CN109126873B - Biochar-ferriporphyrin composite material and preparation method and application thereof - Google Patents
Biochar-ferriporphyrin composite material and preparation method and application thereof Download PDFInfo
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- CN109126873B CN109126873B CN201811015218.9A CN201811015218A CN109126873B CN 109126873 B CN109126873 B CN 109126873B CN 201811015218 A CN201811015218 A CN 201811015218A CN 109126873 B CN109126873 B CN 109126873B
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- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
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- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000004729 solvothermal method Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
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- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 26
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 22
- 230000010355 oscillation Effects 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229960005070 ascorbic acid Drugs 0.000 claims description 11
- 235000010323 ascorbic acid Nutrition 0.000 claims description 11
- 239000011668 ascorbic acid Substances 0.000 claims description 11
- 239000002351 wastewater Substances 0.000 claims description 11
- 239000002028 Biomass Substances 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 241000723346 Cinnamomum camphora Species 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 8
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- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 18
- -1 sulfate radical free radical Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000003213 activating effect Effects 0.000 description 8
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000001994 activation Methods 0.000 description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 206010067482 No adverse event Diseases 0.000 description 2
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- 239000003463 adsorbent Substances 0.000 description 2
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- 231100000719 pollutant Toxicity 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007725 thermal activation Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- VIFYCNBECFTICC-UHFFFAOYSA-N [C].C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Fe] Chemical compound [C].C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Fe] VIFYCNBECFTICC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- 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
- C02F2101/36—Organic compounds containing halogen
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a biochar-ferriporphyrin composite material and a preparation method and application thereof, wherein the biochar-ferriporphyrin composite material comprises biochar and ferriporphyrin, and the ferriporphyrin is loaded on the biochar, and the mass ratio of the biochar to the ferriporphyrin is 5-20: 1. The preparation method comprises the following steps: mixing the biochar, the ferriporphyrin and an organic solvent for solvothermal reaction, filtering, washing and drying to obtain the biochar-ferriporphyrin composite material. The biochar-ferriporphyrin composite material has the advantages of good catalytic activity, good stability, environmental friendliness and the like, and the preparation method has the advantages of simple process, cheap raw materials, low production cost and the like, has the advantages of controllable process, easiness in operation and the like, is suitable for large-scale preparation, and is beneficial to industrial production. The biochar-ferriporphyrin composite material can efficiently activate persulfate to generate sulfate radical free radicals, so that perfluorooctanoic acid in a water body is effectively degraded, and the biochar-ferriporphyrin composite material has very important significance for effectively treating perfluorooctanoic acid in the water body.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment and environmental catalysis, and relates to a biochar-ferriporphyrin composite material as well as a preparation method and application thereof.
Technical Field
Perfluorooctanoic acid is an organic acid commonly used as a surfactant, emulsifier. Perfluoro caprylic acid has a stable chemical structure, has a strong C-F bond, is difficult to degrade from the environment, and is frequently detected in soil, surface water and underground water. Perfluorooctanoic acid is bioaccumulating and may enter the body through food, air and water, causing reduced fertility and other immune system disorders. At present, the treatment method of the perfluorooctanoic acid comprises the following steps: the adsorption method is most widely used, but the adsorption method has disadvantages such as treatment of eluent, secondary pollution, regeneration of adsorbent, and the like.
The persulfate advanced oxidation technology mainly utilizes sulfate radical free radical to oxidize pollutants in a water body, and the sulfate radical free radical has the advantages of high oxidation-reduction potential and long average service life and can effectively degrade perfluorooctanoic acid. Currently, sulfate radicals are generated by persulfate activation, which includes: thermal activation, transition metal activation, electrolytic activation, and the like, with thermal activation being predominant. However, the use of thermally activated persulfates has the following problems: long time, poor activating effect and high energy consumption. In addition, zero-valent iron or ferrous iron is used as a catalyst, and although persulfate can be activated to generate sulfate radicals, the catalysts such as zero-valent iron and ferrous iron are unstable in the environment and are easy to be converted into other substances, so that good catalytic performance cannot be obtained, and the activation effect on persulfate is poor. Therefore, the obtained catalyst for activating the persulfate has good catalytic activity, good stability and environmental friendliness, and has very important significance for effectively activating the persulfate to obtain more sulfate radicals and effectively improving the removal effect of the persulfate advanced oxidation technology on the perfluorooctanoic acid.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a biochar-ferriporphyrin composite material with good catalytic activity, good stability and environmental friendliness, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a biochar-ferriporphyrin composite comprises biochar and ferriporphyrin, wherein the ferriporphyrin is loaded on the biochar; the mass ratio of the biochar to the ferriporphyrin is 5-20: 1.
As a general technical concept, the invention provides a preparation method of the biochar-ferriporphyrin composite material, which comprises the following steps: mixing the biochar, the ferriporphyrin and an organic solvent for solvothermal reaction, filtering, washing and drying to obtain the biochar-ferriporphyrin composite material.
The preparation method is further improved, wherein the mass ratio of the biochar to the ferriporphyrin is 5-20: 1; the ratio of the ferriporphyrin to the organic solvent is 1 g: 500 mL.
In the above preparation method, further improvement, the preparation method of the biochar comprises the following steps: and drying, crushing and sieving the biomass, pyrolyzing, washing and drying the biomass in a nitrogen atmosphere to obtain the biochar.
In the above preparation method, further improvement is provided, in the preparation method of the biochar, the biomass is camphor tree leaves; sieving is to sieve the crushed biomass by a sieve of 80-200 meshes; the pyrolysis is carried out at a temperature of 400 ℃ to 500 ℃; the pyrolysis time is 4-6 h; and in the washing step, the product obtained by pyrolysis is firstly soaked in hydrochloric acid solution with the concentration of 1mol/L for 10 to 16 hours and then washed by water until the pH value of the washing liquid is not changed any more.
In the preparation method, the organic solvent is at least one of N, N-dimethylformamide, ethanol and chloroform; the solvent thermal reaction is carried out at the temperature of 80-100 ℃; the solvothermal reaction time is 8-10 h; the drying is vacuum drying; the vacuum drying is carried out at 30-40 ℃.
As a general technical concept, the invention also provides an application of the biochar-ferriporphyrin composite material or the biochar-ferriporphyrin composite material prepared by the preparation method in removing the perfluorooctanoic acid in the water body.
The application is further improved, and comprises the following steps: mixing the biochar-ferriporphyrin composite material with the perfluoro caprylic acid wastewater, adding persulfate and ascorbic acid to carry out oscillation reaction, and finishing the removal of the perfluoro caprylic acid in the water body; the addition amount of the biochar-ferriporphyrin composite material is 0.1-2.0 g of biochar-ferriporphyrin composite material added in per liter of perfluorooctanoic acid wastewater; the molar ratio of the persulfate to the perfluoro caprylic acid in the perfluoro caprylic acid wastewater is 50-500: 1; the addition amount of the ascorbic acid is such that the concentration of the ascorbic acid in the oscillation reaction system is 1 mmol/L-10 mmol/L.
The application is further improved, wherein the initial concentration of the perfluorooctanoic acid in the perfluorooctanoic acid wastewater is 2 mg/L-100 mg/L; the persulfate is sodium persulfate and/or potassium persulfate.
The application is further improved, wherein the pH value of the reaction system is controlled to be 1-11 in the oscillation reaction process; the oscillation reaction is carried out at the rotating speed of 150-160 rpm; the oscillation reaction is carried out at the temperature of 20-30 ℃; the oscillation reaction time is 1 min-12 h.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a biochar-ferriporphyrin composite material which comprises biochar and ferriporphyrin, wherein the ferriporphyrin is loaded on the biochar. According to the invention, the biochar is a multi-carbon material prepared by high-temperature pyrolysis of biomass, and a porous structure can be formed in the preparation process, so that the biochar has a large specific surface area, can be used as an adsorbent to adsorb pollutants in an environmental medium, and can also be used as a carrier to provide a loading site for particles, and meanwhile, the biochar also has the advantages of simplicity in preparation, low preparation cost (wide raw material source, low raw material price), strong stability and the like. On the basis, the invention takes the biological carbon as a carrier, the iron porphyrin is loaded on the biological carbon, the agglomeration of the iron porphyrin can be reduced, and the biological carbon has rich permanent free radicals and can provide electrons for the iron porphyrin in the catalysis process, thereby improving the catalytic activity and stability of the iron porphyrin and leading the biological carbon-iron porphyrin composite material to have better catalytic activity and stability. In addition, in the invention, the biochar and the iron porphyrin are both environment-friendly materials and have no toxic effect on the environment, so that the composite material prepared by compounding the biochar and the iron porphyrin is also an environment-friendly material and has no toxic effect on the environment. The biochar-ferriporphyrin composite material has the advantages of good catalytic activity, good stability, environmental friendliness and the like, can be widely used for activating persulfate to activate more sulfate radicals, and has very important significance for improving the removal effect of perfluorooctanoic acid in water.
(2) In the biochar-ferriporphyrin composite material, the mass ratio of biochar to ferriporphyrin is optimized to be 5-20: 1, so that the catalytic activity and stability of ferriporphyrin are improved, the reason is that excessive ferriporphyrin is easy to agglomerate if the mass of ferriporphyrin is too high, the stability is poor, better catalytic performance cannot be obtained, and the ideal catalytic effect cannot be achieved if the mass of ferriporphyrin is too low, so that persulfate cannot be effectively activated if the mass of ferriporphyrin is too high or too low, and more sulfate radicals cannot be obtained. Therefore, within the mass ratio range of the biochar and the ferriporphyrin, the biochar and the ferriporphyrin can respectively realize the maximum utilization rate without causing material waste, so that the respective best performance is exerted to the maximum extent, the catalytic activity and the stability of the biochar-ferriporphyrin composite material are best, the persulfate can be effectively activated, and more sulfate radicals can be obtained.
(3) The invention also provides a preparation method of the biochar-ferriporphyrin composite material, which takes biochar and ferriporphyrin as raw materials, disperses the biochar and ferriporphyrin by utilizing an organic solvent (such as N, N-dimethylformamide), and then prepares the biochar-ferriporphyrin composite material with good catalytic activity and stability by a solvothermal synthesis method. The preparation method has the advantages of simple process, cheap raw materials, low production cost and the like, has the advantages of controllable process, easy operation and the like, is suitable for large-scale preparation, and is favorable for industrial production.
(4) In the preparation method, the biochar is prepared by high-temperature pyrolysis of biomass, and has the advantages of wide raw material source, low raw material price, simple process, easy operation, easy popularization and the like.
(5) The invention also provides an application of the biochar-ferriporphyrin composite material in removing the perfluorooctanoic acid in the water body, the biochar-ferriporphyrin composite material, persulfate, ascorbic acid and perfluorooctanoic acid wastewater are mixed for oscillation reaction, sulfate radicals with high oxidation-reduction potential and long average service life are generated by efficiently activating the persulfate through the biochar-ferriporphyrin composite material, and the perfluorooctanoic acid in the water body is effectively degraded by using the sulfate radicals, so that the perfluorooctanoic acid in the water body is effectively removed, and the method has the advantages of simple treatment process, convenience in operation, low cost, high treatment efficiency, good removal effect and the like, and is suitable for large-scale application. In the invention, the addition of the ascorbic acid is beneficial to realizing electronic circulation, and the removal effect of the perfluorooctanoic acid can be greatly improved. Compared with the existing heat activation mode with the widest application, the method for activating persulfate to treat perfluorooctanoic acid by using the biochar-ferriporphyrin composite material as the catalyst has the advantages of shorter time, better treatment effect, less energy consumption and the like, and can avoid energy waste.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is an SEM image of a biochar-ferriporphyrin composite prepared in example 1 of the present invention.
FIG. 2 is a TEM image of the biochar-ferriporphyrin composite prepared in example 1 of the present invention.
Fig. 3 is a diagram showing the removal effect of the biochar-ferriporphyrin composite materials with different addition amounts on perfluorooctanoic acid in a water body in example 2 of the present invention.
Fig. 4 is a diagram illustrating the effect of the biochar-ferriporphyrin composite material on removing perfluorooctanoic acid in a water body under different time conditions in example 3 of the present invention.
Fig. 5 is a diagram illustrating the effect of the biochar-ferriporphyrin composite material on removing perfluorooctanoic acid in a water body under different pH conditions in example 4 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
Example 1
A biochar-ferriporphyrin composite material comprises biochar and ferriporphyrin, wherein the ferriporphyrin is loaded on the biochar, and the mass ratio of the biochar to the ferriporphyrin is 10: 1.
In this example, the biochar-ferriporphyrin composite is prepared from biochar and ferriporphyrin by a solvothermal synthesis method.
The preparation method of the biochar-ferriporphyrin composite material comprises the following steps:
(1) drying camphor tree leaves, crushing, sieving with a 100-mesh sieve, heating to 400 ℃ under nitrogen atmosphere for high-temperature pyrolysis for 6 hours, soaking a product obtained by pyrolysis in 1mol/L hydrochloric acid solution for 12 hours, washing with ultrapure water for several times until the pH value of a washing solution is not changed, and finally drying at 110 ℃ to obtain the charcoal.
(2) 4g of biochar and 0.4g of ferriporphyrin are dispersed in 200mL of N, N-dimethylformamide, heated to 100 ℃ in an oil bath and stirred vigorously for 8h, i.e. the solvothermal reaction is carried out at 100 ℃ for 8 h.
(3) And (3) after the solvothermal reaction in the step (2) is finished, filtering a reaction product, washing the solid matter obtained by filtering for a plurality of times by using ultrapure water until the washing liquid is clear, and drying in vacuum at 40 ℃ to obtain the biochar-ferriporphyrin composite material.
Fig. 1 and 2 are SEM and TEM images of the biochar-ferriporphyrin composite prepared in example 1 of the present invention, respectively. The surface morphology of the biochar-ferriporphyrin composite material can be seen from figure 1, the internal molecular structure and the form of the biochar-ferriporphyrin composite material can be seen from figure 2, and the combination of the two figures shows that the biochar-ferriporphyrin composite material takes biochar as a carrier and ferriporphyrin is successfully loaded on the biochar carrier.
Example 2
An application of a biochar-ferriporphyrin composite material in removing perfluorooctanoic acid in a water body comprises the following steps:
weighing 0g, 0.005g, 0.01g, 0.025g, 0.05g and 0.1g of the biochar-ferriporphyrin composite material prepared in the example 1, respectively adding the materials into 50mL of perfluorooctanoic acid wastewater with the concentration of 50mg/L, adding 0.28744g of sodium persulfate and 0.044g of ascorbic acid, uniformly mixing, wherein the pH value of the obtained mixed solution is 2.89, and carrying out constant-temperature oscillation for 4 hours at 25 ℃ and 160r/min, namely carrying out oscillation reaction under the condition, thereby completing the removal of the perfluorooctanoic acid in the water body.
After the oscillation reaction is finished, detecting the concentration of the residual perfluorooctanoic acid in the solution by using an LC-MS-MS method, and calculating to obtain the removal rate of the biochar-ferriporphyrin composite material with different addition amounts on the perfluorooctanoic acid in the water body, wherein the result is shown in figure 3.
Fig. 3 is a diagram showing the removal effect of the biochar-ferriporphyrin composite materials with different addition amounts on perfluorooctanoic acid in a water body in example 2 of the present invention. As can be seen from fig. 3, the removal rate of perfluorooctanoic acid was very low without adding the biochar-ferriporphyrin composite material, and the removal rate was only 21.2%. By adding the biochar-ferriporphyrin composite material into the system, the removal effect of the perfluorooctanoic acid is greatly improved, and the removal rate of the perfluorooctanoic acid is increased along with the increase of the addition amount, wherein when the addition amount of the biochar-ferriporphyrin composite material is 2g/L, the removal rate of the perfluorooctanoic acid can reach 90.5%, at the moment, the content of the biochar-ferriporphyrin composite material in the reaction system is enough to catalyze persulfate, so that the addition amount of the biochar-ferriporphyrin composite material is continuously increased, and the removal effect of the perfluorooctanoic acid is not greatly improved. The results show that the biochar-ferriporphyrin composite material prepared by the invention has good catalytic activity, can efficiently activate persulfate, and can effectively degrade perfluorooctanoic acid in water.
Example 3
An application of a biochar-ferriporphyrin composite material in removing perfluorooctanoic acid in a water body comprises the following steps:
0.5g of the biochar-ferriporphyrin composite material prepared in the example 1, 2.8744g of sodium persulfate and 0.44g of ascorbic acid are added into 500mL of perfluoro caprylic acid wastewater with the concentration of 50mg/L and uniformly mixed, the pH value of the obtained mixed solution is 2.89, and the mixed solution is oscillated at constant temperature of 25 ℃ and 160r/min, namely the oscillating reaction is carried out under the condition, so that the perfluoro caprylic acid in the water body is removed.
During the shaking reaction, samples were taken at 1min, 2 min, 4 min, 6 min, 8 min, 10min, 15 min, 20min, 25 min, 30 min, 40 min, 60 min, 90 min, 120 min, 4h, 8h and 12h, respectively. The concentration of the residual perfluorooctanoic acid in the solution is detected by an LC-MS-MS method, and the removal rate of the biochar-ferriporphyrin composite material to the perfluorooctanoic acid in the water body under different time conditions is calculated, and the result is shown in figure 4.
Fig. 4 is a diagram illustrating the effect of the biochar-ferriporphyrin composite material on removing perfluorooctanoic acid in a water body under different time conditions in example 3 of the present invention. As can be seen from FIG. 4, the removal rate of perfluorooctanoic acid is 56.8% after 5min of reaction, the removal rate of perfluorooctanoic acid reaches 83.5% after 2h of reaction, and the reaction speed is very high. When the reaction is carried out for 12 hours, the removal rate of the perfluorooctanoic acid reaches 90.9 percent, and the removal effect is excellent. Compared with the mode of thermally activating persulfate to treat perfluorooctanoic acid which is most widely applied at present, the method for activating persulfate to treat perfluorooctanoic acid by using the biochar-ferriporphyrin composite material as the catalyst has the advantages of shorter time, better treatment effect, less energy consumption and the like, and can avoid energy waste.
Example 4
An application of a biochar-ferriporphyrin composite material in removing perfluorooctanoic acid in a water body comprises the following steps:
to 50mL of a water body of perfluorooctanoic acid having a concentration of 50mg/L, 0.05g of the biochar-ferriporphyrin composite material prepared in example 1, 0.28744g of sodium persulfate and 0.044g of ascorbic acid were added, and mixed uniformly to prepare seven groups of mixed solutions. The pH values of the seven groups of mixed liquor are respectively adjusted to 1, 2, 3, 5, 7, 9 and 11, and the seven groups of mixed liquor are subjected to constant temperature oscillation for 4 hours at the temperature of 25 ℃ and at the speed of 160r/min, namely, oscillation reaction is carried out under the conditions, and the removal of the perfluorooctanoic acid in the water body is completed.
After the oscillation reaction is finished, detecting the concentration of the residual perfluorooctanoic acid in the solution by using an LC-MS-MS method, and calculating to obtain the removal rate of the biochar-ferriporphyrin composite material on the perfluorooctanoic acid in the water body under different pH conditions, wherein the result is shown in figure 5.
Fig. 5 is a diagram illustrating the effect of the biochar-ferriporphyrin composite material on removing perfluorooctanoic acid in a water body under different pH conditions in example 4 of the present invention. As can be seen from FIG. 5, the removal effect of the biochar-ferriporphyrin composite material on the perfluorooctanoic acid under an acidic condition is better than that of the perfluorooctanoic acid under an alkaline condition, wherein the removal effect of the biochar-ferriporphyrin composite material on the perfluorooctanoic acid is better when the pH value is 1-3. When the pH is =2, the removal rate of the perfluorooctanoic acid can reach 90.7%, and the pH value of the original reaction solution is 2.89, which indicates that the pH does not need to be adjusted in the actual application process, thereby being convenient for popularization and application.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (8)
1. The preparation method of the biochar-ferriporphyrin composite material is characterized by comprising the following steps of: mixing biochar, ferriporphyrin and an organic solvent according to the mass ratio of 5-20: 1 of biochar to ferriporphyrin and the ratio of 1 g: 500mL of ferriporphyrin to the organic solvent, carrying out solvothermal reaction, filtering, washing and drying to obtain a biochar-ferriporphyrin composite material with ferriporphyrin loaded on biochar; the organic solvent is at least one of N, N-dimethylformamide, ethanol and chloroform; the solvent thermal reaction is carried out at the temperature of 80-100 ℃; the solvothermal reaction time is 8-10 h.
2. The method for preparing biochar according to claim 1, wherein the method for preparing biochar comprises the following steps: and drying, crushing and sieving the biomass, pyrolyzing, washing and drying the biomass in a nitrogen atmosphere to obtain the biochar.
3. The method according to claim 2, wherein the biomass is camphor tree leaves; sieving is to sieve the crushed biomass by a sieve of 80-200 meshes; the pyrolysis is carried out at a temperature of 400 ℃ to 500 ℃; the pyrolysis time is 4-6 h; and in the washing step, the product obtained by pyrolysis is firstly soaked in hydrochloric acid solution with the concentration of 1mol/L for 10 to 16 hours and then washed by water until the pH value of the washing liquid is not changed any more.
4. The production method according to any one of claims 1 to 3, wherein the drying is vacuum drying; the vacuum drying is carried out at 30-40 ℃.
5. Application of the biochar-ferriporphyrin composite material prepared by the preparation method of any one of claims 1-4 in removing perfluorooctanoic acid in a water body.
6. Use according to claim 5, characterized in that it comprises the following steps: mixing the biochar-ferriporphyrin composite material with the perfluoro caprylic acid wastewater, adding persulfate and ascorbic acid to carry out oscillation reaction, and finishing the removal of the perfluoro caprylic acid in the water body; the addition amount of the biochar-ferriporphyrin composite material is 0.1-2.0 g of biochar-ferriporphyrin composite material added in per liter of perfluorooctanoic acid wastewater; the molar ratio of the persulfate to the perfluoro caprylic acid in the perfluoro caprylic acid wastewater is 50-500: 1; the addition amount of the ascorbic acid is such that the concentration of the ascorbic acid in the oscillation reaction system is 1 mmol/L-10 mmol/L.
7. The use according to claim 6, wherein the initial concentration of perfluorooctanoic acid in the perfluorooctanoic acid wastewater is 2mg/L to 100 mg/L; the persulfate is sodium persulfate and/or potassium persulfate.
8. The application of the method as claimed in claim 6 or 7, wherein the pH value of the reaction system is controlled to be 1-11 in the oscillating reaction process; the oscillation reaction is carried out at the rotating speed of 150-160 rpm; the oscillation reaction is carried out at the temperature of 20-30 ℃; the oscillation reaction time is 1 min-12 h.
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| US5274090A (en) * | 1992-11-09 | 1993-12-28 | The Board Of Trustees Of The Leland Stanford Junior University | Tetraphenylporphyrin compounds and method |
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| CN106111196A (en) * | 2016-06-07 | 2016-11-16 | 青岛大学 | A kind of preparation method and application of iron porphyrin chloride/methylene blue@metallic organic framework composite electrode |
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