CN108906071B - Magnetic ternary metal oxide catalyst and preparation method and application thereof - Google Patents
Magnetic ternary metal oxide catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 90
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 10
- 150000002696 manganese Chemical class 0.000 claims abstract description 10
- 239000003814 drug Substances 0.000 claims abstract description 9
- 229940079593 drug Drugs 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 150000002505 iron Chemical class 0.000 claims abstract description 7
- 238000006731 degradation reaction Methods 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 230000015556 catabolic process Effects 0.000 claims description 33
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 claims description 23
- 229960000623 carbamazepine Drugs 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 230000000593 degrading effect Effects 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 13
- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000004098 Tetracycline Substances 0.000 claims description 7
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 claims description 7
- 229960003376 levofloxacin Drugs 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 7
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 7
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 claims description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 7
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 7
- 229940043267 rhodamine b Drugs 0.000 claims description 7
- 229960002180 tetracycline Drugs 0.000 claims description 7
- 229930101283 tetracycline Natural products 0.000 claims description 7
- 235000019364 tetracycline Nutrition 0.000 claims description 7
- 150000003522 tetracyclines Chemical class 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000000975 dye Substances 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 6
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- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 39
- 230000004913 activation Effects 0.000 description 11
- 238000001994 activation Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- UOJLTGJDEASXFF-UHFFFAOYSA-N [Mn].[Co].[Fe] Chemical compound [Mn].[Co].[Fe] UOJLTGJDEASXFF-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- -1 cobalt manganese iron ions Chemical class 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000012425 OXONE® Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 1
- 229910017163 MnFe2O4 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
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Abstract
The invention discloses a magnetic ternary metal oxide catalyst, a preparation method and application thereof, wherein the chemical formula of the catalyst is Co3MnFeO6. The preparation method comprises the following steps: preparing iron salt, manganese salt and cobalt salt into reaction solution, heating to form gel, drying and roasting to obtain the catalyst of the invention. The magnetic ternary metal oxide catalyst has the advantages of excellent magnetic property, good stability, good catalytic property, environmental protection and the like, can efficiently activate peroxymonosulfate to generate sulfate radicals, can efficiently and quickly degrade organic pollutants, is easy to recycle, has good recycling property, has good application value and application prospect, has the advantages of simple process, easy operation, low cost and the like, is suitable for large-scale preparation, and is beneficial to industrial production. The catalyst of the invention can effectively degrade organic pollutants (such as organic dyes and organic medicines), and has a very wide application range.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and relates to a magnetic ternary metal oxide catalyst, and a preparation method and application thereof.
Background
With the rapid development of industry, the discharge amount of organic sewage (water containing organic pollutants, namely organic pollutant water) is rapidly increased, wherein printing and dyeing wastewater and pharmaceutical wastewater become main sources of organic sewage due to the characteristics of large discharge amount, difficult degradation of pollutants and the like. Because the organic sewage contains a large amount of organic dyes and organic medicines, the organic sewage can seriously threaten the water environment and the human health. Therefore, the treatment of organic sewage is imperative.
Among a plurality of sewage treatment technologies, the advanced oxidation technology has the advantages of high degradation rate, simple operation, no secondary pollution and the like, and is widely applied to removal of various refractory organic pollutants. The advanced oxidation technology is a method of using free radicals (HO) generated by reaction·And SO4 ·−) And the organic pollutants are subjected to reactions such as addition, substitution, electron transfer, chemical bond breakage and the like, so that the technology for degrading the pollutants in the water is realized. Wherein the hydroxyl radical (HO) is generated by hydrogen peroxide·) The traditional Fenton advanced oxidation technology has obvious defects, such as: the treatment has strict requirements on the pH environment of the wastewater, the utilization rate of hydrogen peroxide is low, the stability is poor and the like. Therefore, in recent years, potassium hydrogen persulfate complex salts have been used to generate sulfate radicals (SO)4 ·−) Have received a high degree of attention.
The activation of the potassium hydrogen persulfate complex salt is the key of the advanced oxidation technology based on sulfate radicals. Common activation modes include thermal activation, transition metal activation and ultraviolet light activation, wherein the transition metal activation is a research hotspot due to good controllability, low energy consumption and high efficiency. At present, the limiting factor of the development of transition metal activation is the lack of a catalyst which has good stability, high activation efficiency, easy recycling, low price and environmental friendliness. In recent years, homogeneous metal ion catalysts are developed into single-element metal oxide heterogeneous catalysts, and the problems of ion leaching and stability of the catalysts are well solved. Although further developed binary metal oxides can improve the activation efficiency, the activation efficiency thus obtained still cannot meet the actual demand, and needs to be further improved. Obviously, the existing monobasic or dibasic metal oxide catalyst still has the problems of insufficient catalytic performance and the like, and can not meet the actual requirement. Therefore, how to effectively overcome the problems to obtain the green and environment-friendly magnetic ternary metal oxide catalyst with excellent magnetic property, good stability and good catalytic performance has important significance for expanding the application field and the application range of the advanced oxidation technology.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art, provide a magnetic ternary metal oxide catalyst with excellent magnetic property, good stability, good catalytic performance and environmental protection, and also provide a preparation method of the magnetic ternary metal oxide catalyst with simple process, easy operation and low cost, and application of the magnetic ternary metal oxide catalyst in degrading organic pollutants.
In order to solve the technical problems, the invention adopts the technical scheme that:
a magnetic ternary metal oxide catalyst with a chemical formula of Co3MnFeO6。
As a general technical concept, the present invention also provides a method for preparing the above-mentioned magnetic ternary metal oxide catalyst, comprising the steps of:
s1, dissolving iron salt, manganese salt and cobalt salt in deionized water, and adding a nitric acid solution and an ethylene glycol solution to obtain a reaction solution;
s2, heating the reaction solution obtained in the step S1 until gel is formed;
and S3, drying and roasting the gel obtained in the step S2 to obtain the magnetic ternary metal oxide catalyst.
In the above preparation method, further improvement is provided, in the step S1, the molar ratio of the iron salt, the manganese salt, and the cobalt salt is 3: 1.
In a further improvement of the above preparation method, in step S1, the iron salt is at least one of ferric nitrate, ferric chloride and ferric sulfate; the manganese salt is at least one of manganese nitrate, manganese chloride and manganese sulfate; the cobalt salt is at least one of cobalt nitrate, cobalt chloride and cobalt sulfate; the mass concentration of the nitric acid solution is 65 percent; the mass concentration of the ethylene glycol solution is 99.0%.
In the preparation method, the reaction solution obtained in the step S1 is heated to 78-82 ℃ and kept for 2-3 h in the step S2.
In a further improvement of the above preparation method, in step S3, the drying is performed at a temperature of 118 ℃ to 123 ℃; the drying time is 5-8 h; the heating rate in the roasting process is 3-5 ℃/min; the roasting is carried out at the temperature of 300-500 ℃; the roasting time is 3-5 h.
As a general technical concept, the invention also provides an application of the magnetic ternary metal oxide catalyst or the magnetic ternary metal oxide catalyst prepared by the preparation method in degrading organic pollutants.
The application is further improved, and the method for degrading organic pollutants in water by using the magnetic ternary metal oxide catalyst comprises the following steps: the magnetic ternary metal oxide catalyst, the peroxymonosulfate and the organic pollutant water body are mixed for degradation reaction, and the degradation of the organic pollutant in the water body is completed.
The application is further improved, wherein the addition amount of the magnetic ternary metal oxide catalyst is 0.1-0.6 g of the magnetic ternary metal oxide catalyst added in each liter of organic pollutant water; the addition amount of the peroxymonosulfate is 0.1g to 0.6g of peroxymonosulfate added in each liter of organic pollutant water.
In the application, the further improvement is that the peroxymonosulfate is potassium peroxymonosulfate composite salt with the chemical formula of 2KHSO5·KHSO4·K2SO4(ii) a The organic pollutants in the organic pollutant water body are organic dyes and/or organic medicines; the initial concentration of the organic pollutants in the organic pollutant water body is 5 mg/L-50 mg/L; the pH value of the organic pollutant water body is 2.5-11; the time of the degradation reaction is 10min to 30 min.
In the above application, further improvement, the organic dye is rhodamine B or acid orange G; the organic drug is levofloxacin, tetracycline or carbamazepine.
Compared with the prior art, the invention has the following advantages:
(1) the invention provides a magnetic ternary metal oxide catalyst with a chemical formula of Co3MnFeO6. In the present invention, Co, Mn and Fe are respectively Co2+、Co3+、Mn2+、Mn3+、Mn4+、Fe2+、Fe3+The valence state of the cobalt and the manganese exists in the catalyst, the cobalt and the manganese activate the peroxymonosulfate through oxidation-reduction cycle reaction, the iron element mainly provides active sites for reaction substrates and magnetism for the catalyst, and the activation efficiency of the peroxymonosulfate can be obviously improved through the synergistic effect of the three elements, so that the degradation effect of organic pollutants can be obviously improved. The magnetic ternary metal oxide catalyst has the advantages of excellent magnetic property, good stability, good catalytic property, environmental protection and the like, can efficiently activate peroxymonosulfate to generate sulfate radicals, can efficiently and quickly degrade organic pollutants, is easy to recycle, has good recycling property, low requirement on water quality environment, and has good application value and application prospect.
(2) The invention also provides a preparation method of the magnetic ternary metal oxide catalyst, which comprises the steps of taking iron salt, manganese salt and cobalt salt as raw materials, uniformly dispersing the raw materials in a mixed solution of ethylene glycol and water, then carrying out hydrolytic polycondensation on metal ions in the solution under the catalytic action of nitric acid to form a metal gel precursor, and finally roasting the metal gel precursor at high temperature to prepare the magnetic ternary metal oxide catalyst with excellent magnetic property, good stability and good catalytic property. The preparation method has the advantages of simple process, easy operation, low cost and the like, is suitable for large-scale preparation, and is beneficial to industrial production.
(3) The invention also provides an application of the magnetic ternary metal oxide catalyst in degrading organic pollutants, for example, the magnetic ternary metal oxide catalyst is used for degrading organic pollutants in water, the magnetic ternary metal oxide catalyst, the peroxymonosulfate and the organic pollutants are mixed to carry out degradation reaction so as to effectively remove the organic pollutants in the water, the magnetic ternary metal oxide catalyst has the advantages of simple treatment process, easy operation, mild treatment condition (the reaction is carried out at room temperature), less raw material (catalyst and oxidant) consumption, low treatment cost, low energy consumption, good economic benefit, high treatment efficiency, good degradation effect and the like, can be widely used for degrading the organic pollutants (such as organic dyes and organic medicines) in the water, has wide application range, has low requirement on the pH value of the treated wastewater, and is suitable for strong acidity or wastewater, has a very wide application range.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is an XRD chart of the magnetic ternary metal oxide catalyst prepared in example 1 of the present invention.
Fig. 2 is a time-degradation efficiency diagram corresponding to the case where the magnetic ternary metal oxide catalyst in example 2 of the present invention degrades rhodamine B and acid orange G in a water body.
FIG. 3 is a graph of VSM before and after the use of the magnetic ternary metal oxide catalyst in example 2 of the present invention.
FIG. 4 is a degradation diagram of the magnetic ternary metal oxide catalyst of the present invention.
Fig. 5 is a time-degradation efficiency diagram corresponding to when the magnetic ternary metal oxide catalyst degrades levofloxacin and tetracycline in a water body in example 3 of the present invention.
Fig. 6 is a graph of time-degradation efficiency when the magnetic ternary metal oxide catalyst degrades carbamazepine solutions of different pH in example 4 of the present invention.
FIG. 7 is a graph of time-degradation efficiency for different catalyst compositions of the present invention in example 5 to degrade carbamazepine solution.
Fig. 8 is a graph of cycle number-degradation effect corresponding to repeated degradation of the carbamazepine solution by the magnetic ternary metal oxide catalyst in example 6 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
In the following examples of the present invention, unless otherwise specified, materials and instruments used are commercially available, processes used are conventional, apparatuses used are conventional, and the obtained data are average values of three or more repeated experiments.
Example 1:
a magnetic ternary metal oxide catalyst with chemical formula of Co3MnFeO6。
A preparation method of the magnetic ternary metal oxide catalyst in the embodiment includes the following steps:
(1) 3.49 g Co (NO) was weighed out at room temperature3)2·6H2O，1.00 g Mn(NO3)2·4H2O and 1.60 g Fe (NO)3)3·9H2And (3) dispersing O in 20 mL of deionized water by ultrasonic dispersion to completely dissolve the O, adding 5 mL of 65 mass percent nitric acid solution under magnetic stirring, and then adding 10 mL of 99.0 mass percent ethylene glycol solution to obtain a reaction solution, namely the reaction system.
(2) And (2) heating the reaction solution obtained in the step (1) to 80 ℃ in a water bath, and keeping for 3 hours until the solution forms a gel-like substance (gel).
(3) Drying the gel-like substance obtained in the step (1) in an oven at 120 ℃, wherein the drying time is 6 h; transferring the dried product into a muffle furnace, heating to 400 ℃ at the speed of 3 ℃/min, and roasting for 3h to obtain the magnetic ternary metal oxide catalyst.
Fig. 1 is an XRD chart of the magnetic ternary metal oxide catalyst prepared in example 1 of the present invention. As can be seen from fig. 1, the peak values of the (111), (220), (311), (400), (331), (422), (511) and (440) crystal planes are characteristic peaks of the ternary metal oxide of cobalt manganese iron, and no other miscellaneous peaks appear, indicating that no other substances are generated except the ternary metal oxide of cobalt manganese iron.
Example 2:
an application of a magnetic ternary metal oxide catalyst in degrading organic pollutants, in particular to a method for degrading organic pollutants in a water body by using a magnetic ternary metal oxide catalyst, which comprises the following steps:
two portions of the magnetic ternary metal oxide catalyst prepared in example 1, 10mg each, were weighed, added to 100mL of 50mg/L rhodamine B solution (pH = 4.74) and 100mL of 50mg/L acid orange G solution (pH = 6.71), and 20mg of potassium hydrogen peroxymonosulfate complex salt (2 KHSO) was added under continuous stirring5·KHSO4·K2SO4) And carrying out degradation reaction at room temperature to finish the degradation of the organic dye in the water body.
In the degradation reaction process, the solutions with different reaction times (2 min, 4min, 8min, 12min, 20 min) are taken for concentration measurement, and the degradation efficiency of rhodamine B and acid orange G is calculated, and the result is shown in figure 2.
Fig. 2 is a time-degradation efficiency diagram corresponding to the case where the magnetic ternary metal oxide catalyst in example 2 of the present invention degrades rhodamine B and acid orange G in a water body. As can be seen from FIG. 2, the removal rate of the magnetic ternary metal oxide catalyst of the invention to rhodamine B and acid orange G is more than 99% within 20 minutes, which shows that the catalyst of the invention has better degradation effect to different dyes.
The magnetic ternary metal oxide catalyst prepared in example 1 was used as Co before use3MnFeO6The magnetic ternary metal oxide catalyst collected after the degradation of the dye in example 2 was used as Co after use3MnFeO6They were subjected to magnetic property test, and the results are shown in FIG. 3. FIG. 3 is a graph of VSM before and after the use of the magnetic ternary metal oxide catalyst in example 2 of the present invention. As is clear from FIG. 3, the magnetic saturation value of the magnetic ternary metal oxide catalyst before use was 10.92 emu g-1(ii) a After use, the magnetic saturation value of the magnetic ternary metal oxide catalyst is 10.39 emu g-1It is said that the magnetic property of the catalyst is reduced little before and after use, and basicallyNeglect, namely the magnetic ternary metal oxide catalyst has better magnetic stability. In addition, as can be seen from the inset in fig. 3, the catalyst can be well collected by the external magnetic field before and after use, and the easy recycling of the catalyst is ensured.
FIG. 4 is a degradation diagram of the magnetic ternary metal oxide catalyst of the present invention. As can be seen from FIG. 4, the ternary metal oxide of cobalt manganese iron first excites the peroxymonosulfate to produce SO by the redox reaction of cobalt manganese iron and peroxymonosulfate4 ·−，SO4 ·−Further reaction with water may also produce HO·In SO4 ·−And HO•Under the combined action of the two components, the organic pollutants are degraded and removed; meanwhile, the oxidized cobalt manganese iron ions are promoted to be reduced into high-valence cobalt manganese iron ions through oxidation reduction circulation reaction, so that the recycling of the cobalt manganese iron ions is realized, and the continuous and effective operation of the whole degradation reaction is ensured.
Example 3:
an application of a magnetic ternary metal oxide catalyst in degrading organic pollutants, in particular to a method for degrading organic pollutants in a water body by using a magnetic ternary metal oxide catalyst, which comprises the following steps:
two portions of the magnetic ternary metal oxide catalyst prepared in example 1, 10mg each, were weighed, added to 100mL of a 20mg/L levofloxacin solution (pH = 6.54) and 100mL of a 20mg/L tetracycline solution (pH = 6.36), and 20mg of potassium hydrogen peroxymonosulfate complex salt (2 KHSO) was added under continuous stirring5·KHSO4·K2SO4) And carrying out degradation reaction at room temperature to finish the degradation of the organic medicine in the water body.
In the degradation reaction process, the solutions with different reaction times (2 min, 4min, 8min, 12min, 20 min) are taken for concentration measurement, and the degradation efficiency of levofloxacin and tetracycline is calculated, and the result is shown in fig. 5.
Fig. 5 is a time-degradation efficiency diagram corresponding to when the magnetic ternary metal oxide catalyst degrades levofloxacin and tetracycline in a water body in example 3 of the present invention. As can be seen from FIG. 5, the removal rate of the magnetic ternary metal oxide catalyst of the present invention to levofloxacin and tetracycline is up to 99% in 20 minutes, which indicates that the catalyst of the present invention has a good degradation effect to different organic drugs.
Example 4:
an application of a magnetic ternary metal oxide catalyst in degrading organic pollutants, in particular to a method for degrading organic pollutants in a water body by using a magnetic ternary metal oxide catalyst, which comprises the following steps:
10 parts of the magnetic ternary metal oxide catalyst prepared in example 1, 10mg each, were weighed out, added to carbamazepine solutions having pH values of 2.5, 3, 4, 5, 6, 7, 8, 9, 10, 11 (each solution had a volume of 100mL and a concentration of 5 mg/L), and 20mg of potassium hydrogen peroxymonosulfate complex salt (2 KHSO) was added under continuous stirring5·KHSO4·K2SO4) And carrying out degradation reaction at room temperature to finish the degradation of the carbamazepine in the water body.
In the degradation reaction process, the solutions with different reaction times (2 min, 4min, 8min, 12min, 20min, 30 min) are taken for concentration measurement, and the degradation efficiency of the magnetic ternary metal oxide catalyst on the carbamazepine solutions with different pH values is calculated, and the result is shown in fig. 6.
Fig. 6 is a graph of time-degradation efficiency when the magnetic ternary metal oxide catalyst degrades carbamazepine solutions of different pH in example 4 of the present invention. As can be seen from FIG. 6, the catalyst of the present invention can achieve a good degradation effect on a carbamazepine solution with a pH of 2.5-11, which indicates that the catalyst has a good removal effect on a hardly degradable pharmaceutically active organic substance, carbamazepine, and also indicates that the catalyst of the present invention has a very low requirement on the pH environment of a water sample, and is suitable for the treatment of organic pollutants water bodies with different pH values.
Example 5:
the method for investigating the influence of the catalysts with different components on the degradation effect of the organic pollutants comprises the following steps:
10mg of the magnetic ternary metal oxide catalyst prepared in example 1 was weighed,adding into 100mL carbamazepine solution with pH of 5.63 and concentration of 5mg/L, and adding 20mg potassium peroxymonosulfate complex salt (2 KHSO) under stirring5·KHSO4·K2SO4) And carrying out degradation reaction for 30min at room temperature to finish the degradation of the carbamazepine in the water body.
With Mn3O4、Fe3O4、Co3O4、MnFe2O4、CoFe2O4、CoMn2O4Magnetic ternary Metal oxide catalyst (Co) in place of example 13MnFeO6) The carbamazepine solution was subjected to degradation under the same conditions.
In the degradation reaction process, the solutions with different reaction times (2 min, 4min, 8min, 12min, 20min, 30 min) are taken for concentration measurement, and the degradation efficiency of the catalyst with different components on the carbamazepine solution is calculated, and the result is shown in fig. 7.
FIG. 7 is a graph of time-degradation efficiency for different catalyst compositions of the present invention in example 5 to degrade carbamazepine solution. As can be seen from FIG. 7, the magnetic ternary metal oxide catalyst (Co) of the present invention3MnFeO6) The obvious degradation effect on carbamazepine is due to other binary or unitary metal oxides, which is mainly because the Co, Mn and Fe in the magnetic ternary metal oxide catalyst are respectively Co2+、Co3+、Mn2+、Mn3+、Mn4+、Fe2+、Fe3+The cobalt and manganese activate the peroxymonosulfate through oxidation-reduction cycle reaction, the iron element mainly provides active sites for reaction substrates and magnetism for catalysts, and the activation efficiency of the peroxymonosulfate can be remarkably improved through the synergistic effect of the three elements, so that the degradation effect of organic pollutants can be remarkably improved.
Example 6:
the recycling performance of the magnetic ternary metal oxide catalyst for degrading organic pollutants is inspected, and the method comprises the following steps:
(1) 10mg of the magnetic material prepared in example 1 were weighedAdding ternary metal oxide catalyst into carbamazepine solution of 100mL, pH 5.63 and concentration 5mg/L, and adding 20mg potassium hydrogen peroxymonosulfate complex salt (2 KHSO) under continuous stirring5·KHSO4·K2SO4) And carrying out degradation reaction for 30min at room temperature to finish the degradation of the carbamazepine in the water body.
(2) And (3) after the degradation reaction is finished, removing the magnetic ternary metal oxide catalyst in the reaction system in the step (1) by using an external magnetic field mode, washing and drying, and continuously using the obtained magnetic ternary metal oxide catalyst for degrading the carbamazepine in the water body.
(3) Repeating the operations in the steps (1) to (2) for 3 times. Namely, four degradations of the carbamazepine solution were accomplished using the magnetic ternary metal oxide catalyst prepared in example 1.
Fig. 8 is a graph of cycle number-degradation effect corresponding to repeated degradation of the carbamazepine solution by the magnetic ternary metal oxide catalyst in example 6 of the present invention. In FIG. 8, 1st, 2nd, 3rd, and 4th represent the first, second, third, and fourth degradations, respectively. As can be seen from fig. 8, the degradation efficiency of the magnetic ternary metal oxide catalyst of the present invention is still as high as 91% after four repeated degradations of the carbamazepine solution, which indicates that the magnetic ternary metal oxide catalyst of the present invention still maintains a high catalytic activity after four repeated degradations, and also indicates that the magnetic ternary metal oxide catalyst of the present invention has a high stability and can be recycled.
In conclusion, the magnetic ternary metal oxide catalyst has the advantages of excellent magnetic property, good stability, good catalytic property, environmental protection and the like, can efficiently activate peroxymonosulfate to generate sulfate radicals, can efficiently degrade organic pollutants, can finally effectively remove the organic pollutants in water, and has good application value and application prospect.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (9)
1. The magnetic ternary metal oxide catalyst for degrading organic pollutants is characterized by having a chemical formula of Co3MnFeO6(ii) a The preparation method of the magnetic ternary metal oxide catalyst comprises the following steps:
(1) dissolving ferric salt, manganese salt and cobalt salt into deionized water, and adding a nitric acid solution and an ethylene glycol solution to obtain a reaction solution; the molar ratio of the ferric salt to the manganese salt to the cobalt salt is 1: 3;
(2) heating the reaction solution obtained in the step (1) until gel is formed;
(3) and (2) drying and roasting the gel obtained in the step (1) to obtain the magnetic ternary metal oxide catalyst.
2. A method for preparing the magnetic ternary metal oxide catalyst of claim 1, comprising the steps of:
s1, dissolving iron salt, manganese salt and cobalt salt in deionized water, and adding a nitric acid solution and an ethylene glycol solution to obtain a reaction solution; the molar ratio of the ferric salt to the manganese salt to the cobalt salt is 1: 3;
s2, heating the reaction solution obtained in the step S1 until gel is formed;
and S3, drying and roasting the gel obtained in the step S2 to obtain the magnetic ternary metal oxide catalyst.
3. The preparation method according to claim 2, wherein in the step S1, the iron salt is at least one of ferric nitrate, ferric chloride and ferric sulfate; the manganese salt is at least one of manganese nitrate, manganese chloride and manganese sulfate; the cobalt salt is at least one of cobalt nitrate, cobalt chloride and cobalt sulfate; the mass concentration of the nitric acid solution is 65 percent; the mass concentration of the ethylene glycol solution is 99.0%.
4. The production method according to claim 2 or 3, wherein in step S2, the reaction solution obtained in step S1 is heated to 78 ℃ to 82 ℃ for 2 to 3 hours;
in the step S3, the drying is performed at a temperature of 118 to 123 ℃; the drying time is 5-8 h; the heating rate in the roasting process is 3-5 ℃/min; the roasting is carried out at the temperature of 300-500 ℃; the roasting time is 3-5 h.
5. Use of the magnetic ternary metal oxide catalyst according to claim 1 or the magnetic ternary metal oxide catalyst prepared by the preparation method according to any one of claims 2 to 4 for degrading organic pollutants.
6. The use of claim 5, wherein the degradation of organic pollutants in a body of water using a magnetic ternary metal oxide catalyst comprises the steps of: the magnetic ternary metal oxide catalyst, the peroxymonosulfate and the organic pollutant water body are mixed for degradation reaction, and the degradation of the organic pollutant in the water body is completed.
7. The application of claim 6, wherein the addition amount of the magnetic ternary metal oxide catalyst is 0.1-0.6 g per liter of organic pollutant water; the addition amount of the peroxymonosulfate is 0.1g to 0.6g of peroxymonosulfate added in each liter of organic pollutant water.
8. Use according to claim 6 or 7, wherein the salt of peroxymonosulfate is a potassium hydrogen peroxymonosulfate complex salt of formula 2KHSO5·KHSO4·K2SO4(ii) a The organic pollutant in the organic pollutant water body is organic dyeAnd/or an organic drug; the initial concentration of the organic pollutants in the organic pollutant water body is 5 mg/L-50 mg/L; the pH value of the organic pollutant water body is 2.5-11; the time of the degradation reaction is 10min to 30 min.
9. The use according to claim 8, wherein the organic dye is rhodamine B or acid orange G; the organic drug is levofloxacin, tetracycline or carbamazepine.
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| CN111871422A (en) * | 2020-07-21 | 2020-11-03 | 上海交通大学 | Application of calcium-manganese oxide catalyst in degradation of organic pollutants in wastewater and soil |
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| CN113117690A (en) * | 2021-04-21 | 2021-07-16 | 宁夏大学 | Preparation method of cobalt-manganese spinel catalyst and application of catalyst in catalytic oxidation degradation of tetracycline in water |
| CN113769756A (en) * | 2021-08-05 | 2021-12-10 | 宁波神筹环保设备有限公司 | Novel iron-manganese oxide catalyst and application thereof |
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