CN113600166A - Biomass-based catalyst for advanced oxidation and preparation method and application thereof - Google Patents
Biomass-based catalyst for advanced oxidation and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 244000269722 Thea sinensis Species 0.000 claims abstract description 39
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- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
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- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical group OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 59
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 11
- 239000002957 persistent organic pollutant Substances 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
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- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 2
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/391—
-
- B01J35/393—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention discloses a biomass-based catalyst for advanced oxidation and a preparation method and application thereof, which comprises the steps of crushing green tea leaves, putting the crushed green tea leaves into deionized water for water bath heating, filtering, and collecting the filtered green tea leaves respectively to obtain solid residues and a green tea extracting solution; freeze-drying the solid residue, sieving, and pyrolyzing under the protection of inert gas to obtain green tea residue biochar; fully and uniformly mixing the green tea residue biochar and the ferric salt solution to form a mixed solution; introducing inert gas into the mixed solution to remove air, then adding absolute ethyl alcohol, uniformly stirring, then adding the green tea extracting solution into the uniformly mixed solution, fully stirring to obtain a black mixed solution, performing suction filtration, alternately washing the obtained black solid sample by using deionized water and absolute ethyl alcohol, and finally drying to obtain the black solid sample. Compared with zero-valent iron loaded biochar prepared by a traditional chemical liquid phase method, the green tea extract reducing agent is cheap and easy to obtain, is safe and pollution-free, has better dispersity of nano zero-valent iron, and increases effective reaction sites.
Description
Technical Field
The invention belongs to the technical field of water pollution treatment, relates to an advanced oxidation technology, and particularly relates to a biomass-based catalyst for advanced oxidation and a preparation method and application thereof.
Background
Para-nitrophenol has high toxicity, carcinogenicity and bioaccumulation, and is generally released into the environment from industries such as dyes, plasticizers, pesticides and pharmaceuticals. The p-nitrophenol has the characteristics of wide range, high toxicity and low degradation speed, which causes serious environmental problems, so that the finding of an efficient environment-friendly method for solving the problems has certain practical significance.
The existing methods for treating p-nitrophenol wastewater mainly comprise a biochemical method, an adsorption method, a liquid membrane method and a chemical oxidation method. The biochemical method has large floor area and low degradation rate, secondary pollution can be generated by an adsorption method and a liquid membrane method, the research on the high-efficiency clean chemical oxidation method mainly focuses on photochemical oxidation and a combination technology thereof, and few reports on the treatment of p-nitrophenol wastewater by an ultrasonic-enhanced ozone oxidation technology are reported, but the research depth is not enough and is not enough to be applied to industrial treatment.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problems of the prior advanced oxidation technology for degrading organic pollutants in water and the technical defects of catalyst preparation, and provides a method for degrading p-nitrophenol organic pollutants in water by using biomass as a catalyst to catalytically activate persulfate.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a biomass-based catalyst for advanced oxidation comprises the following steps:
(1) pulverizing green tea residue, heating in deionized water in water bath, filtering, and collecting solid residue and green tea extractive solution;
(2) freeze-drying the solid residue obtained in the step (1), sieving, and then pyrolyzing under the protection of inert gas to obtain green tea residue biochar;
(3) fully and uniformly mixing the green tea residue biochar obtained in the step (2) with an iron salt solution to form a mixed solution;
(4) introducing inert gas into the mixed solution obtained in the step (3) to remove air, then adding absolute ethyl alcohol and uniformly stirring, then adding the green tea extracting solution obtained in the step (1) into the uniformly mixed solution, and fully stirring to obtain black mixed solution;
(5) and (4) carrying out suction filtration on the black mixed liquid obtained in the step (4), alternately washing the obtained black solid sample by using deionized water and absolute ethyl alcohol, and finally drying to obtain the black solid sample.
Specifically, in the step (1), the water bath heating temperature is controlled to be 80-100 ℃, and the heating time is 1-2 hours.
In the step (2), heating the pyrolysis to 500-700 ℃ at a speed of 4-6 ℃/min, preserving the heat for 30-600 min, and washing the product obtained by pyrolysis with deionized water and absolute ethyl alcohol alternately to obtain the green tea residue biochar.
In the step (3), the mass ratio of the ferric salt solution to the green tea residue biochar is 0.4-1; wherein the ferric salt solution is a ferrous sulfate heptahydrate solution with the molar concentration of 0.14-0.7 moL/L.
In the step (4), the volume ratio of the absolute ethyl alcohol to the mixed liquid to the green tea extracting solution is 1: 1-2: 1.
Further, the invention also claims the biomass-based catalyst for advanced oxidation prepared by the preparation method.
Furthermore, the invention also claims the application of the biomass-based catalyst in degrading organic pollutants in water.
Preferably, the organic contaminant is p-nitrophenol.
Specifically, the degradation method comprises the following steps: adding a biomass-based catalyst and persulfate into the water body to catalyze persulfate to carry out advanced oxidation degradation on the p-nitrophenol in the water body.
Preferably, in the degradation process, in the biomass-based catalyst, the mass ratio of zero-valent iron to biochar is 0.2-1, the persulfate is potassium persulfate, and the molar ratio of potassium persulfate to p-nitrophenol is 10: 1-400: 1.
Has the advantages that:
the invention takes green tea extract as a reducing agent and green tea residue as raw materials to prepare biomass-based preparation of nano zero-valent iron-loaded biochar; the obtained nano zero-valent iron-loaded biochar is used as a catalyst to be applied to advanced oxidative catalytic degradation of organic pollutants in water, and further used as a catalyst to catalyze persulfate, so that the persulfate is used as an advanced oxidation system to degrade p-nitrophenol organic pollutants, and the environment is purified; the method specifically comprises the following steps:
(1) compared with zero-valent iron-loaded biochar prepared by a traditional chemical liquid phase method, the green tea extract reducing agent is cheap and easy to obtain, safe and pollution-free, the nano zero-valent iron has better dispersibility, effective reaction sites are increased, and the material prepared by the method is used as the catalyst for catalyzing and activating a high oxidation system constructed by persulfate, so that the capacity of the formed advanced oxidation system for degrading organic pollutants is stronger, and the catalyst has strong oxidation resistance and stability, is a novel, environment-friendly and low-cost catalyst with huge potential, provides a green technology for repairing organic pollution of water, has a good application prospect in the field of water treatment, and provides assistance for green development.
(2) The catalyst of the invention utilizes cheap and easily available raw materials such as green tea and the like, rapidly prepares the nano zero-valent iron loaded biochar by loading iron with lower cost, improves the dispersibility of the nano zero-valent iron on the biochar by tea polyphenol, prevents agglomeration, and enables an advanced oxidation system formed by activating persulfate by the tea polyphenol as the catalyst to have oxidation resistance and effective reaction activity for a long time. The preparation method is simple and suitable for industrial production, pollution is not generated in the preparation process, and a new idea is provided for the preparation of the nano zero-valent iron-loaded biochar and the advanced oxidative degradation of organic pollutants in water.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
Fig. 1 is an electron microscope scanning image of the original biochar (a), the zero-valent iron-loaded biochar (b) prepared by the present invention, and the zero-valent iron-loaded biochar (c) prepared by the conventional chemical liquid phase method, respectively.
FIG. 2 is a graph showing the effect of different amounts of zero-valent iron-loaded biochar prepared by the two methods of the present invention on the degradation of p-nitrophenol.
FIG. 3 is a graph showing the effect of the exposure time of zero-valent iron-supported biochar catalysts prepared in examples of the present invention and comparative examples in air.
FIG. 4 is a graph showing the influence of pH on the degradation of p-nitrophenol by potassium persulfate catalyzed by zero-valent iron-loaded biochar prepared by the method.
FIG. 5 shows the degradation of potassium persulfate in real water by the zero-valent iron-supported biochar prepared by the method of the invention.
FIG. 6 shows the catalytic performance of the zero-valent iron-loaded biochar prepared by the invention after repeated use.
FIG. 7 shows the total Fe leaching amount of the advanced oxidation system of zero-valent iron-loaded biochar catalyzed potassium persulfate prepared by the method under different pH environments.
Detailed Description
The invention will be better understood from the following examples.
Example 1
The method comprises the following steps: pulverizing 50g of green tea residue with a pulverizer, adding into 200mL of deionized water, heating in water bath at 80 deg.C for 1h, and filtering to obtain solid green tea extract;
step two: freeze-drying the filtered solid green tea residue obtained in the step one, sieving with a 100-mesh sieve, heating the sieved material to 500 ℃ at 4 ℃/min in an atmosphere furnace under the protection of nitrogen, pyrolyzing for 30min, and washing the pyrolyzed material with deionized water and absolute ethyl alcohol for several times to obtain green tea residue Biochar (BC) (see figure 1 a);
step three: BC (2g) from step two was mixed with 50mL of FeSO in a three-necked flask4·7H2Fully and uniformly mixing the O to form a mixed solution;
step four: introducing nitrogen into the mixed solution in the third step for 10min, pouring 50mL of absolute ethyl alcohol into the mixed solution, stirring the mixed solution for 1h, then adding 50mL of green tea extracting solution into the uniformly mixed solution, and stirring the mixed solution to be black;
step five: and (3) performing vacuum filtration to obtain a black solid sample, sequentially washing the black solid sample with deionized water and absolute ethyl alcohol for several times, putting the black solid sample into a vacuum drying oven for drying, and drying to obtain the green-method-prepared nano zero-valent iron-loaded biochar (G-nZVI-BC) (see figure 1 b).
The BC and G-nZVI-BC materials obtained are detected by a Scanning Electron Microscope (SEM), and the results are shown in FIG. 1(a) and FIG. 1 (b).
Comparative example
The method comprises the following steps: crushing 50g of green tea leaves by using a crusher, putting the crushed green tea leaves into 200mL of deionized water, heating the crushed green tea leaves for 1h in a water bath at the temperature of 80 ℃, and filtering the mixture to obtain green tea residues;
step two: freeze-drying the green tea residue obtained in the first step, sieving the dried green tea residue with a 100-mesh sieve, heating the sieved material to 500 ℃ at a speed of 4 ℃/min in an atmosphere furnace under the protection of nitrogen, pyrolyzing the material for 30min, and washing the pyrolyzed material with deionized water and absolute ethyl alcohol for several times to obtain green tea residue Biochar (BC);
step three: BC (2g) from step two was mixed with 50mL of FeSO in a three-necked flask4·7H2Fully and uniformly mixing the O to form a mixed solution;
step four: introducing nitrogen into the mixed solution in the third step for 10min, pouring 50mL of absolute ethyl alcohol into the mixed solution, stirring the mixed solution for 1h, and then adding 50mL of NaBH into the uniformly mixed solution4The solution is stirred and the mixed solution is black;
step five: and (3) performing vacuum filtration to obtain a black solid sample, sequentially washing the black solid sample with deionized water and absolute ethyl alcohol for several times, putting the black solid sample into a vacuum drying oven for drying, and drying to obtain the nano zero-valent iron-loaded biochar (C-nZVI-BC) prepared by the traditional chemical liquid phase method (see figure 1C).
As a result of SEM scanning of FIG. 1, the degree of nZVI agglomeration was smaller and the dispersibility of zero-valent iron particles was better in G-nZVI-BC (FIG. 1b) than in C-nZVI-BC (FIG. 1C). The reason is mainly because polyphenol and antioxidant exist in the extracting solution, so that excessive aggregation of the nano zero-valent iron particles can be effectively prevented, the dispersity of the nano zero-valent iron particles is further improved, and effective reaction sites are further increased.
Example 2
Comparing the performance of C-nZVI-BC and G-nZVI-BC in catalyzing potassium Persulfate (PDS) to degrade p-nitrophenol (PNP) under the condition that the nanometer zero-valent iron (nZVI) prepared in the example 1 supports the Biochar (BC), the samples with the mass ratio of the nanometer zero-valent iron to the biochar of (0.2, 0.4, 0.6, 1):1 are obtained for comparison by the preparation processes described in the above example 1 and the comparative example, respectively.
The mass ratio of nZVI to BC on C-nZVI-BC/G-nZVI-BC (0.2, 0.4, 0.6, 1):1, and the initial concentrations of C-nZVI-BC and G-nZVI-BC in PNP were 0.8G/L, and they were added to 100mL brown glass bottles, respectively, PDS and PNP were added to each glass bottle, the molar ratio of PDS to PNP was 100:1, and the initial concentration of PNP was 10mg/L, the pH was adjusted to 5.0, and the reaction temperature was room temperature (20 ℃). When the reaction is carried out, 1mL of reaction solution and 50. mu.L of Na with a concentration of 1mol/L are taken out at 2min, 5min, 10min, 20min, 30min, 60min and 90min respectively2S2O3And mixed to terminate the reaction, the sample was kept at 4 ℃ and the concentration of PNP in the solution was measured using High Performance Liquid Chromatography (HPLC) over 24 h. The results of the measurements are shown in FIGS. 2a and 2b, respectively.
The results show that the two systems have significantly different rules for degrading PNP. The mass ratio of nZVI to BC is increased from 0.2 to 0.4, and the removal rate of PNP by the two systems is increased to a certain extent. However, the mass ratio of nZVI to BC is continuously increased from 0.4 to 1, the removal rate of PNP by the prepared C-nZVI-BC catalytic PDS super-oxidation system is rather reduced, the removal rate of PNP is only 90.33% (as shown in fig. 2a), the degradation rate of PNP by the prepared G-nZVI-BC catalytic PDS super-oxidation system is further increased, and the removal rate of PNP reaches 99.07% (as shown in fig. 2 b). The removal rate of PNP by the catalytic PDS super-oxidation system of the final example is higher than that of the comparative example.
Compared with a C-nZVI-BC catalyzed PDS super oxidation system, the tea polyphenol in G-nZVI-BC further improves Fe0The dispersion on BC prevents the agglomeration of nZVI on BC, so that the degradation rate of PNP is further improved. And the increase of the nZVI loading capacity on the C-nZVI-BC leads to further reduction of the dispersity on the BC, thereby inhibiting the catalytic activity of the C-nZVI-BC, and leading to certain reduction of the removal rate of PNP by a comparative example catalytic PDS super oxidation system. The mass ratio of nZVI to BC in the subsequent example G-nZVI-BC was determined to be 0.4, taking the catalytic performance and economy into consideration.
Example 3
The prepared G-nZVI-BC and C-nZVI-BC materials are exposed in the air for a long time to further determine the oxidation resistance and stability of the G-nZVI-BC in the air.
The initial concentration of C-nZVI-BC and G-nZVI-BC in PNP is 0.8G/L, the mass ratio of nZVI to BC is 0.4:1, the mixture is respectively added into a 100mL brown glass bottle, PDS and PNP are added into each glass bottle, the molar ratio of PDS to PNP is 100:1, the initial concentration of PNP is 10mg/L, the pH value is adjusted to be 5.0, and the reaction is carried out at the reaction temperature of room temperature (20 ℃) for 0-3 months. When the reaction is carried out, 1mL of reaction solution and 50 μ L of Na with the concentration of 1mol/L are respectively taken out at 2min, 5min, 10min, 20min, 30min, 60min and 90min2S2O3Mixed to terminate the reaction, the sample was stored at 4 ℃ and the PNP concentration in solution was determined using HPLC over 24 h. The results of the measurements are shown in FIG. 3, and the results of the removal rates are shown in Table 1.
TABLE 1PDS removal efficiency of PNP
Therefore, the catalytic efficiency of the G-nZVI-BC of the invention is basically kept unchanged, while the catalytic efficiency of the C-nZVI-BC is greatly reduced due to the inactivation of the particles, and the oxidation resistance of the nZVI can be enhanced by substances such as tea polyphenol derived from green tea extract on the surface of the G-nZVI-BC. The super oxidation system constructed by the prepared G-nZVI-BC catalyzed PDS has higher stability than that constructed by the C-nZVI-BC catalyzed PDS, so that the material has effective reaction activity for a long time, and the practical application potential of the invention in the field of water treatment is increased.
Example 4
Influence of pH on degradation of PNP in water body by the prepared G-nZVI-BC catalyzed PDS.
The initial concentration of G-nZVI-BC in the PNP is 0.8G/L, the mass ratio of nZVI to BC is 0.4:1, the mixture is added into a 100mL brown glass bottle, PDS and PNP are added into the glass bottle, the molar ratio of PDS to PNP is 100:1, the initial concentration of PNP is 10mg/L, and the pH value is adjusted to be 2.15-9.23. The reaction temperature was room temperature (20 ℃). When the reaction is carried out, 1mL of reaction solution and 50. mu.L of Na with a concentration of 1mol/L are taken out at 2min, 5min, 10min, 20min, 30min, 60min and 90min respectively2S2O3Mixed to terminate the reaction, the sample was stored at 4 ℃ and the PNP concentration in solution was determined using HPLC over 24 h. The determination result is shown in FIG. 4, and the result shows that the super-oxidation system constructed by the G-nZVI-BC catalyst prepared by the invention has good PNP removing effect within a wider pH range of 2.15-9.23.
Example 5
In order to further determine the practical application value of the super oxidation system constructed by the G-nZVI-BC catalyst, the prepared G-nZVI-BC is applied to a practical water body to remove PNP.
Collecting natural water body on the surface and underground water body respectively, filtering with cellulose acetate membrane with pore diameter of 0.45 μm to obtain background solution, adding PNP 10mg/L, and storing the sample at 4 deg.C. The initial concentration of G-nZVI-BC is 0.8G/L, the mass ratio of nZVI to BC is 0.4, the molar ratio of PDS to PNP is 100:1, and the initial concentration of PNP is 10 mg/L. The reaction was carried out in a 100mL brown glass vial at room temperature (20 ℃). When the reaction is carried out, 1mL of reaction solution and 50. mu.L of Na with a concentration of 1mol/L are taken out at 2min, 5min, 10min, 20min, 30min, 60min and 90min respectively2S2O3Mixed to terminate the reaction, the sample was stored at 4 ℃ and the PNP concentration in solution was determined using HPLC over 24 h. The results of the measurements are shown in FIG. 5, which shows that PNP are present in the surface water group after 90min of reactionThe degradation rate is 92.48%, and the PNP degradation rate of the underground water group is 94.41%, which shows that the degradation process has no significant influence on both underground water and surface water.
The degradation degree of PNP in surface water body and underground water body means that the super oxidation system constructed by the G-nZVI-BC catalyst prepared by the invention is feasible in river and underground water remediation.
Example 6
The prepared G-nZVI-BC was evaluated for catalytic performance after repeated use.
The initial concentration of G-nZVI-BC was 0.8G/L, the mass ratio of nZVI to BC was 0.4, the molar ratio of PDS to PNP was 100:1, the initial concentration of PNP was 10mg/L, and the pH was adjusted to 5.0. The reaction was carried out in a 100mL brown glass vial at room temperature (20 ℃). When the reaction is carried out, 1mL of reaction solution and 50. mu.L of Na with a concentration of 1mol/L are taken out at 2min, 5min, 10min, 20min, 30min, 60min and 90min respectively2S2O3Mixed to terminate the reaction, the sample was stored at 4 ℃ and the PNP concentration in solution was determined using HPLC over 24 h. The determination result is shown in FIG. 6, and the result shows that after 5 times of repeated use of G-nZVI-BC, the PNP removal rate can still reach 90.04% after the fifth time of use, and the reaction rate is higher.
Example 7
In order to further determine the good recycling property of the G-nZVI-BC, the total Fe leaching rate of a super oxidation system constructed by the prepared G-nZVI-BC catalyst under different pH conditions is determined.
The initial concentration of G-nZVI-BC is 0.8G/L, the mass ratio of nZVI to BC is 0.4, the molar ratio of PDS to PNP is 100:1, the initial concentration of PNP is 10mg/L, and the pH is adjusted to be 2.14-9.03. The reaction was carried out in a 100mL brown glass vial at room temperature (20 ℃). When the reaction is carried out, 1mL of reaction solution and 50. mu.L of Na with a concentration of 1mol/L are taken out at 2min, 5min, 10min, 20min, 30min, 60min and 90min respectively2S2O3Mixed to terminate the reaction, the sample was stored at 4 ℃ and the PNP concentration in solution was determined using HPLC over 24 h. As a result of measurement, referring to FIG. 7, it was found that almost no leaching of Fe was observed at the initial pH values of 4.95 to 9.03, whereas leaching of Fe was observed at the initial pH values of 4.02 and 3.21 and 2.14, leaching of 1.51mg/L, 2.36mg/L and 3.57mg/L iron was detected, respectively. That is, only 3.57X 10 of 1g G-nZVI-BC was leached out under strong acidic condition (initial pH of 2.14)-3g of Fe (0.357% by mass). This is because the iron-loaded biochar forms a large amount of Fe-O-C chemical bonds between Fe and C, and most Fe belongs to a more stable chemical state.
Therefore, under acidic conditions, only a very small amount of Fe is leached out from G-nZVI-BC, and the G-nZVI-BC has good stability in a system for removing PNP by the cooperation of PDS.
The present invention provides a biomass-based catalyst for advanced oxidation, a preparation method and an application thereof, and a method and a way for implementing the technical scheme are numerous, the above description is only a preferred embodiment of the present invention, and it should be noted that, for a person skilled in the art, a plurality of improvements and modifications can be made without departing from the principle of the present invention, and the improvements and modifications should be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. A preparation method of a biomass-based catalyst for advanced oxidation is characterized by comprising the following steps:
(1) pulverizing green tea residue, heating in deionized water in water bath, filtering, and collecting solid residue and green tea extractive solution;
(2) freeze-drying the solid residue obtained in the step (1), sieving, and then pyrolyzing under the protection of inert gas to obtain green tea residue biochar;
(3) fully and uniformly mixing the green tea residue biochar obtained in the step (2) with an iron salt solution to form a mixed solution;
(4) introducing inert gas into the mixed solution obtained in the step (3) to remove air, then adding absolute ethyl alcohol and uniformly stirring, then adding the green tea extracting solution obtained in the step (1) into the uniformly mixed solution, and fully stirring to obtain black mixed solution;
(5) and (4) carrying out suction filtration on the black mixed liquid obtained in the step (4), alternately washing the obtained black solid sample by using deionized water and absolute ethyl alcohol, and finally drying to obtain the black solid sample.
2. The preparation method of the biomass-based catalyst for advanced oxidation according to claim 1, wherein in the step (1), the temperature of water bath heating is controlled to be 80-100 ℃, and the heating time is 1-2 h.
3. The preparation method of the biomass-based catalyst for advanced oxidation according to claim 1, wherein in the step (2), the temperature of pyrolysis is raised to 500-700 ℃ at a rate of 4-6 ℃/min, the temperature is maintained for 30-600 min, and the product obtained by pyrolysis is washed alternately with deionized water and absolute ethyl alcohol to obtain the green tea residue biochar.
4. The method for preparing a biomass-based catalyst for advanced oxidation according to claim 1, wherein in the step (3), the mass ratio of the ferric salt solution to the green tea residue biochar is 0.4-1; wherein the ferric salt solution is a ferrous sulfate heptahydrate solution with the molar concentration of 0.14-0.7 moL/L.
5. The method for preparing a biomass-based catalyst for advanced oxidation according to claim 1, wherein in the step (4), the volume ratio of the absolute ethanol to the mixed solution to the green tea extract is 1:1 to 2: 1.
6. The biomass-based catalyst for advanced oxidation prepared by the preparation method of any one of claims 1 to 5.
7. Use of the biomass-based catalyst for advanced oxidation according to claim 6 for degrading organic pollutants in a body of water.
8. The use of claim 7, wherein the organic contaminant is p-nitrophenol.
9. The use of claim 8, wherein the biomass-based catalyst and the persulfate are added to the water to catalyze the high-level oxidative degradation of p-nitrophenol in the water by the persulfate.
10. The application of the biomass-based catalyst according to claim 9, wherein the mass ratio of zero-valent iron to biochar is 0.2-1, the persulfate is potassium persulfate, and the molar ratio of the potassium persulfate to the p-nitrophenol is 10: 1-400: 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110526311A (en) * | 2019-09-07 | 2019-12-03 | 中国地质科学院水文地质环境地质研究所 | Utilize the medicament of green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer |
| CN114042456A (en) * | 2021-12-03 | 2022-02-15 | 浙江工业大学 | Method for preparing Fe-based catalyst by using biomass as raw material and application of Fe-based catalyst |
| CN115739084A (en) * | 2022-10-20 | 2023-03-07 | 北京市生态环境保护科学研究院 | Heterogeneous catalyst for degrading organic dye in water and synthetic method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107486237A (en) * | 2017-08-30 | 2017-12-19 | 昆明理工大学 | A kind of formyl chloride tea stalk base charcoal adsorption catalyst and preparation method thereof |
| CN107930629A (en) * | 2017-11-15 | 2018-04-20 | 南京理工大学 | The preparation method of support type charcoal catalysis material |
| CN109225221A (en) * | 2018-10-24 | 2019-01-18 | 南京理工大学 | The preparation method of charcoal load Zero-valent Iron catalysis material |
-
2021
- 2021-09-02 CN CN202111024924.1A patent/CN113600166A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107486237A (en) * | 2017-08-30 | 2017-12-19 | 昆明理工大学 | A kind of formyl chloride tea stalk base charcoal adsorption catalyst and preparation method thereof |
| CN107930629A (en) * | 2017-11-15 | 2018-04-20 | 南京理工大学 | The preparation method of support type charcoal catalysis material |
| CN109225221A (en) * | 2018-10-24 | 2019-01-18 | 南京理工大学 | The preparation method of charcoal load Zero-valent Iron catalysis material |
Non-Patent Citations (1)
| Title |
|---|
| BO WANG等: "Activation of persulfate by green nano-zero-valent iron-loaded biochar for the removal of p-nitrophenol: Performance, mechanism and variables effects", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110526311A (en) * | 2019-09-07 | 2019-12-03 | 中国地质科学院水文地质环境地质研究所 | Utilize the medicament of green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer |
| CN114042456A (en) * | 2021-12-03 | 2022-02-15 | 浙江工业大学 | Method for preparing Fe-based catalyst by using biomass as raw material and application of Fe-based catalyst |
| CN114042456B (en) * | 2021-12-03 | 2023-11-10 | 浙江工业大学 | Method for preparing Fe-based catalyst by taking biomass as raw material and application of Fe-based catalyst |
| CN115739084A (en) * | 2022-10-20 | 2023-03-07 | 北京市生态环境保护科学研究院 | Heterogeneous catalyst for degrading organic dye in water and synthetic method |
| CN115739084B (en) * | 2022-10-20 | 2023-11-17 | 北京市生态环境保护科学研究院 | Heterogeneous catalyst for degrading organic dye in water and synthesis method |
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