CN117244524B - Iron-containing carbon-based material, preparation method and application thereof - Google Patents
Iron-containing carbon-based material, preparation method and application thereof Download PDFInfo
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- CN117244524B CN117244524B CN202311427469.9A CN202311427469A CN117244524B CN 117244524 B CN117244524 B CN 117244524B CN 202311427469 A CN202311427469 A CN 202311427469A CN 117244524 B CN117244524 B CN 117244524B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 67
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 31
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- SPFYMRJSYKOXGV-UHFFFAOYSA-N Baytril Chemical compound C1CN(CC)CCN1C(C(=C1)F)=CC2=C1C(=O)C(C(O)=O)=CN2C1CC1 SPFYMRJSYKOXGV-UHFFFAOYSA-N 0.000 claims description 5
- LSQZJLSUYDQPKJ-NJBDSQKTSA-N amoxicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=C(O)C=C1 LSQZJLSUYDQPKJ-NJBDSQKTSA-N 0.000 claims description 5
- 229960003022 amoxicillin Drugs 0.000 claims description 5
- 239000000356 contaminant Substances 0.000 claims description 5
- 229960000740 enrofloxacin Drugs 0.000 claims description 5
- LSQZJLSUYDQPKJ-UHFFFAOYSA-N p-Hydroxyampicillin Natural products O=C1N2C(C(O)=O)C(C)(C)SC2C1NC(=O)C(N)C1=CC=C(O)C=C1 LSQZJLSUYDQPKJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 abstract description 38
- 239000003344 environmental pollutant Substances 0.000 abstract description 19
- 231100000719 pollutant Toxicity 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 10
- 238000004064 recycling Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 9
- 238000003911 water pollution Methods 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 description 78
- 239000000463 material Substances 0.000 description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 12
- 230000003115 biocidal effect Effects 0.000 description 10
- 229910001385 heavy metal Inorganic materials 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- -1 carboxyl graphene Chemical compound 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 101100454340 Catharanthus roseus LAMT gene Proteins 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 241001092080 Hydrangea Species 0.000 description 2
- 235000014486 Hydrangea macrophylla Nutrition 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 238000009360 aquaculture Methods 0.000 description 2
- 244000144974 aquaculture Species 0.000 description 2
- 229910001567 cementite Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GECHUMIMRBOMGK-UHFFFAOYSA-N sulfapyridine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=CC=CC=N1 GECHUMIMRBOMGK-UHFFFAOYSA-N 0.000 description 2
- 229960002211 sulfapyridine Drugs 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDYZIJYBMGIQMJ-UHFFFAOYSA-N enoxacin Chemical compound N1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 IDYZIJYBMGIQMJ-UHFFFAOYSA-N 0.000 description 1
- 229960002549 enoxacin Drugs 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 230000004634 feeding behavior Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000009309 intensive farming Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- 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
-
- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
-
- 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
-
- 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
-
- 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
- C02F2101/40—Organic compounds containing sulfur
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the technical field of water pollution treatment, in particular to an iron-containing carbon-based material, a preparation method and application thereof. The invention provides a preparation method of an iron-containing carbon-based material, which comprises the following steps: a) Mixing and stirring melamine, biochar and ethanol solution for 1-2 h, and then mixing and stirring the mixture with FeCl 3 for 3-4 h to obtain mixed feed liquid; b) Drying the mixed solution, and grinding to obtain precursor powder; c) And (3) calcining the precursor powder slowly in a protective gas atmosphere to obtain the iron-containing carbon-based material. The iron-containing carbon-based material prepared by the method can synchronously adsorb and remove the composite pollutants comprising hexavalent chromium and antibiotics, has better removal effect, and has good recycling performance in the process of removing the composite pollutants.
Description
Technical Field
The invention relates to the technical field of water pollution treatment, in particular to an iron-containing carbon-based material, a preparation method and application thereof.
Background
The antibiotics Enrofloxacin (ENT) and Amoxicillin (AMT) are common growth promoters in intensive farming. The antibiotics enriched in natural bodies of water are typically from municipal wastewater, surface runoff through animal manure fertilized soil, and aquaculture wastewater produced during aquaculture. Enrichment of ENT and AMT in animals ultimately produces toxic effects by feeding behavior in humans. In addition, in domestic and industrial wastewater, not only organic pollutants such as antibiotics are present, but also enrichment of various heavy metals such as Cr (VI) and the like is accompanied. Thus, contamination in actual aquatic environments has a complexity.
Compared with single heavy metal or antibiotic pollution, the problem of heavy metal and antibiotic combined pollution is more difficult to solve. Semiconductor photocatalytic technology has been widely used for simultaneous removal of antibiotics and Cr (VI) due to hole-electron pairs having oxidation and reduction properties. However, even under light conditions, the presence of Cr (VI) still inhibits degradation of enoxacin. In addition, the large energy consumption hampers the application of the photocatalytic process in complex pollutants.
Adsorption is a simple and effective method for removing heavy metals or antibiotic contamination. Adsorbents of Fe 3 C composite materials supported on Biochar (BC) or Carbon Nanotubes (CNT) have been used to remove Cr (VI). In the composite material, the adsorption of Cr (VI) is mainly mediated by complexation of carboxyl groups in the CNT, and the reduction of Cr (VI) can also be induced by alcohols, reducing phenols or aldehydes in the carbonaceous material. At the same time, the atomic hydrogen, fe 2+ and Fe 0 in the Fe 3 C particles can also reduce Cr (VI). However, these composites have limited adsorption capacity for Cr (VI) and a maximum adsorption capacity of only 23.7-23.8 mg/g. The polyacrylic acid grafted carboxyl graphene/titanium nanotube composite material adsorbs ENR mainly by electrostatic interaction, but the maximum adsorption amount is only 13.4mg/g. Magnetic multiwall carbon nanotubes (MMWCNT) can only remove 23.5mg/g of AMT by van der waals interactions between the hexagonally arranged carbon atoms in the graphite sheets of MMWCNT and the aromatic skeleton of AMT.
A single carbonaceous material is not effective in removing Cr (VI) and antibiotics. Inyang et al synthesized a mixed MCNT-loaded BC material by slow pyrolysis after dip coating biomass with carboxyl-functionalized CNT solutions of varying concentrations. BC is a carrier of CNTs that significantly increase the physicochemical properties of BC. The mixed MCNT-BC nanocomposite has good adsorption capacity on methylene blue. The material can also remove the composite solution of Pb (II) and sulfapyridine at the same time, and compared with BC, the removal efficiency of sulfapyridine is obviously improved. The abundance of pi electrons in the composite material makes the composite material have excellent adsorption performance. However, these carbonaceous composites are difficult to degrade antibiotics. Therefore, it is necessary to provide an iron carbide supported composite carbon-based material which is low in cost, simple and convenient to prepare and capable of synchronously removing heavy metals and antibiotics.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an iron-containing carbon-based material, a preparation method and an application thereof, wherein the iron-containing carbon-based material prepared by the present invention can synchronously adsorb and remove a composite pollutant including hexavalent chromium and antibiotics, has a better removal effect, and has good recycling performance in the removal of the composite pollutant.
The invention provides a preparation method of an iron-containing carbon-based material, which comprises the following steps:
A) Mixing and stirring melamine, biochar and ethanol solution for 1-2 h, and then mixing and stirring the mixture with FeCl 3 for 3-4 h to obtain mixed feed liquid;
B) Drying the mixed solution, and grinding to obtain precursor powder;
c) Calcining the precursor powder in a protective gas atmosphere to obtain the iron-containing carbon-based material.
Preferably, the mass ratio of the melamine to the biochar is 0.5-1: 0.5 to 1;
The dosage ratio of the biochar to the ethanol solution is 0.5-1 g: 15-25 mL.
Preferably, the mass ratio of the biochar to the FeCl 3 is 0.5-1: 1 to 8.
Preferably, in step C), the shielding gas may be nitrogen; the flow rate of the shielding gas is 30-50 mL/min.
Preferably, in step C), the calcining comprises:
Heating to 450-550 ℃ from room temperature, preserving heat for 1-3 h, heating to 500-800 ℃ and preserving heat for 1-3 h;
the heating rate is 3-5 ℃/min.
Preferably, in step C), after the calcining, the method further includes: naturally cooling to room temperature;
After cooling to room temperature, further comprising: grinding to 100 mesh.
Preferably, the specific surface area of the iron-containing carbon-based material is 412-696 m 2/g, and the average pore diameter is 1.95-3.01 nm.
The invention also provides the iron-containing carbon-based material prepared by the preparation method.
The invention also provides an application of the iron-containing carbon-based material in polluted water and soil remediation.
Preferably, the iron-containing carbon-based material is used as an adsorbent for treating composite pollutants;
The complex pollutants comprise heavy metals and antibiotics;
The antibiotic comprises enrofloxacin and/or amoxicillin.
The invention provides a preparation method of an iron-containing carbon-based material, which comprises the following steps: a) Mixing and stirring melamine, biochar and ethanol solution for 1-2 h, and then mixing and stirring the mixture with FeCl 3 for 3-4 h to obtain mixed feed liquid; b) Drying the mixed solution, and grinding to obtain precursor powder; c) Calcining the precursor powder in a protective gas atmosphere to obtain the iron-containing carbon-based material. The iron-containing carbon-based material prepared by the method can synchronously adsorb and remove the composite pollutants comprising hexavalent chromium and antibiotics, has better removal effect, and has good recycling performance in the process of removing the composite pollutants.
Experimental results show that along with the increase of the concentration of Cr (VI), the efficiency of MBCFe for removing Enrofloxacin (ENT) is sequentially increased, the efficiency of MBCFe and MBCFe3 for removing ENT is increased and then reduced, the efficiency of MBCFe for removing ENT is greater than that of a control when the concentration of Cr (VI) is less than 1mmol/L, and the efficiency of removing ENT is only reduced by 8.58% when the concentration reaches 2 mmol/L. When the Cr (VI) concentration is 0.3mmol/L, MBCFe1 has no effect on the removal efficiency of Amoxicillin (AMT). Under the composite system, the antibiotics have no obvious influence on the Cr (VI) removal efficiency, the Cr (VI) removal efficiency can reach more than 80%, and the antibiotics have good Cr (VI) removal capability in the composite pollution system.
The iron-containing carbon-based material is used for recycling Cr (VI) and antibiotic composite pollutants, the composite material still has good removal capability after being recycled for four times under a composite pollution system, and the removal efficiency of ENT and AMT in a composite pollution recycling removal experiment is reduced by 28.7% and 20.5% in the fourth time compared with the first time. After the fourth cycle is achieved, the Cr (VI) removal efficiency is reduced by 6.59%, so that the composite material has good recycling performance and reproducibility on Cr (VI), the repair cost can be effectively reduced, and a theoretical basis is provided for the application of the Fe 3 C loaded composite carbon-based material in the actual composite polluted water and soil repair.
Drawings
FIG. 1 is an XRD pattern for MBCFe, MBCFe2, and MBCFe 3;
FIG. 2 is an SEM image of MBCFe, MBCFe2, and MBCFe 3;
FIG. 3 is a TEM image of MBCFe, MBCFe2, and MBCFe 3;
FIG. 4 is a graph of MBCFe, MBCFe, and MBCFe3 kinetics of removal for 0.1mmol/L ENT, 0.1mmol/LAMT, and 0.1mmol/L Cr (VI);
FIG. 5 is a graph showing the removal efficiency of MBCFe, MBCFe, 2, and MBCFe3 for ENT, AMT, and Cr (VI) at various concentrations;
FIG. 6 is MBCFe, MBCFe, and MBCFe3, under conditions of controlling Cr (VI) concentration, for removal efficiencies of 0.3mmol/L ENT (a) and 0.3mmol/L AMT (b);
FIG. 7 is a graph showing the removal efficiency of MBCFe, MBCFe, 2, and MBCFe3 for 1mmol/L Cr (VI) in the presence of antibiotics under conditions of adjusting ENT and AMT concentrations;
FIG. 8 is a graph showing the efficiency of MBCFe for removal of ENT/Cr (VI) and AMT/Cr (VI) complex contamination after four cycles of use, and the XRD pattern of the material after each cycle.
FIG. 9 shows the removal efficiency of the test MBCFe2, MBCFe3 and the comparative material (BCM@Fe) on ENT (a), AMT (b) and Cr (VI) (c) at various concentrations.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of an iron-containing carbon-based material, which comprises the following steps:
A) Mixing and stirring melamine, biochar and ethanol solution for 1-2 h, and then mixing and stirring the mixture with FeCl 3 for 3-4 h to obtain mixed feed liquid;
B) Drying the mixed solution, and grinding to obtain precursor powder;
C) And (3) calcining the precursor powder slowly in a protective gas atmosphere to obtain the iron-containing carbon-based material.
In step A):
mixing and stirring melamine, biochar and ethanol solution for 1-2 h, and then mixing and stirring the mixture with FeCl 3 for 3-4 h to obtain mixed feed liquid.
In certain embodiments of the invention, the mass ratio of melamine to biochar is 0.5 to 1:0.5 to 1, such as 1:1.
In certain embodiments of the invention, the ratio of biochar to ethanol solution is 0.5 to 1g: 15-25 mL.
In certain embodiments of the invention, the mass ratio of biochar to FeCl 3 is 0.5-1: 1 to 8.
The mixing and stirring are magnetic stirring.
In step B):
And drying the mixed feed liquid, and grinding to obtain precursor powder.
In certain embodiments of the invention, the drying is at a temperature of 80-105 ℃, such as 80 ℃, for a time of 24-72 hours, such as 48 hours.
In certain embodiments of the invention, the grinding is to 100 mesh.
In step C):
Calcining the precursor powder in a protective gas atmosphere to obtain the iron-containing carbon-based material.
In certain embodiments of the invention, the shielding gas is nitrogen. The flow rate of the shielding gas is 30-50 mL/min, such as 50mL/min.
In certain embodiments of the invention, the calcining comprises:
Heating to 450-550 ℃ from room temperature, preserving heat for 1-3 h, heating to 500-800 ℃ and preserving heat for 1-3 h.
The heating rate is 3-5 ℃/min.
In certain embodiments, the calcining comprises:
Heating from room temperature (heating rate is 3 ℃/min) to 550 ℃, preserving heat for 2 hours, and heating again (heating rate is 5 ℃/min) to 800 ℃ and preserving heat for 2 hours.
After the calcination, the method further comprises: cooling to room temperature, in particular naturally cooling to room temperature.
In certain embodiments of the present invention, after cooling to room temperature, further comprising: grinding to 100 mesh.
In certain embodiments of the invention, the specific surface area of the iron-containing carbon-based material is 412 to 696m 2/g and the average pore size is 1.95 to 3.01nm.
The invention also provides the iron-containing carbon-based material prepared by the preparation method.
In some embodiments of the invention, when the mass content of iron in the iron-containing carbon-based material is 30% -32%, the iron-containing carbon-based material radially grows by taking biochar as a substrate, needle-shaped structures are uniformly distributed on the surface, the bottom is large, the crown is small, and the overall shape is similar to that of hydrangea. In the iron-containing carbon-based material, when the mass content of iron is more than 32% and not more than 40%, the formed needle-shaped structure is restrained from growing transversely and radially due to space limitation, the thickness of a sheet layer is changed, and the large pore channels are gradually changed into more small compact pore channels.
The invention also provides an application of the iron-containing carbon-based material in polluted water and soil remediation.
Specifically, the invention also provides an application of the iron-containing carbon-based material as an adsorbent for treating composite pollutants; the complex contaminants include heavy metals and antibiotics. The antibiotics include Enrofloxacin (ENT) and/or Amoxicillin (AMT). The heavy metal is hexavalent chromium.
Experimental results show that the iron-containing carbon-based material provided by the invention has a good removal effect on Cr (VI) and antibiotic composite pollutants. Meanwhile, the method has good recycling performance in the process of removing the composite pollutants. Thus, the present invention claims the use of the iron-containing carbon-based material as an adsorbent for the treatment of Cr (VI) and antibiotic complex contaminants.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
In order to further illustrate the present invention, the following examples are provided to illustrate an iron-containing carbon-based material, a method for preparing the same and an application thereof in detail, but should not be construed as limiting the scope of the present invention.
Example 1
Preparation of precursor materials:
0.5g of melamine and 0.5g of biochar are weighed into a polytetrafluoroethylene beaker, 20mL of absolute ethanol solution is added, after magnetic stirring for 1h, 1g of FeCl 3 is added into the mixed solution, and stirring is continued for 3h. And (3) putting the mixed solution into an oven, drying at 80 ℃ for 48 hours, grinding to powder (100 meshes) to obtain precursor powder, and drying and storing at room temperature.
Preparation of iron-containing carbon-based materials:
Placing the precursor powder into a tube furnace, calcining at a high temperature under a nitrogen atmosphere, wherein the nitrogen flow rate is 50mL/min; the calcining comprises: heating from room temperature (heating rate is 3 ℃/min) to 550 ℃, preserving heat for 2 hours, and heating again (heating rate is 5 ℃/min) to 800 ℃ and preserving heat for 2 hours. Naturally cooling to room temperature, grinding to 100 meshes to obtain the iron-containing carbon-based material (the mass content of iron in the iron-containing carbon-based material is 30.2%), and drying and storing at normal temperature, wherein the mass content of iron is MBCFe.
Example 2
Preparation of precursor materials:
0.5g of melamine and 0.5g of biochar are weighed into a polytetrafluoroethylene beaker, 20mL of absolute ethanol solution is added, after magnetic stirring for 1h, 2g of FeCl 3 is added into the mixed solution, and stirring is continued for 3h. And (3) putting the mixed solution into an oven, drying at 80 ℃ for 48 hours, grinding to powder (100 meshes) to obtain precursor powder, and drying and storing at room temperature.
Preparation of iron-containing carbon-based materials:
Placing the precursor powder into a tube furnace, calcining at a high temperature under a nitrogen atmosphere, wherein the nitrogen flow rate is 50mL/min; the calcining comprises: heating from room temperature (heating rate is 3 ℃/min) to 550 ℃, preserving heat for 2 hours, and heating again (heating rate is 5 ℃/min) to 800 ℃ and preserving heat for 2 hours. Naturally cooling to room temperature, grinding to 100 meshes to obtain the iron-containing carbon-based material (the mass content of iron in the iron-containing carbon-based material is 30.9%), and drying and storing at normal temperature, wherein the mass content of iron is MBCFe.
Example 3
Preparation of precursor materials:
0.5g of melamine and 0.5g of biochar are weighed into a polytetrafluoroethylene beaker, 20mL of absolute ethanol solution is added, after magnetic stirring for 1h, 3g of FeCl 3 is added into the mixed solution, and stirring is continued for 3h. And (3) putting the mixed solution into an oven, drying at 80 ℃ for 48 hours, grinding to powder (100 meshes) to obtain precursor powder, and drying and storing at room temperature.
Preparation of iron-containing carbon-based materials:
Placing the precursor powder into a tube furnace, calcining at a high temperature under a nitrogen atmosphere, wherein the nitrogen flow rate is 50mL/min; the calcining comprises: heating from room temperature (heating rate is 3 ℃/min) to 550 ℃, preserving heat for 2 hours, and heating again (heating rate is 5 ℃/min) to 800 ℃ and preserving heat for 2 hours. And naturally cooling to room temperature, and grinding to 100 meshes to obtain the iron-containing carbon-based material (the mass content of iron in the iron-containing carbon-based material is 32.5%), namely MBCFe, and drying and storing at normal temperature.
Figure 1 is an XRD pattern of MBCFe, MBCFe2 and MBCFe 3. As can be seen from fig. 1, the crystal forms of the three materials are basically consistent, and Fe 3 C peaks appear at 2θ=37.75 °, 42.89 °, 45.87 °, 51.83 °, 70.84 ° and 83.05 °, corresponding to the peak shapes shown in PDF cards 01-085-1317 of Fe 3 C, and the peak intensities are MBCFe2> MBCFe3> MBCFe1 in sequence. All three show graphite carbon at the position of 2 theta = 26.55 degrees, and are (002) crystal faces of the graphite carbon, so that the three materials all have stable graphite structures, and the structures are favorable for promoting the electron conduction capacity of the materials, so that reduction or oxidative degradation of pollutants is promoted. Meanwhile, the peak intensity of the characteristic peak of graphite increases with the increase of the iron content.
Fig. 2 is an SEM image of MBCFe, MBCFe2, and MBCFe 3. Fig. 2 (a) is an SEM image of MBCFe, on the surface of which needle structures are uniformly distributed, and the needle structures grow radially on BC as a substrate, have large bottoms and small crowns, and have an overall shape similar to that of an hydrangea. Fig. 2 (b) is an SEM image of MBCFe 2. As the iron content increases, MBCFe has a large number of plate-like structures stacked alternately within the indicated range, forming a cell structure smaller than 100 nm. Fig. 2 (c) is an SEM image of MBCFe, and the structure of MBCFe is transited from needle-like structure to sheet-like stacked structure, compared to MBCFe and MBCFe, MBCFe3, and dense pores smaller than 20nm are further formed. Therefore, when the iron content is small, the surface of the composite carbon material mainly forms an acicular structure under the promotion of a small amount of iron; along with the increase of the iron content, the surface needle-shaped structure transversely grows under the catalysis of more iron to form a sheet-shaped structure, and the sheet-shaped structures are mutually stacked to form a new pore canal; when the iron content increases, the stacked sheet structure that has been formed is inhibited from both lateral and radial growth due to space constraints, and the sheet thickness begins to change from large cells to more small dense cells.
Fig. 3 is a TEM image of MBCFe, MBCFe2, and MBCFe 3. Fig. 3 (a) is a TEM image of MBCFe, and it can be seen that MBCFe is a curved multi-walled Carbon Nanotube (CNTs) structure with limited space, filled with Fe 3 C spheres. The length of the tubular structure is less than 1 mu m, the pipe diameter is 50-100 nm, and the diameter of the tubular structure is consistent with that of an internally filled Fe 3 C ball. The diameter of the Fe 3 C sphere is 20-80 nm, which is smaller than the diameter of CNTs, and the Fe 3 C spheres are all positioned at the end of the tube, which shows that iron is used as a catalyst to promote the formation of the structure. MBCFe1 the tube-to-tube construction is relatively loose. As a result of high-resolution TEM observation on the edge of the Fe 3 C sphere in MBCFe, as shown in a graph (d) in FIG. 3, a gray structure of the outer layer and a clear lattice structure of the black inner layer of the Fe 3 C sphere are formed, and after measurement, the lattice spacing of the gray structure is 0.34nm, corresponding to a graphite carbon (002) crystal face, the lattice spacing of the black part is 0.20nm, corresponding to a Fe 3 C (121) crystal face, which indicates that the material forms Fe 3 C crystals with good crystallization. Fig. 3 (b) is a TEM image of MBCFe, and compared with MBCFe, MBCFe is found to have a more densely packed CNTs structure on a microscopic scale, with a tube diameter of 80-100 nm, and fe 3 C is also loaded at the ends of the CNTs. In addition to the CNTs structure, there is a graphene-like carbon structure attached to it, which is presumed to correspond to the lamellar overlapping morphology of MBCFe surfaces in connection with FIG. 2, panel (b). Fig. 3 (c) is a TEM image of MBCFe, MBCFe3 has a denser CNTs structure than the former two, and the boundaries between dense tubular structures are less obvious. The size of the iron ball filled in the material is about 50nm, and a multi-layer carbon structure is arranged outside the material for limiting the area and wrapping. This particular profile corresponds to the SEM profile of MBCFe in fig. 2 (c). High-resolution TEM observation of the edge of the Fe 3 C sphere in MBCFe2, as shown in fig. 3 (e), and high-resolution TEM observation of the edge of the Fe 3 C sphere in MBCFe3, as shown in fig. 3 (f), revealed that the lattice information of the Fe 3 C sphere in the high-resolution TEM images of MBCFe and MBCFe3 was consistent with MBCFe1, both of which revealed that these two materials had a Fe 3 C structure.
Specific surface area of iron-containing carbon-based materials prepared in examples 1 to 3 were studied:
BET parameters of MBCFe, MBCFe, and MBCFe3 are shown in Table 1.
BET parameters of tables 1MBCFe1, MBCFe2, and MBCFe3
As can be seen from Table 1, the specific surface area of the iron-containing carbon-based material was MBCFe < MBCFe > MBCFe1 in this order from the large to the small, and the sizes were 696m 2/g、598m2/g and 412m 2/g, respectively. Analysis is carried out by combining the results of SEM, the MBCFe sheet-like stacked structure effectively increases the specific surface area of the material, and simultaneously significantly promotes the formation of more micropores. When the iron content is highest, MBCFe is slightly inhibited by the fact that part of micropores disappear due to thickening and extrusion of the sheet-shaped structure. The data in Table 1 show that the micropore volume of the three materials is Yu Jiekong pore volumes, and the structure ensures that the materials have excellent conductive performance and micropore adsorption performance. The total pore volume and the mesoporous pore volume of the three materials increase with the increase of the iron content, and the mesoporous pore volume of MBCFe is 0.11cm 3/g.
Application example 1
Test of removal efficiency of iron-containing carbon-based materials for three contaminants:
MBCFe1, MBCFe, 2, and MBCFe were tested for removal efficiency of 0.1mmol/L ENT, 0.1mmol/LAMT, and 0.1mmol/L Cr (VI), respectively.
The specific operation process is as follows:
After accurately weighing 10mg MBCFe1, MBCFe, and MBCFe3, each was placed in a 50mL brown glass bottle, and each was added with 15mL of 0.1mmol/L Cr (VI), 0.1mmol/L ENT, and 0.1mmol/LAMT solutions, respectively, where Cr (VI) was formulated with potassium dichromate. Then the glass bottle is put into a shaking table for horizontal oscillation, the oscillation speed is 180r/min, and the experimental temperature is 30 ℃. The experiment set ten time points, 5min, 10min, 20min, 30min, 60min, 120min, 240min, 360min, 480min and 720min, respectively, and three samples were set in parallel. The experiments were sampled sequentially in the time sequence set, centrifuged and filtered through a 0.22 μm filter. The concentration of Cr (VI) in the filtrate is measured by a color development method at 542nm wavelength by using UV-VIs, and the color developing agent is diphenyl carbodihydrazide; antibiotic concentrations were measured by HPLC.
FIG. 4 is a graph of the removal kinetics of MBCFe, MBCFe, 2, and MBCFe3 for 0.1mmol/L ENT, 0.1mmol/LAMT, and 0.1mmol/L Cr (VI).
Wherein, FIG. 4, panel (a) is a graph of the kinetics of removal of MBCFe, MBCFe, and MBCFe3 versus 0.1mmol/L ENT. As can be seen from the graph (a) in FIG. 4, the removal rates of the three materials for ENT are relatively fast, and the removal efficiency can reach 49.7%, 74.5% and 82.1% within 1 h. The three materials all reach equilibrium after 12h of reaction, the removal efficiencies are 53.7%, 97.7% and 97.6%, respectively, and the removal amounts at the time of the equilibrium are 28.9mg/g,52.6mg/g and 52.6mg/g, respectively. MBCFe2 has a removal efficiency after 2 hours that is similar to MBCFe, probably due to the large specific surface area it has.
Panel (b) in FIG. 4 is a graph of removal kinetics after MBCFe, MBCFe, 2, and MBCFe3 reacted with 0.1mmol/L AMT. As can be seen from the graph (b) in FIG. 4, the three materials can rapidly remove a certain amount of pollutants within 5min, the removal efficiencies are 23.6%, 39.2% and 54.6%, respectively, the removal efficiencies are slowly increased along with the reaction time, the equilibrium is reached at 12h, the removal efficiencies are 59.3%, 96.5% and 99.7%, respectively, and the corresponding removal amounts are 37.3mg/g, 60.7mg/g and 62.7mg/g, respectively.
Panel (c) in FIG. 4 is a plot of MBCFe, MBCFe2, and MBCFe3 versus 0.1mmol/L of Cr (VI) removal kinetics. As can be seen from FIG. 4 (c), all of the Cr (VI) in the solution was removed by the three materials at 5 min.
Application example 2
Test of removal efficiency of iron-containing carbon-based materials for different concentrations of pollutants
The efficiency of the removal of ENT, AMT and Cr (VI) by MBCFe1, MBCFe2 and MBCFe3 was tested at different concentrations.
The specific operation process is as follows:
The concentration of Cr (VI) in the experiment is 0.1mmol/L, 0.5mmol/L, 1mmol/L, 2mmol/L and 4mmol/L, the concentration gradients of ENT and AMT are 0.1mmol/L, 0.2mmol/L, 0.3mmol/L, 0.4mmol/L and 0.5mmol/L, respectively, and the reaction time is 12h.
FIG. 5 is a graph showing the removal efficiencies of MBCFe, MBCFe, 2, and MBCFe3 for ENT, AMT, and Cr (VI) at various concentrations.
Wherein, graph (a) in fig. 5 is MBCFe1, MBCFe2, and MBCFe3 for ENT removal efficiency at different concentrations. Panel (b) in FIG. 5 shows the removal efficiencies of MBCFe, MBCFe2, and MBCFe for AMT at various concentrations. Panel (c) in FIG. 5 shows the removal efficiencies of MBCFe, MBCFe2, and MBCFe for Cr (VI) at various concentrations.
As can be seen from fig. 5, the efficiency of MBCFe composite removal of three contaminants decreases with increasing concentration.
Wherein MBCFe has maximum efficiency of ENT and AMT removal at each concentration, 97.6%, 79.9%, 61.2%, 52.6% and 47.5% efficiency of ENT removal at 0.5mmol/L, and 127mg/g efficiency of ENT removal at different concentrations. The removal efficiency of AMT with different concentrations is 99.7%, 90.4%, 61.2%, 64.9% and 57.6%, respectively, and the removal capacity of AMT at 0.5mmol/L is 181mg/g, which is 1.42 times of the ENT removal capacity.
MBCFe1, although less efficient than the other two materials, had slightly higher Cr (VI) removal efficiencies than the other two materials at different concentrations, 100%, 77.9%, 52.6% and 29.6% Cr (VI) removal efficiencies, respectively, at 4mmol/L, were 92.4mg/g Cr (VI) removal capacity.
Application example 3
Test of the Effect of composite Material on antibiotic removal efficiency in the Presence of Cr (VI)
In the combined pollution removal experiment, the concentrations of ENT and AMT are firstly set unchanged, and the influence of Cr (VI) on the removal of antibiotics of the material is analyzed by regulating and controlling the concentration of Cr (VI).
The specific operation process is as follows:
the complex pollutant removal experiment was set as follows:
the concentration of antibiotics was fixed and the concentration of different Cr (VI) was set to investigate the effect of Cr (VI) on the removal of antibiotics from the material. The concentration of ENT and AMT is 0.3mmol/L, and the concentration of Cr (VI) is set to 0mmol/L, 0.3mmol/L, 1mmol/L and 2mmol/L; the reaction time was 12h.
FIG. 6 is a graph showing the removal efficiency of MBCFe, MBCFe, and MBCFe3 for ENT (a) at 0.3mmol/L and AMT (b) at 0.3mmol/L under the control of Cr (VI) concentration.
Wherein, the graph (a) in FIG. 6 shows the efficiency of removing ENT by three materials when Cr (VI) of different concentrations are added to the ENT solution of 0.3 mmol/L. As the concentration of Cr (VI) increases, the efficiency of MBCFe for ENT removal increases sequentially, MBCFe and MBCFe are increased and then decreased, MBCFe is higher than the control for ENT removal when the concentration of Cr (VI) is less than 1mM, and the efficiency of ENT removal is only reduced by 8.58% when the concentration reaches 2 mM. MBCFe2 and MBCFe have similar trends in this system. FIG. 6 (b) shows the AMT removal efficiency of three materials when different concentrations of Cr (VI) were added to 0.3mmol/L of the AMT solution. When the concentration of Cr (VI) is 0.3mmol/L, MBCFe1 has no influence on the removal efficiency of the AMT; the AMT removal efficiencies of MBCFe and MBCFe3 were 63.5% and 72.3%, respectively. Therefore, the material can achieve the co-removal of Cr (VI) and ENT/AMT combined pollution.
Application example 4
Test of the Effect of composite materials on Cr (VI) removal efficiency in the Presence of antibiotics
MBCFe1, MBCFe2 and MBCFe3, and the removal efficiency of the antibiotics on Cr (VI) is detected in the presence and absence of the antibiotics.
The specific operation process is as follows:
the concentration of Cr (VI) was fixed and the concentration of different antibiotics was set to investigate the effect of the presence of antibiotics on Cr (VI) removal of the material. The Cr (VI) concentration was 1mmol/L, and the ENT and AMT concentrations were set to 0mmol/L, 0.05mmol/L, 0.15mmol/L, and 0.25mmol/L, respectively. The reaction time was 12h.
FIG. 7 shows the removal efficiency of MBCFe, MBCFe, 2, and MBCFe3 for 1mmol/L Cr (VI) in the presence of antibiotics under conditions of adjusting ENT and AMT concentrations.
Wherein, the graph (a) in FIG. 7 shows the removal efficiency of MBCFe1, MBCFe2 and MBCFe to 1mmol/L Cr (VI) in the presence of antibiotics under the condition of adjusting and controlling ENT concentration. Panel (b) of FIG. 7 shows the removal efficiency of MBCFe1, MBCFe2, and MBCFe3 on 1mmol/LCr (VI) in the presence of antibiotics under the control of AMT concentration.
From fig. 6 and fig. 7, it can be seen that the addition of the antibiotic does not have a significant effect on the Cr (VI) removal ability of the material, probably because the Cr (VI) removal rate of the material is relatively high, cr (VI) is preferentially adsorbed, and the Cr (VI) removal ability is good in the complex pollution system, which indicates that the Cr (VI) affinity of the material is relatively high.
Application example 5
Combined pollution cycle removal experiment
The material is recycled to remove the pollutants.
The specific operation process is as follows:
Calcining the material adsorbed with the composite pollutant molecules in a tube furnace at 800 ℃ for 1h, wherein the heating rate is 10 ℃/min, and the atmosphere is nitrogen. The calcined material was used for the next cycle of reaction. XRD characterization is needed to be carried out on the material obtained after each adsorption experiment, and the change of the crystal morphology of the material surface after each cyclic reaction is recorded. The other experimental steps were the same as the removal kinetics experiments.
FIG. 8 is a graph showing the efficiency of MBCFe for removal of ENT/Cr (VI) and AMT/Cr (VI) complex contamination after four cycles of use, and the XRD pattern of the material after each cycle.
Wherein, the graph (a) in fig. 8 shows the removal efficiency of MBCFe for ENT/Cr (VI) and AMT/Cr (VI) combined pollution after four times of recycling, the graph (b) in fig. 8 shows the XRD pattern after the material reacts with ENT/Cr (VI), and the graph (c) in fig. 8 shows the XRD pattern after the material reacts with AMT/Cr (VI).
As can be seen from fig. 8, MBCFe a 3 gradually decreased the efficiency of ENT and AMT removal with increasing cycle number in the combined pollution cycle removal experiment, compared to the first time, the second time decreased by 17.3% and 2.9%, the third time decreased by 22.7% and 19.4%, respectively, and the fourth time decreased by 28.7% and 20.5%, respectively, which may be due to the formation of iron oxide. After the fourth cycle was reached, the Cr (VI) removal efficiency was reduced to 76.5% by only 6.59%, indicating that MBCFe has good recycling properties for Cr (VI). In the AMT/Cr (VI) combined pollution system, MBCFe3 has better removal efficiency in the previous two cycles, but the removal efficiency starts to decrease after the third time, which is probably due to the decrease of the removal performance caused by the aging of the material.
In conclusion, MBCFe C composite materials still have good removing capacity after being circulated for four times under a composite pollution system, have good recycling property and regenerability, can effectively reduce the repairing cost, and provide theoretical basis for the application of Fe 3 C loaded composite carbon-based materials in actual composite pollution soil and water repairing.
Application example 6
Comparative experiments with the iron carbide Supported composite carbon-based material (BCM@Fe) of published patent (CN 116712976A) example 1
The efficiency of ENT, AMT and Cr (VI) removal by MBCFe, MBCFe3 and the comparative material (BCM@Fe) was tested at different concentrations and the specific procedure was as follows:
Concentration gradients of ENT and AMT set in the experiment are respectively 0.2mmol/L, 0.3mmol/L, 0.4mmol/L and 0.5mmol/L, reaction time of MBCFe and MBCFe3 with antibiotics is 12h, and reaction time of a contrast material (BCM@Fe) with antibiotics is 24h. The Cr (VI) concentration was 0.1mmol/L and 0.5mmol/L, respectively, and the reaction time was 12 hours.
FIG. 9 shows the removal efficiency of the test MBCFe2, MBCFe3 and the comparative material (BCM@Fe) on ENT (a), AMT (b) and Cr (VI) (c) at various concentrations. In fig. 9, MBCFe2, MBCFe3 provide a maximum 0.656 fold improvement in ENT removal efficiency over the comparative material (bcm@fe); MBCFe2, MBCFe3 had 1.55 to 1.71 times the removal efficiency of AMT compared to the control material (BCM@Fe), and MBCFe, MBCFe had 1.56 to 2.60 times the removal efficiency of 0.1mM Cr (VI) compared to the control material (BCM@Fe).
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. Use of an iron-containing carbon-based material for simultaneous adsorption removal of complex contaminants including hexavalent chromium and antibiotics;
The antibiotics comprise enrofloxacin and/or amoxicillin;
the preparation method of the iron-containing carbon-based material comprises the following steps:
A) Mixing and stirring melamine, biochar and ethanol solution for 1-2 hours, and then mixing and stirring the mixture with FeCl 3 for 3-4 hours to obtain mixed feed liquid;
The mass ratio of the melamine to the biochar is 0.5-1: 0.5-1; the dosage ratio of the biochar to the ethanol solution is 0.5-1 g: 15-25 mL; the mass ratio of the biochar to the FeCl 3 is 0.5-1: 1-8;
b) Drying the mixed solution, and grinding to obtain precursor powder;
c) Calcining the precursor powder in a protective gas atmosphere to obtain an iron-containing carbon-based material;
The calcining comprises:
Heating to 450-550 ℃ from room temperature, preserving heat for 1-3 h, heating to 500-800 ℃ and preserving heat for 1-3 h; the heating rate is 3-5 ℃/min.
2. The use according to claim 1, wherein in step C) the shielding gas is nitrogen; the flow rate of the shielding gas is 30-50 mL/min.
3. The use according to claim 1, characterized in that in step C), after the calcination, it further comprises: naturally cooling to room temperature;
After cooling to room temperature, further comprising: grinding to 100 mesh.
4. The use according to claim 1, wherein the specific surface area of the iron-containing carbon-based material is 412-696 m 2/g and the average pore size is 1.95-3.01 nm.
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| The adsorption and reduction of anionic Cr(VI) in groundwater by novel iron carbide loaded on N-doped carbon nanotubes: Effects of Fe-confinement;Kunyuan Liu, et al;Chemical Engineering Journal;20220922;第452卷;文章第139357(1-13)页 * |
| Ultralight Coral-like hierarchical Fe/CNTs/Porous carbon composite derived from biomass with tunable microwave absorption performance;Wei Li, et al;Applied Surface Science;20210922;第571卷;文章第151349(2)页第2节，第151349(4)页右栏 * |
| Wei Li, et al.Ultralight Coral-like hierarchical Fe/CNTs/Porous carbon composite derived from biomass with tunable microwave absorption performance.Applied Surface Science.2021,第571卷文章第151349(2)页第2节，第151349(4)页右栏. * |
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