. Obtaining the poplar sawdust biochar loaded iron nanoparticles.
The further proposal is that the pyrolysis temperature in the step (2) is 500--1。
The further scheme is that the biochar in the step (2) is dried, ground and sieved by a 100-mesh sieve.
In a further scheme, the ferric salt in the step (3) is FeSO4·7H2O was dissolved in 250 ml deionized water.
Further scheme is that the mass ratio of the ferric salt and the poplar sawdust biochar in the step (3) is 5: 3.
In a further scheme, the mass ratio of the sodium borohydride solution in the step (3) to the iron salt is 2:5, wherein the volume of the sodium borohydride solution is 250 ml.
Further, the drying in the step (3) is carried out for 12 hours at 80 ℃.
The invention also aims to provide a method for repairing TC pollution in water by using the poplar sawdust biochar loaded with nano zero-valent iron prepared by the scheme, the biochar material is used for catalyzing persulfate to degrade TC in water, when the initial concentration of TC is 20-100 mg/L, the addition amount of the biochar material is 0.05-0.2 g/L, and the addition amount of persulfate is 0.238-1.904 g/L.
Has the advantages that: (1) the invention adopts poplar sawdust as a preparation material of the biochar, poplar is the tree species which is most widely distributed in the world and has the strongest adaptability, the material is easy to obtain, the cost is low, and the woody biomass has high carbon yield, strong cation exchange capacity, large specific surface area and strong adsorption capacity. (2) The method for removing TC in water by activating the sodium persulfate adsorption degradation system through the composite material and the application thereof are characterized in that the sodium persulfate is activated to generate SO while the TC in water is efficiently adsorbed by the composite material4 •-Active substances such as free radicals degrade TC in the water body, and finally the TC is removed through adsorption-degradation reaction of the composite material.
Drawings
FIG. 1 is an XRD spectrum of a poplar sawdust biochar loaded nano zero-valent iron composite material prepared in an example;
FIG. 2 is a graph showing the adsorption effect of different addition amounts of the poplar sawdust biochar-loaded nano zero-valent iron composite material on TC prepared in the example.
Fig. 3 is a graph of the degradation effect of the poplar sawdust biochar-loaded nano zero-valent iron composite material prepared in the example on TC with different concentrations.
Fig. 4 is a graph of the degradation effect of the poplar sawdust biochar-loaded nano zero-valent iron composite material on TC in different pH environments, which is prepared in the example.
Detailed Description
The technical solutions in the embodiments of the present invention are described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Specific embodiment of preparation method of poplar sawdust biochar loaded nano zero-valent iron composite material
The composite material is synthesized by adopting a liquid phase reduction coprecipitation method:
(1) material pretreatment: washing poplar sawdust with deionized water for 4 times, drying in a 70 ℃ oven for 48 hours, crushing, sieving with a 2 mm sieve, putting a certain amount of processed biomass in a 50.0 ml ceramic crucible, and completely wrapping the crucible with tinfoil to better isolate oxygen;
(2) preparing poplar sawdust biochar: the interior of the muffle furnace is set to be an oxygen-limited environment, the initial temperature is 20 ℃, the temperature is increased to 500 ℃ at the speed of 5 ℃/min, and the heating is stopped after the constant temperature is kept for 2 h. Cooling to room temperature, taking out the sample, grinding the sample through a 0.154 mm sieve (100 meshes) to obtain poplar sawdust biochar, and storing for later use;
(3) the biological charcoal of poplar sawdust loads nano zero-valent iron: 2.5 g of FeSO are weighed4·7H2Dissolving O in deionized water with a certain volume, transferring to a 250 ml volumetric flask for constant volume after ferric salt is completely dissolved, transferring the solution to a 1000 ml three-neck flask after constant volume, adding 1.5 g of the poplar sawdust biochar prepared in the step (2) into the solution, continuously introducing nitrogen, stirring for 1 h through a stirrer, and uniformly mixing the biochar with the solution while discharging oxygen. Under stirring, 250 ml of newly prepared NaBH 0.1 mol/L is added dropwise into the mixed solution at 5 ml/min4And (3) aging the solution for 1 h after the dropwise addition is finished, filtering in vacuum to separate out black particles, washing for three times respectively by using deoxidized deionized water and absolute ethyl alcohol, placing the solution into a vacuum drying oven, drying for 12 h at the temperature of 80 ℃, and storing. Finally obtaining the poplar sawdust biochar loaded iron nanoparticles.
Example 1
In this example, the adsorption effect of the nano zero-valent iron composite material loaded with different amounts of poplar sawdust biochar on TC was compared, and an appropriate amount was selected for the subsequent degradation experiment.
Preparing 100 ml of TC solution of 30 mg/L in a 100 ml conical flask, weighing the poplar sawdust biochar-loaded nano zero-valent iron composite materials with different masses, adding the poplar sawdust biochar-loaded nano zero-valent iron composite materials into the pollutant solution, placing the conical flask in an oscillator, rotating at 160 rpm, keeping the temperature at 25 ℃, keeping the pH value at 5, and adsorbing for 2 hours.
The TC removal effect data is shown in FIG. 2, and the results show that the TC removal rates after adsorbing for 2 hours are respectively 27.45%, 55.97%, 74.32% and 83.57% from 0.05 g/L to 0.4 g/L, 0.05 g/L, 0.1 g/L, 0.2 g/L and 0.4 g/L of the nano zero-valent iron material loaded on the poplar sawdust biochar. The adsorption performance of the composite material is good, the adsorption removal rate is continuously increased along with the increase of the addition amount of the composite material, and the TC in the water can be effectively removed only by improving the quality of the composite material.
Example 2
In the embodiment, the degradation condition of activated persulfate of the poplar sawdust biochar-loaded nano zero-valent iron composite material under the condition of different TC pollutant concentrations is tested to verify the applicability of the material.
Preparing 100 ml of TC solution with a certain concentration in a 100 ml conical flask, adding 5 mg of poplar sawdust biochar loaded nano zero-valent iron composite material into the pollutant solution, placing the conical flask in an oscillator at the rotating speed of 160 rpm, the temperature of 25 ℃, the pH value of 5, adsorbing for 2 hours, adding 5 mM sodium persulfate solution, and continuing to react for 2 hours.
The TC removal effect data are shown in FIG. 3, and the adsorption and degradation efficiencies of the poplar sawdust biochar-loaded nano zero-valent iron composite on TC are 94.1%, 93.1%, 88.7%, 85.4%, 83%, 80.3% and 78.7% respectively according to the initial TC concentrations of 20 mg/L, 30 mg/L, 40 mg/L, 50 mg/L, 60 mg/L, 80 mg/L and 100 mg/L. The degradation rate can reach nearly 80% even if the initial concentration of TC reaches 100 mg/L, which shows that the material has good adsorption effect on TC and can effectively activate persulfate to obtain good degradation effect.
Example 3
The embodiment tests the degradation condition of activated persulfate of the poplar sawdust biochar-loaded nano zero-valent iron composite material on TC pollutants under different pH conditions so as to verify the application range of the pH of the material.
Preparing 100 ml TC solution of 30 mg/L in a 100 ml conical flask, adding 5 mg poplar sawdust biochar loaded nano zero-valent iron composite material into the pollutant solution, placing the conical flask in an oscillator, rotating at 160 rpm, adjusting the pH value at 25 ℃, adsorbing for 2 h, adding 5 mM sodium persulfate solution, and continuing to react for 2 h.
The data of the removal effect of TC are shown in FIG. 4, and the results show that the removal rate of TC after adsorptive degradation is 90.1%, 93.1%, 88.4%, 85.7% and 83.5% respectively as the pH of the solution is increased from 3 to 11, pH 3, pH 5, pH 7, pH 9 and pH 11. The degradation effect is slightly influenced by pH, which shows that the material has wide pH application range and can be used in all pH environments.
The foregoing is merely an example of the embodiments of the present invention, and it should be noted that, for those skilled in the art, several modifications can be made without departing from the technical principle of the present invention, and these modifications should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a poplar sawdust biochar loaded nano zero-valent iron composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) material pretreatment: cleaning, drying and crushing poplar sawdust, and then placing the poplar sawdust in a pyrolysis reaction container;
(2) preparing poplar sawdust biochar: setting the interior of the muffle furnace to be in an oxygen-limited environment, carrying out high-temperature carbonization for a period of time, cooling to room temperature, and grinding and sieving to obtain poplar sawdust biochar;
(3) the biological charcoal of poplar sawdust loads nano zero-valent iron: weighing a certain amount of ferric salt, dissolving in a certain volume of deionized water, transferring to a 1000 ml three-neck flask after the ferric salt is dissolved, adding the poplar sawdust biochar prepared in the step (2) into the solution, continuously introducing nitrogen, stirring for 1 h through a stirrer, and uniformly mixing the biochar with the solution while discharging oxygen.
2. Under stirring, newly prepared NaBH is added dropwise into the mixed solution at a rate of 5 ml/min4And (3) aging the solution for 1 h after the dropwise addition is finished, filtering in vacuum to separate out black particles, and washing for three times and drying by using deoxidized deionized water and absolute ethyl alcohol respectively.
3. Obtaining the poplar sawdust biochar loaded iron nanoparticles.
4. The preparation method of poplar sawdust biochar-loaded nano zero-valent iron according to claim 1, wherein the preparation method comprises the following steps: the pyrolysis temperature in the step (2) is 500--1。
5. The preparation method of poplar sawdust biochar-loaded nano zero-valent iron according to claim 1, wherein the preparation method comprises the following steps: and (3) drying the biochar in the step (2), grinding and sieving by a 100-mesh sieve.
6. The preparation method of poplar sawdust biochar-loaded nano zero-valent iron according to claim 1, wherein the preparation method comprises the following steps: the ferric salt in the step (3) is FeSO4·7H2O was dissolved in 250 ml deionized water.
7. The preparation method of poplar sawdust biochar-loaded nano zero-valent iron according to claim 1, wherein the preparation method comprises the following steps: the mass ratio of the ferric salt to the poplar sawdust biochar in the step (3) is 5: 3.
8. The preparation method of poplar sawdust biochar-loaded nano zero-valent iron according to claim 1, wherein the preparation method comprises the following steps: NaBH in step (3)4The mass ratio of the solution volume of 250 ml to the iron salt is 2: 5.
9. The preparation method of poplar sawdust biochar-loaded nano zero-valent iron according to claim 1, wherein the preparation method comprises the following steps: and (4) drying in the step (3) for 12 hours at 80 ℃.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113943030A (en) * | 2021-11-29 | 2022-01-18 | 中国科学院南京土壤研究所 | Biomass carbon-coated nano zero-valent iron composite material for treating chlorobenzene-polluted water body by activating peroxymonosulfate and preparation and application thereof |
| CN114226721A (en) * | 2021-11-30 | 2022-03-25 | 南开大学 | Graphite carbon coated nano zero-valent iron composite material and preparation method and application thereof |
| CN114433020A (en) * | 2021-12-21 | 2022-05-06 | 扬州大学 | Composite material of zero-valent iron fixed by biochar, preparation method thereof and application thereof in removing tetracycline in water |
| CN114570421A (en) * | 2022-04-01 | 2022-06-03 | 合肥工业大学 | Yeast in-situ fixed nano zero-valent ferromagnetic material and preparation method and application thereof |
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| CN115722227A (en) * | 2022-12-28 | 2023-03-03 | 国科大杭州高等研究院 | Iron slag-doped wine-making sludge biochar material and preparation method and application thereof |
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| CN113943030A (en) * | 2021-11-29 | 2022-01-18 | 中国科学院南京土壤研究所 | Biomass carbon-coated nano zero-valent iron composite material for treating chlorobenzene-polluted water body by activating peroxymonosulfate and preparation and application thereof |
| CN114226721A (en) * | 2021-11-30 | 2022-03-25 | 南开大学 | Graphite carbon coated nano zero-valent iron composite material and preparation method and application thereof |
| CN114226721B (en) * | 2021-11-30 | 2022-08-16 | 南开大学 | Graphite carbon coated nano zero-valent iron composite material and preparation method and application thereof |
| CN114433020A (en) * | 2021-12-21 | 2022-05-06 | 扬州大学 | Composite material of zero-valent iron fixed by biochar, preparation method thereof and application thereof in removing tetracycline in water |
| CN114570421A (en) * | 2022-04-01 | 2022-06-03 | 合肥工业大学 | Yeast in-situ fixed nano zero-valent ferromagnetic material and preparation method and application thereof |
| CN114789040B (en) * | 2022-04-28 | 2023-11-17 | 辽宁石油化工大学 | Ball-milling zero-valent iron sulfur/biochar doped composite material and preparation method and application thereof |
| CN114789040A (en) * | 2022-04-28 | 2022-07-26 | 辽宁石油化工大学 | Ball-milled zero-valent iron-doped sulfur/biochar composite material and preparation method and application thereof |
| CN114939424A (en) * | 2022-05-16 | 2022-08-26 | 齐鲁工业大学 | Bimetallic charcoal catalyst, preparation method and application |
| CN114984911A (en) * | 2022-06-13 | 2022-09-02 | 陕西学前师范学院 | Preparation method of high-adsorption-performance biochar-nano zero-valent iron compound |
| CN115338245A (en) * | 2022-07-19 | 2022-11-15 | 广州珠矶科技有限公司 | Method for removing soil organic matter by efficiently catalyzing sodium persulfate |
| CN115282927A (en) * | 2022-09-13 | 2022-11-04 | 广州大学 | Removal of tetracycline in water by using zero-valent manganese biochar composite material |
| CN115282927B (en) * | 2022-09-13 | 2023-10-20 | 广州大学 | Removal of tetracycline in water by zero-valent manganese biochar composite material |
| CN115532263A (en) * | 2022-11-03 | 2022-12-30 | 清华大学 | Iron-carbon composite material and irradiation preparation method and application method thereof |
| CN115722251A (en) * | 2022-12-14 | 2023-03-03 | 昆明理工大学 | Preparation method and application of hetero-atom-doped algae-based biochar loaded nano zero-valent metal catalyst |
| CN115722251B (en) * | 2022-12-14 | 2024-01-30 | 昆明理工大学 | Preparation method and application of heteroatom doped algae-based biochar loaded nano zero-valent metal catalyst |
| CN115722227A (en) * | 2022-12-28 | 2023-03-03 | 国科大杭州高等研究院 | Iron slag-doped wine-making sludge biochar material and preparation method and application thereof |
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