CN108568315B - ZIF-8 molecular sieve supported multi-metal Fenton catalyst and preparation method and application thereof - Google Patents
ZIF-8 molecular sieve supported multi-metal Fenton catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 74
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 60
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 15
- 229910052927 chalcanthite Inorganic materials 0.000 claims abstract description 12
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000000967 suction filtration Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 229910052603 melanterite Inorganic materials 0.000 claims abstract description 8
- 238000000975 co-precipitation Methods 0.000 claims abstract description 5
- 230000032683 aging Effects 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 81
- 239000011259 mixed solution Substances 0.000 claims description 54
- 239000002351 wastewater Substances 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
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- 239000000843 powder Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
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- 239000000706 filtrate Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- YBHILYKTIRIUTE-UHFFFAOYSA-N berberine Chemical compound C1=C2CC[N+]3=CC4=C(OC)C(OC)=CC=C4C=C3C2=CC2=C1OCO2 YBHILYKTIRIUTE-UHFFFAOYSA-N 0.000 description 10
- 229940093265 berberine Drugs 0.000 description 10
- QISXPYZVZJBNDM-UHFFFAOYSA-N berberine Natural products COc1ccc2C=C3N(Cc2c1OC)C=Cc4cc5OCOc5cc34 QISXPYZVZJBNDM-UHFFFAOYSA-N 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 125000002883 imidazolyl group Chemical group 0.000 description 1
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- 230000003993 interaction Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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Classifications
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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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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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
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention provides a ZIF-8 molecular sieve loaded multi-metal Fenton catalyst, which is prepared by the following steps: takes ZIF-8 molecular sieve as a carrier and FeSO4·7H2O、CuSO4·5H2O and CoSO4·7H2And O is used as a precursor, the catalyst is prepared by a coprecipitation method, and then the catalyst is obtained through aging, suction filtration, washing, drying and calcination. The invention also provides a preparation method and application of the multi-metal Fenton catalyst. The multi-metal Fenton catalyst provided by the invention has high wastewater treatment efficiency and wide application range, and is not easy to cause secondary pollution.
Description
Technical Field
The invention relates to a catalyst, in particular to a ZIF-8 molecular sieve loaded multi-metal Fenton catalyst, and a preparation method and application thereof.
Background
With the economic development of China and the increase of the demand of people on medical care, the pharmaceutical industry of China rapidly grows, and the wastewater discharged by the pharmaceutical industry becomes a main source of water environment pollution. The pharmaceutical wastewater is taken as high-concentration refractory wastewater, is mainly typified by traditional Chinese medicine extraction wastewater, chemical pharmaceutical wastewater, antibiotic wastewater and the like, and is mainly characterized by complex components, various organic pollutants, high concentration and the like. The biodegradability of the wastewater is poor, the wastewater is difficult to discharge up to the standard by adopting the conventional process, and in addition, the environmental situation of China is severe, and the discharge index is improved year by year, so that a process for efficiently treating the pharmaceutical wastewater is needed to be developed to improve the treatment efficiency of the pharmaceutical wastewater.
In the process of treating wastewater by a chemical oxidation method, the Fenton technology has the characteristics of high treatment efficiency, relatively low cost, easy industrialization and the like, and gradually becomes a chemical oxidation method which is applied more in industrial wastewater at present. The traditional Fenton technology uses Fe2+Is a catalyst, catalyzes H2O2OH is generated by decomposition, is an active substance with extremely strong oxidizing power, has the oxidation potential of 2.8eV and the electron affinity of 569.3kJ, has very strong addition reaction characteristic, can indiscriminately oxidize most organic matters in water, and is particularly suitable for removing organic pollutants which are difficult to biodegrade or are difficult to effectively oxidize by common chemical oxidation. However, in the case of the conventional homogeneous Fenton system, the reaction proceeds efficiently only at a pH of 2 to 4, so that the pH of the wastewater needs to be adjusted repeatedly, which increases the treatment cost, and the homogeneous Fenton systemThe catalyst of the Fenton system is dissolved in the wastewater, and a large amount of iron-containing sludge is generated after the reaction is finished, so that the post-treatment is complicated. In recent years, in order to overcome the above technical defects and to more fully exploit the oxidation advantages of the fenton technique, researchers have put more efforts on both the modification of the catalyst and the improvement of the reaction conditions, and the heterogeneous fenton technique has become a new research hotspot. The iron ions are fixed on the carrier to form a solid-phase catalyst, so that a heterogeneous Fenton-like system is formed, the pH value range of the reaction is widened, the catalyst is recycled, secondary pollution is avoided, and the defect of the homogeneous Fenton technology is greatly improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a ZIF-8 molecular sieve loaded multi-metal Fenton catalyst which has high wastewater treatment efficiency and wide application range and is not easy to cause secondary pollution.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a ZIF-8 molecular sieve supported multi-metal Fenton catalyst is prepared by the following steps:
takes ZIF-8 molecular sieve as a carrier and FeSO4·7H2O、CuSO4·5H2O and CoSO4·7H2And O is used as a precursor, the catalyst is prepared by a coprecipitation method, and then the catalyst is obtained through aging, suction filtration, washing, drying and calcination.
Further, the ZIF-8 molecular sieve is a porous crystalline material of zeolite-imidazolate-framework structure.
Further, the ZIF-8 molecular sieve is granular, fibrous, layered or film-shaped.
Further, the sum of the mass of the iron element, the copper element and the cobalt element in the catalyst is 0-20% and is not 0% of the mass of the catalyst.
Further, the ZIF-8 molecular sieve supported multi-metal Fenton catalyst is prepared by the following steps:
(1) separately prepared Fe2+、Cu2+、Co2+Molar concentration ofFeSO in a ratio of 1:1:1 to 5:1:14·7H2O、CuSO4·5H2O and CoSO4·7H2Stirring the water solution of O uniformly to obtain a mixed solution;
(2) adding 1mol/L H into the mixed solution obtained in the step (1)2SO4Uniformly stirring the solution, and adjusting the pH value to 2-3 to obtain a mixed solution;
(3) adding a ZIF-8 molecular sieve into the mixed solution obtained in the step (2), and uniformly stirring to obtain a ZIF-8 dispersion solution;
(4) adding 1mol/L NaOH solution into the ZIF-8 dispersion liquid obtained in the step (3), and adjusting the pH value to 9-11 to obtain a solution with precipitate;
(5) carrying out suction filtration on the solution with the precipitate obtained in the step (4) to obtain filter residue and filtrate, washing the filter residue to be neutral by using deionized water, carrying out vacuum drying on the washed filter residue at 60 ℃ for 8h, then carrying out drying at 100 ℃ for 2h, and grinding to obtain solid powder;
(6) and (4) burning the solid powder obtained in the step (5) for 2 hours in a muffle furnace at 500 ℃ to obtain the ZIF-8 molecular sieve supported multi-metal Fenton catalyst.
The second technical problem to be solved by the invention is to provide a preparation method of the ZIF-8 molecular sieve supported multi-metal Fenton catalyst.
In order to solve the technical problems, the technical scheme is as follows:
a preparation method of a ZIF-8 molecular sieve supported multi-metal Fenton catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) separately prepared Fe2+、Cu2、Co2+FeSO with a molar concentration ratio of 1:1:1 to 5:1:14·7H2O、CuSO4·5H2O and CoSO4·7H2Stirring the water solution of O uniformly to obtain a mixed solution;
(2) adding 1mol/L H into the mixed solution obtained in the step (1)2SO4Uniformly stirring the solution, and adjusting the pH value to 2-3 to obtain a mixed solution;
(3) adding a ZIF-8 molecular sieve into the mixed solution obtained in the step (2), and uniformly stirring to obtain a ZIF-8 dispersion solution;
(4) adding 1mol/L NaOH solution into the ZIF-8 dispersion liquid obtained in the step (3), and adjusting the pH value to 9-11 to obtain a solution with precipitate;
(5) carrying out suction filtration on the solution with the precipitate obtained in the step (4) to obtain filter residue and filtrate, washing the filter residue with deionized water until the pH value of the filtrate is 7, carrying out vacuum drying on the washed filter residue at 60 ℃ for 8h, then drying at 100 ℃ for 2h, and grinding to obtain solid powder;
(6) and (4) burning the solid powder obtained in the step (5) for 2 hours in a muffle furnace at 500 ℃ to obtain the ZIF-8 molecular sieve supported multi-metal Fenton catalyst.
The third technical problem to be solved by the invention is to provide the application of the ZIF-8 molecular sieve loaded multi-metal Fenton catalyst in wastewater treatment.
Further, the method for treating the wastewater by adopting the ZIF-8 molecular sieve loaded multi-metal Fenton catalyst comprises the following steps:
(1) taking a wastewater sample to be treated, and adjusting the pH value of the wastewater sample to be less than or equal to 7;
(2) adding H with the mass content of 30% into the wastewater sample after the pH value is adjusted in the step (1)2O2Adding a ZIF-8 molecular sieve loaded multi-metal Fenton catalyst into the solution to obtain a mixed solution;
(3) fully stirring the mixed solution obtained in the step (2) for reaction, controlling the stirring speed to be 100-500 r/min, controlling the reaction time to be 10-60min, and controlling the pH value in the reaction process to be less than or equal to 7;
(4) and (4) adjusting the pH value of the mixed solution after the reaction in the step (3) to 7, standing and layering the mixed solution into precipitate and supernatant, wherein the supernatant is treated effluent.
Further, in the step (2), the wastewater sample is mixed with H2O2The volume ratio of the solution is 200: 1-1000: 1, and the ZIF-8 molecular sieve supported multi-metal Fenton catalyst and H are2O2The mass ratio of the solution is 10: 1-50: 1.
Further, the wastewater is pharmaceutical wastewater.
Compared with the prior art, the invention has the following beneficial effects:
1) the ZIF-8 molecular sieve is used as a carrier. The molecular sieve is a porous material capable of sieving molecules on a molecular level, the zeolite is one of the most representative ones, the crystal structure of the zeolite is a three-dimensional lattice formed by connecting silicon (aluminum) oxygen tetrahedrons, and the lattice has cavities and channels with various sizes and has great openness. The imidazole ester framework compound (ZIFs) is a novel nano-sized MOFs (metal organic framework compound) porous material, which is a porous crystal material with a zeolite topological structure formed by complexing N atoms on imidazole rings to divalent transition metal ions, and ZIFs with different structures can be formed by modulating ligands or interaction among the ligands. It integrates the advantages of zeolite and MOFs, on one hand, ZIFs has the thermal stability similar to zeolite and reaches over 500 ℃; on the other hand, the regulation of ligand functionalization similar to MOFs ensures that the pore channel of the ZIFs has adjustability and controllability, the ZIF-8 used in the invention is one of the ZIFs, and compared with other molecular sieves, the ZIF-8 has higher load rate in the invention.
2) The performance of a metal catalyst (Fe) added with a small amount of other metals (Cu and Co) is much higher than that of a single metal (Fe), and the selectivity and stability of the catalyst can be improved, especially the activity of a bimetallic catalyst of an eighth group element is better than that of the single metal catalyst, so that the invention uses copper and cobalt as the bimetallic catalyst to be added into the original Fe catalyst, and the catalytic activity, selectivity and stability are greatly improved.
3) The application range is wide: the catalyst prepared by doping copper-cobalt metal enlarges the pH value range of the treated wastewater, and can effectively treat acidic and neutral wastewater with the pH value ranging from 0 to 7.
4) The treatment efficiency is high: the catalyst prepared by the copper-cobalt coprecipitation method has higher activity, so the removal rate of CODcr of pharmaceutical wastewater can reach more than 70 percent, and the removal rate of CODcr of wastewater treated by the existing iron-Fenton catalytic system is only about 60 percent generally.
5) According to the invention, by adopting a multi-metal coprecipitation method, the binding force between the metal and the carrier is increased, and the metal ions of iron, copper and cobalt entering a reaction system in the reaction process are effectively reduced, so that the secondary pollution is effectively avoided, and the metal ions of iron, copper and cobalt can not be detected when the solution after the reaction system is detected.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, which are illustrative of the invention and are not to be construed as limiting the invention.
Example 1
A ZIF-8 molecular sieve supported multi-metal Fenton catalyst is prepared by the following steps:
weighing a certain amount of FeSO4·7H2O、CuSO4·5H2O and CoSO4·7H2O, with a prepared concentration of 0.5mol/L Fe2+、0.5mol/L Cu2+、0.5mol/L Co2+Uniformly stirring the aqueous solution to obtain a mixed solution; respectively taking 100mL of mixed solution, adding 1mol/L of H into a beaker2SO4The method comprises the steps of regulating the pH value of a solution to 2-3 to obtain a mixed solution, adding 300mg of ZIF-8 molecular sieve into the mixed solution, uniformly stirring to obtain a ZIF-8 dispersion solution, adding 1mol/L NaOH solution to regulate the pH value to 9-11, precipitating the solution at the moment, carrying out suction filtration on the solution with the precipitate to obtain filter residue and filtrate, washing the filter residue to be neutral by deionized water, drying the washed filter residue in vacuum at 60 ℃ for 8 hours, then drying at 100 ℃ for 2 hours, and grinding to obtain solid powder; and (3) burning the solid powder in a muffle furnace at 500 ℃ for 2h to obtain the ZIF-8 molecular sieve supported multi-metal Fenton catalyst.
The method for treating berberine waste water by adopting the catalyst comprises the following steps:
(1) the pH value of the berberine waste water effluent raw water solution is 6.5-7.5, the concentration is 10mg/L, 200mL of the solution is added into a 500mL beaker;
(2) firstly adding H with the content of 30 percent2O2Adding 0.5mL of solution, and adding a multi-metal Fenton catalyst 2 loaded by a ZIF-8 molecular sieve00mg to obtain a mixed solution;
(3) fully stirring the mixed solution obtained in the step (2) for reaction, wherein the stirring speed is controlled at 200r/min, the stirring reaction time is 30min, and the pH value in the reaction process is controlled to be less than or equal to 7;
(4) after the reaction is finished, adjusting the pH value to 7 by using a sodium hydroxide solution, standing and layering the solution into a precipitate and a supernatant, wherein the supernatant is treated effluent. The CODcr values of the water quality before and after the water sample treatment are shown in Table 1:
| CODcr(mg/L) | CODcr removal Rate (%) | |
| Before treatment | 800mg/L | |
| After treatment | 232mg/L | |
| 71 |
TABLE 1
Example 2
A ZIF-8 molecular sieve supported multi-metal Fenton catalyst is prepared by the following steps:
weighing a certain amount of FeSO4·7H2O、CuSO4·5H2O and CoSO4·7H2O, with a prepared concentration of 1mol/L Fe2+、0.5mol/L Cu2+、0.5mol/L Co2+Uniformly stirring the aqueous solution to obtain a mixed solution; respectively taking 100mL of mixed solution, adding 1mol/L of H into a beaker2SO4The method comprises the steps of regulating the pH value of a solution to 2-3 to obtain a mixed solution, adding 300mg of ZIF-8 molecular sieve into the mixed solution, uniformly stirring to obtain a ZIF-8 dispersion solution, adding 1mol/L NaOH solution to regulate the pH value to 9-11, precipitating the solution at the moment, carrying out suction filtration on the solution with the precipitate to obtain filter residue and filtrate, washing the filter residue to be neutral by deionized water, drying the washed filter residue in vacuum at 60 ℃ for 8 hours, then drying at 100 ℃ for 2 hours, and grinding to obtain solid powder; and (3) burning the solid powder in a muffle furnace at 500 ℃ for 2h to obtain the ZIF-8 molecular sieve supported multi-metal Fenton catalyst.
The method for treating berberine waste water by adopting the catalyst comprises the following steps:
(1) the pH value of the berberine waste water effluent raw water solution is 6.5-7.5, the concentration is 10mg/L, and 1mol/L H is added2SO4Adjusting pH to 2-3, adding 200mL of the above solution into a 500mL beaker;
(2) firstly adding H with the content of 30 percent2O2Adding 200mg of a ZIF-8 molecular sieve-loaded multi-metal Fenton catalyst into 1mL of the solution to obtain a mixed solution;
(3) fully stirring the mixed solution obtained in the step (2) for reaction, wherein the stirring speed is controlled at 300r/min, the stirring reaction time is 30min, and the pH value in the reaction process is controlled to be less than or equal to 7;
(4) after the reaction is finished, adjusting the pH value to 7 by using a sodium hydroxide solution, standing and layering the solution into a precipitate and a supernatant, wherein the supernatant is treated effluent. The CODcr values of the water quality before and after the water sample treatment are shown in Table 2:
| CODcr(mg/L) | CODcr removal Rate (%) | |
| Before treatment | 900mg/L | |
| After treatment | 135mg/L | |
| 85 |
TABLE 2
Example 3
A ZIF-8 molecular sieve supported multi-metal Fenton catalyst is prepared by the following steps:
weighing a certain amount of FeSO4·7H2O、CuSO4·5H2O and CoSO4·7H2O, with a prepared concentration of 1.5mol/L Fe2+、0.5mol/L Cu2+、0.5mol/L Co2+Uniformly stirring the aqueous solution to obtain a mixed solution; respectively taking 100mL of mixed solution, adding 1mol/L of H into a beaker2SO4Adjusting the pH value of the solution to 2-3 to obtain a mixed solution, adding 300mg of ZIF-8 molecular sieve into the mixed solution, uniformly stirring to obtain a ZIF-8 dispersion solution, adding 1mol/L NaOH solution to adjust the pH value to 9-11, precipitating the solution at the moment, and performing suction filtration on the solution with precipitate to obtain the productWashing the filter residue and the filtrate with deionized water to neutrality, vacuum drying the washed filter residue at 60 deg.C for 8 hr, drying at 100 deg.C for 2 hr, and grinding to obtain solid powder; and (3) burning the solid powder in a muffle furnace at 500 ℃ for 2h to obtain the ZIF-8 molecular sieve supported multi-metal Fenton catalyst.
The method for treating berberine waste water by adopting the catalyst comprises the following steps:
(1) the pH value of the berberine waste water effluent raw water solution is 6.5-7.5, the concentration is 20mg/L, and 1mol/L H is added2SO4Adjusting pH to 4-5, adding 200mL of the above solution into a 500mL beaker;
(2) firstly adding H with the content of 30 percent2O2Adding 200mg of a ZIF-8 molecular sieve-loaded multi-metal Fenton catalyst into 2mL of the solution to obtain a mixed solution;
(3) fully stirring the mixed solution obtained in the step (2) for reaction, wherein the stirring speed is controlled at 400r/min, the stirring reaction time is 60min, and the pH value in the reaction process is controlled to be less than or equal to 7;
(4) after the reaction is finished, adjusting the pH value to 7 by using a sodium hydroxide solution, standing and layering the solution into a precipitate and a supernatant, wherein the supernatant is treated effluent. The CODcr values of the water quality before and after the water sample treatment are shown in Table 3:
| CODcr(mg/L) | CODcr removal Rate (%) | |
| Before treatment | 1350mg/L | |
| After treatment | 337.5mg/L | |
| 75 |
TABLE 3
Example 4
A ZIF-8 molecular sieve supported multi-metal Fenton catalyst is prepared by the following steps:
weighing a certain amount of FeSO4·7H2O、CuSO4·5H2O and CoSO4·7H2O, the preparation concentration is 2mol/L Fe2+、1mol/L Cu2+、1mol/L Co2+Uniformly stirring the aqueous solution to obtain a mixed solution; respectively taking 100mL of mixed solution, adding 1mol/L of H into a beaker2SO4Adjusting the pH value of the solution to 2-3 to obtain a mixed solution, adding 200mg of ZIF-8 molecular sieve into the mixed solution, uniformly stirring to obtain a ZIF-8 dispersion solution, adding 1mol/L NaOH solution to adjust the pH value to 9-11, precipitating the solution at the moment, performing suction filtration on the solution with the precipitate to obtain filter residue and filtrate, washing the filter residue to be neutral by deionized water, drying the washed filter residue for 8 hours in vacuum at 60 ℃, then drying for 2 hours at 100 ℃, and grinding to obtain solid powder; and (3) burning the solid powder in a muffle furnace at 500 ℃ for 2h to obtain the ZIF-8 molecular sieve supported multi-metal Fenton catalyst.
The method for treating berberine waste water by adopting the catalyst comprises the following steps:
(1) the pH value of the berberine waste water effluent raw water solution is 6.5-7.5, the concentration is 5mg/L, 200mL of the solution is added into a 500mL beaker;
(2) firstly adding H with the content of 30 percent2O2Adding 100mg of a multi-element metal Fenton catalyst loaded by a ZIF-8 molecular sieve into 3mL of the solution to obtain a mixed solution;
(3) fully stirring the mixed solution obtained in the step (2) for reaction, wherein the stirring speed is controlled at 500r/min, the stirring reaction time is 60min, and the pH value in the reaction process is controlled to be less than or equal to 7;
(4) after the reaction is finished, adjusting the pH value to 7 by using a sodium hydroxide solution, standing and layering the solution into a precipitate and a supernatant, wherein the supernatant is treated effluent. The CODcr values of the water quality before and after the water sample treatment are shown in Table 4:
| CODcr(mg/L) | CODcr removal Rate (%) | |
| Before treatment | 750mg/L | |
| After treatment | 225mg/L | |
| 70 |
TABLE 4
Example 5
A ZIF-8 molecular sieve supported multi-metal Fenton catalyst is prepared by the following steps:
weighing a certain amount of FeSO4·7H2O、CuSO4·5H2O and CoSO4·7H2O, the preparation concentration is 2.5mol/L Fe2+、0.5mol/L Cu2+、0.5mol/L Co2+Uniformly stirring the aqueous solution to obtain a mixed solution; respectively taking 100mL of mixed solution, adding 1mol/L of H into a beaker2SO4Adjusting the pH value of the solution to 2-3 to obtain a mixed solution, adding 400mg of ZIF-8 molecular sieve into the mixed solution, uniformly stirring to obtain a ZIF-8 dispersion solution, adding 1mol/L NaOH solution to adjust the pH value to 9-11, precipitating the solution at the moment, performing suction filtration on the solution with the precipitate to obtain filter residue and filtrate, washing the filter residue to be neutral by deionized water, performing vacuum drying on the washed filter residue at 60 ℃ for 8 hours, drying at 100 ℃ for 2 hours, and grinding to obtain solid powder; and (3) burning the solid powder in a muffle furnace at 500 ℃ for 2h to obtain the ZIF-8 molecular sieve supported multi-metal Fenton catalyst.
The method for treating berberine waste water by adopting the catalyst comprises the following steps:
(1) the pH value of the berberine waste water effluent raw water solution is 6.5-7.5, the concentration is 15mg/L, and 1mol/L H is added2SO4Adjusting pH to 2-3, adding 200mL of the above solution into a 500mL beaker;
(2) firstly adding H with the content of 30 percent2O2Adding 300mg of a ZIF-8 molecular sieve-loaded multi-metal Fenton catalyst into 1.5mL of the solution to obtain a mixed solution;
(3) fully stirring the mixed solution obtained in the step (2) for reaction, wherein the stirring speed is controlled at 100r/min, the stirring reaction time is 50min, and the pH value in the reaction process is controlled to be less than or equal to 7;
(4) after the reaction is finished, adjusting the pH value to 7 by using a sodium hydroxide solution, standing and layering the solution into a precipitate and a supernatant, wherein the supernatant is treated effluent. The CODcr values of the water quality before and after the water sample treatment are shown in Table 4:
| CODcr(mg/L) | CODcr removal Rate (%) | |
| Before treatment | 950mg/L | |
| After treatment | 266mg/L | |
| 72 |
TABLE 5
Tables 1-5 show that the CODcr removal rate of the wastewater in examples 1-5 is above 70%, which indicates that the catalyst provided by the invention has higher treatment efficiency.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A ZIF-8 molecular sieve supported multi-metal Fenton catalyst is characterized in that: the preparation method comprises the following steps:
takes ZIF-8 molecular sieve as a carrier and FeSO4·7H2O、CuSO4·5H2O and CoSO4·7H2And O is used as a precursor, the catalyst is prepared by a coprecipitation method, and then the catalyst is obtained through aging, suction filtration, washing, drying and calcination.
2. The ZIF-8 molecular sieve supported multi-metal fenton catalyst according to claim 1, wherein: the ZIF-8 molecular sieve is a porous crystal material with a zeolite-imidazolate-framework structure.
3. The ZIF-8 molecular sieve supported multi-metal fenton catalyst according to claim 2, wherein: the ZIF-8 molecular sieve is granular, fibrous, layered or film-shaped.
4. The ZIF-8 molecular sieve supported multi-metal fenton catalyst according to claim 3, wherein: the sum of the mass of the iron element, the copper element and the cobalt element in the catalyst is 0-20% of the mass of the catalyst and is not 0.
5. The ZIF-8 molecular sieve supported multi-metal Fenton catalyst of claim 4, wherein: the preparation method comprises the following steps:
(1) separately prepared Fe2+、Cu2+、Co2+FeSO with a molar concentration ratio of 1:1:1 to 5:1:14·7H2O、CuSO4·5H2O and CoSO4·7H2Stirring the water solution of O uniformly to obtain a mixed solution;
(2) adding 1mol/L H into the mixed solution obtained in the step (1)2SO4Uniformly stirring the solution, and adjusting the pH value to 2-3 to obtain a mixed solution;
(3) adding a ZIF-8 molecular sieve into the mixed solution obtained in the step (2), and uniformly stirring to obtain a ZIF-8 dispersion solution;
(4) adding 1mol/L NaOH solution into the ZIF-8 dispersion liquid obtained in the step (3), and adjusting the pH value to 9-11 to obtain a solution with precipitate;
(5) carrying out suction filtration on the solution with the precipitate obtained in the step (4) to obtain filter residue and filtrate, washing the filter residue to be neutral by using deionized water, carrying out vacuum drying on the washed filter residue at 60 ℃ for 8h, then carrying out drying at 100 ℃ for 2h, and grinding to obtain solid powder;
(6) and (4) burning the solid powder obtained in the step (5) for 2 hours in a muffle furnace at 500 ℃ to obtain the ZIF-8 molecular sieve supported multi-metal Fenton catalyst.
6. The method for preparing the ZIF-8 molecular sieve supported multi-metal fenton catalyst according to claim 4, wherein the method comprises the following steps: the method comprises the following steps:
(1) separately prepared Fe2+、Cu2+、Co2+FeSO with a molar concentration ratio of 1:1:1 to 5:1:14·7H2O、CuSO4·5H2O and CoSO4·7H2Stirring the water solution of O uniformly to obtain a mixed solution;
(2) adding 1mol/L H into the mixed solution obtained in the step (1)2SO4Uniformly stirring the solution, and adjusting the pH value to 2-3 to obtain a mixed solution;
(3) adding a ZIF-8 molecular sieve into the mixed solution obtained in the step (2), and uniformly stirring to obtain a ZIF-8 dispersion solution;
(4) adding 1mol/L NaOH solution into the ZIF-8 dispersion liquid obtained in the step (3), and adjusting the pH value to 9-11 to obtain a solution with precipitate;
(5) carrying out suction filtration on the solution with the precipitate obtained in the step (4) to obtain filter residue and filtrate, washing the filter residue with deionized water until the pH value of the filtrate is 7, carrying out vacuum drying on the washed filter residue at 60 ℃ for 8h, then drying at 100 ℃ for 2h, and grinding to obtain solid powder;
(6) and (4) burning the solid powder obtained in the step (5) for 2 hours in a muffle furnace at 500 ℃ to obtain the ZIF-8 molecular sieve supported multi-metal Fenton catalyst.
7. The use of the ZIF-8 molecular sieve supported multi-metal fenton catalyst of claim 4 for treating wastewater.
8. Use according to claim 7, characterized in that: the method for treating the wastewater by adopting the ZIF-8 molecular sieve loaded multi-metal Fenton catalyst comprises the following steps:
(1) taking a wastewater sample to be treated, and adjusting the pH value of the wastewater sample to be less than or equal to 7;
(2) adding H with the mass content of 30% into the wastewater sample after the pH value is adjusted in the step (1)2O2Adding a ZIF-8 molecular sieve loaded multi-metal Fenton catalyst into the solution to obtain a mixed solution;
(3) fully stirring the mixed solution obtained in the step (2) for reaction, controlling the stirring speed to be 100-500 r/min, controlling the reaction time to be 10-60min, and controlling the pH value in the reaction process to be less than or equal to 7;
(4) and (4) adjusting the pH value of the mixed solution after the reaction in the step (3) to 7, standing and layering the mixed solution into precipitate and supernatant, wherein the supernatant is treated effluent.
9. Use according to claim 8, characterized in that: in the step (2), the wastewater sample and H2O2The volume ratio of the solution is 200: 1-1000: 1, and the ZIF-8 molecular sieve supported multi-metal Fenton catalyst and H are2O2The mass ratio of the solution is 10: 1-50: 1.
10. Use according to claim 7 or 8 or 9, characterized in that: the wastewater is pharmaceutical wastewater.
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