CN109999818B - Activated persulfate magnetic solid-phase catalyst and preparation method and application thereof - Google Patents
Activated persulfate magnetic solid-phase catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical class S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 239000007790 solid phase Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001868 water Inorganic materials 0.000 claims abstract description 26
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 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 12
- 230000000593 degrading effect Effects 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
- 229940011182 cobalt acetate Drugs 0.000 claims description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 7
- 239000000356 contaminant Substances 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 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 claims description 5
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- OVSKIKFHRZPJSS-DOMIDYPGSA-N 2-(2,4-dichlorophenoxy)acetic acid Chemical compound OC(=O)[14CH2]OC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-DOMIDYPGSA-N 0.000 claims description 2
- CXOFVDLJLONNDW-UHFFFAOYSA-N Phenytoin Chemical compound N1C(=O)NC(=O)C1(C=1C=CC=CC=1)C1=CC=CC=C1 CXOFVDLJLONNDW-UHFFFAOYSA-N 0.000 claims description 2
- 229960002036 phenytoin Drugs 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [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 2
- 229940043267 rhodamine b Drugs 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 16
- 238000006731 degradation reaction Methods 0.000 abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract description 3
- 239000010941 cobalt Substances 0.000 abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011949 solid catalyst Substances 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 239000002562 thickening agent Substances 0.000 abstract 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000003344 environmental pollutant Substances 0.000 description 11
- 231100000719 pollutant Toxicity 0.000 description 11
- 238000001362 electron spin resonance spectrum Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- -1 sulfate radicals Chemical class 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 238000011835 investigation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002077 nanosphere Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RVWUHFFPEOKYLB-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1(C)CCCC(C)(C)[NH+]1[O-] RVWUHFFPEOKYLB-UHFFFAOYSA-N 0.000 description 1
- LIDGFHXPUOJZMK-UHFFFAOYSA-N 2,6-dimethyl-1-oxidopyridin-1-ium Chemical compound CC1=CC=CC(C)=[N+]1[O-] LIDGFHXPUOJZMK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- PHCDZUPEIPGYOG-UHFFFAOYSA-N [Fe].[Co].[Zn] Chemical group [Fe].[Co].[Zn] PHCDZUPEIPGYOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- 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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- 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
- B01J23/80—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 zinc, cadmium or mercury
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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
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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
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/34—Organic compounds containing oxygen
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Abstract
The invention provides an activated persulfate magnetic solid-phase catalyst and a preparation method and application thereof. The method of the invention takes acetate as a zinc source, a cobalt source and an iron source, and has the advantages that metal cations and coordination groups of the acetate are easy to perform special form bridging and complex agglomeration with citric acid, the method is beneficial to growth control of crystal forms and crystal sizes, and organic solvents such as glycol and the like are not needed for forming sol as a thickening agent, so that the method is simpler and more economic. The catalyst has high degradation efficiency and degradation rate on organic pollutants, stable performance and good recycling effect, is a magnetic solid catalyst and is convenient to separate from water.
Description
Technical Field
The invention relates to the technical field of catalyst preparation and application, in particular to an activated persulfate magnetic solid-phase catalyst and a preparation method and application thereof.
Background
In recent years, human activities discharge a large amount of refractory organic pollutants, such as medical compounds, pesticides, surfactants, dyes and the like, into the environment, which not only causes water resource crisis, but also directly threatens human health. Conventional physicochemical and biological treatment techniques are often ineffective at removing these persistent contaminants.
Based on the generation of sulfate radicals (SO) by activation of persulfates4 -SR-AOPs) is a new technology developed in recent years for treating refractory organic pollutants, and especially for the success of remediation of groundwater and soil contaminated by organic pollutants, making it a great deal of attention and research. The SR-AOPs technology has the advantages of good stability and solubility of the oxidant, wider pH application range, strong oxidizing capability and the like. SO (SO)4 -Long life in water and greatly increased SO4 -The opportunity of contact with organic pollutants, favouring their degradation and mineralization.
The current methods for activating persulfate include heat treatment, ultraviolet radiation, microwave treatment, transition metal ion catalytic activation and the like. The three technologies need additional energy, and the equipment system is complex and high in cost. The transition metal ion catalytic activation method has mild reaction conditions and simple operation, but the introduced metal ions need to be further removed after the reaction is finished, so that the process operation cost is increased, and the toxicity risk of the effluent is increased. The development of the heterogeneous activated persulfate technology overcomes some key problems of the homogeneous technology, such as no free metal ions are introduced into a water body any more, and the separation of the catalyst and the active component is realized. However, the currently developed solid catalyst is limited by the contact area in water and is influenced by the electron transfer and circulation rate of the reaction system, and most of the solid catalyst has low catalytic efficiency and certain selectivity, and is difficult to meet the actual requirements. The nano catalyst can increase the specific surface area and the exposure degree of active sites and improve the catalytic activity, but the solid-liquid separation is difficult to realize.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an activated persulfate magnetic solid-phase catalyst and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing an activated persulfate magnetic solid-phase catalyst, comprising the steps of:
(1) dissolving zinc acetate, cobalt acetate and ferric nitrate in a nitric acid solution, and uniformly mixing to obtain a mixed solution A, wherein the dosage of the zinc acetate, the cobalt acetate and the ferric nitrate is as follows: the molar quantity ratio of Zn, Co and Fe elements is 1: 2-x: x, wherein 0 is less than 2;
(2) adding citric acid into the mixed solution A, stirring and heating at 60-100 ℃ until the solution is brown sol, wherein the molar quantity ratio of the citric acid to Zn element is (2-9) to 1;
(3) heating the brown sol to 100-220 ℃ in the air, and keeping for 6-15 hours to obtain a solid substance;
(4) grinding the solid substance obtained in the step (3), roasting at the temperature of 400-1000 ℃, and keeping for 2-20 hours;
(5) and naturally cooling the roasted solid, washing with inorganic acid and water successively, and drying.
The method takes citric acid as a chelating agent and zinc acetate (Zn (CH)3COO)2) Cobalt acetate (Co (CH)3COO)2) Iron nitrate (Fe (NO)3)3) Respectively used as a zinc source, a cobalt source and an iron source, and synthesizing the target catalyst by a sol combustion method. The method of the invention takes acetate as a zinc source, a cobalt source and an iron source, and has the advantages that metal cations and coordination groups of the acetate are easy to perform special form bridging and complex agglomeration with citric acid, thereby being beneficial to the growth control of crystal forms and crystal sizes. In addition, the sol is formed without using organic solvent such as ethylene glycolThickener, the method is simpler and more economical.
Preferably, the zinc acetate, the cobalt acetate and the ferric nitrate are used in the following amounts: x is 1.4.
Preferably, the molar quantity ratio of the citric acid to the Zn element is 6:1
Preferably, in the step (2), the solution is stirred and heated at 90 ℃ until the solution is brown sol, and the stirring and heating time is 4 to 6 hours.
More preferably, in step (2), the solution is heated with stirring at 90 ℃ until the solution is a tan sol, and the stirring and heating time is 5 hours.
Preferably, the tan sol is heated to 170 ℃ in air in step (3) for 12 hours.
Preferably, the calcination temperature in step (4) is 600 ℃ and the calcination time is 6 hours.
Preferably, the heating in step (3) is carried out at a ramp rate of less than 20 ℃/min.
More preferably, the heating in step (3) is carried out at a heating rate of 10 ℃/min.
Preferably, the temperature rise rate of the calcination in the step (4) is 5-10 ℃/min.
Preferably, the mass fraction of the nitric acid solution is 3% -13.7%.
More preferably, the mass fraction of the nitric acid solution is 5.8%.
Preferably, the inorganic acid in the step (5) is hydrochloric acid solution, and the pH of the hydrochloric acid solution is 2-3.
More preferably, the pH of the hydrochloric acid solution is 2.45.
Preferably, the process of washing with mineral acid and water comprises the steps of: weighing 0.5g of roasted solid in a beaker, adding 100mL of hydrochloric acid solution with the pH value of 2-3, stirring, washing for 20min, centrifuging, and repeating for three times; washed with ultrapure water again for 2 times and then dried.
Preferably, in step (5), the temperature for drying after washing is 50 to 100 ℃.
More preferably, in step (5), the temperature of drying after washing is 70 ℃.
Preferably, the stirring rotation speed in the washing in the step (5) is 200-400r/min, and the centrifugal rotation speed is 8000-10000 r/min.
Preferably, the stirring speed is 300r/min and the centrifugal speed is 10000r/min during washing in the step (5).
The invention also provides the activated persulfate magnetic solid-phase catalyst prepared by any one of the methods.
The catalyst is zinc-iron-cobalt trimetal oxide (ZnFe)xCo2-xO4) The catalyst is brown solid powder, has magnetism, can be easily adsorbed on a magnet material, has large specific surface area, high dispersity in water, high catalytic efficiency, easy solid-liquid separation and good stability in water, and can still maintain high catalytic activity after repeated degradation.
The invention also provides an application of the catalyst in degrading organic pollutants in water.
The invention also provides a method for degrading organic pollutants in water, which is to add the catalyst and persulfate into water and mix the mixture evenly.
The above-mentioned activated persulfate magnetic solid-phase catalyst (ZnFe)xCo2-xO4) When used in combination with Persulfate (PMS), generates hydroxyl radicals (HO. cndot.) and SO4 -The catalyst has magnetism and is easy to recycle. The catalytic degradation activity and efficiency of the invention are obviously higher than those of the conventional heterogeneous Fenton catalyst.
Preferably, the organic contaminants include at least one of bisphenol a, phenytoin, 2-chlorophenol, 2, 4-dichlorophenoxyacetic acid, rhodamine B, methylene blue.
The invention has the beneficial effects that: the invention provides an activated persulfate magnetic solid-phase catalyst and a preparation method and application thereof. The magnetic solid-phase catalyst for activating persulfate prepared by the invention has the following advantages:
(1) the catalyst has low requirements on the reaction conditions of the system, and has high removal efficiency and rate on the organic pollutants difficult to degrade at room temperature;
(2) the catalyst has an irregular blocky structure with dense phase nano pores, has a huge specific surface area, and has easy contact with pollutants and PMS;
(3) the catalyst has good stability in the process of removing organic pollutants;
(4) the catalyst is a magnetic solid, can be easily recovered by using a magnetic material, and is convenient to recycle;
(5) the catalyst of the invention can utilize pollutants as electron donors of a system to promote the rapid cyclic migration of electrons.
Drawings
FIG. 1 shows an example of an activated persulfate magnetic solid-phase catalyst (ZnFe) prepared according to the present inventionxCo2-xO4) SEM and TEM electron micrographs of (a).
FIG. 2 shows an example of an activated persulfate magnetic solid-phase catalyst (ZnFe) prepared according to the present inventionxCo2-xO4) HRTEM of (g).
FIG. 3 shows TEMPO trapping singlet oxygen at different reaction times in different reaction systems according to an embodiment of the present invention1O2) EPR spectrum of
FIG. 4 shows an embodiment of the present invention in which DMPO captures hydroxyl radicals (HO.) and sulfate radicals (SO) in different reaction systems4 -·.) EPR spectrum.
FIG. 5 is a graph showing the effect of the examples of the present invention and comparative examples on the degradation of bisphenol A.
FIG. 6 is a graph showing the effect of the activated persulfate magnetic solid-phase catalyst prepared according to the embodiment of the present invention on the degradation of organic pollutants.
FIG. 7 is a diagram illustrating the recycling degradation effect of the activated persulfate magnetic solid-phase catalyst prepared in the embodiment of the present invention on degrading bisphenol A.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The preparation method of the activated persulfate magnetic solid-phase catalyst provided by the embodiment of the invention comprises the following steps:
(1) 2.195g of Zn (CH)3COO)2·2H2O、1.494g Co(CH3COO)2·4H2O、5.656g Fe(NO)3·9H2Dissolving O in a nitric acid solution with the mass fraction of 5.8%, and uniformly mixing to obtain a mixed solution A;
(2) adding 11.526g of citric acid into the mixed solution A, stirring for 10min until the solid is completely dissolved, and then stirring for 5h at 90 ℃ until the solution is in a tan sol state to obtain a tan sol;
(3) transferring the brown sol obtained in the step (2) into a ceramic crucible, putting the ceramic crucible into an oven, and drying at 170 ℃ at a heating rate of 10 ℃/min to obtain a dried solid substance;
(4) fully grinding the solid matter obtained in the step (3), putting the ground solid matter into a muffle furnace, roasting at 600 ℃, and keeping the temperature for 6 hours at the heating rate of 5 ℃/min;
(5) naturally cooling the roasted solid to form powder, washing the roasted and cooled powder with hydrochloric acid with the pH value of 2.45 for 3 times, washing with ultrapure water for 2 times, drying at 70 ℃, and grinding to obtain the activated persulfate magnetic solid-phase catalyst (ZnFe)xCo2-xO4)；
Wherein, the method for washing the inorganic acid and the water comprises the following steps: weighing 0.5g of roasted solid in a beaker, adding 100mL of hydrochloric acid solution with the pH value of 2.45, stirring and washing for 20min, centrifuging, and repeating for three times; and then washing the mixture for 2 times by using ultrapure water, and then drying the mixture, wherein the drying temperature after washing is 70 ℃, the stirring rotation speed during washing is 300r/min, and the centrifugal rotation speed is 10000 r/min.
Characterization of the results of the product:
1. TEM and SEM: FIG. 1 shows ZnFe prepared in the examplesxCo2-xO4TEM and SEM images of (a). As can be seen from FIG. 1, ZnFexCo2-xO4Is in the shape of a nano sphere with uniform size, and the particle size of the nano sphere is 20-50 nm. As can be seen from FIG. 2, ZnFexCo2-xO4The nanosphere has clear lattice stripes, and the lattice widths are 0.205 nm, 0.291 nm and 0.254nm respectively, which shows that the material has good crystallinity and obvious crystal structure.
2. Catalytic performance
Group A: ZnFe prepared in example 1 was added to waterxCo2-xO4Potassium Persulfate (PMS) and bisphenol A (BPA), with 2,2,6, 6-tetramethylpiperidine oxide (TEMPO) added, investigation of TEMPO for the capture of singlet oxygen (TEMPO)1O2) EPR spectrum of (1).
Group B: ZnFe prepared in example 1 was added to waterxCo2-xO4Potassium persulfate, TEMPO addition, investigation of TEMPO Capture of singlet oxygen: (1O2) EPR spectrum of (1).
Group C: (ii) Potassium persulfate was added to water, and after TEMPO addition, TEMPO was examined for the capture of singlet oxygen (ii) TEMPO1O2) EPR spectrum of (1).
Group D: ZnFe prepared in example 1 was added to waterxCo2-xO4Potassium persulfate and bisphenol A, addition of lutidine N-oxide (DMPO), investigation of DMPO capture of hydroxyl (HO.) and Sulfate (SO) radicals4 -·.) EPR spectrum.
Group E: ZnFe prepared in example 1 was added to waterxCo2-xO4Potassium persulfate, DMPO addition, investigation of the capture of hydroxyl (HO.) and Sulfate (SO) radicals by DMPO4 -·.) EPR spectrum.
And F group: potassium persulfate was added to water and after DMPO addition, the capture of hydroxyl (HO.) and Sulfate (SO) radicals by DMPO was examined4 -·.) EPR spectrum.
FIG. 3 shows TEMPO trapping singlet oxygen at different reaction times in different reaction systems1O2) EPR spectrum of (1), FIG. 4 isDMPO captures hydroxyl radical (HO) and sulfate radical (SO) in different reaction systems4 -·.) EPR spectrum. As can be seen from the figure, in ZnFexCo2-xO4/PMS/H2O and ZnFexCo2-xO4The reaction system of PMS/BPA has obvious HO and SO4 -A, and1O2EPR signal of (b), indicating ZnFexCo2-xO4Has strong activation capability to PMS. In ZnFexCo2-xO4In a PMS/BPA system, the intensity of three free radical signals is obviously stronger than that of ZnFexCo2-xO4/PMS/H2O system, wherein,1O2the signal intensity of (A) is ZnFexCo2-xO4/PMS/H22.8 times of that of O system, HO & SO4 -The signal strength of is ZnFexCo2-xO4/PMS/H23.1 times in the O system. The generation of the three free radicals in the system is obviously promoted by adding the pollutant BPA, which shows that the pollutant can directly provide electrons for the system, and the catalyst has important significance for further decomposition and mineralization of the pollutant.
Example 2
The method for degrading organic pollutants in water, which is an embodiment of the invention, comprises the following steps:
(1) adding 0.1g of the catalyst prepared in the example 1 into 100mL of 10mg/L bisphenol A solution, keeping the temperature at 25 ℃, and continuously stirring for 10min to ensure that the pollutants and the catalyst reach adsorption equilibrium;
(2) adding 0.307g (1mmol) of potassium persulfate, and mixing uniformly;
(3) the reaction was carried out for 30 minutes.
Samples were taken at different time points to determine bisphenol A concentration.
Example 3
As a method for degrading organic pollutants in water according to an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is: the organic contaminant is 2-chlorophenol (2-CP).
Example 4
As a method for degrading organic pollutants in water according to an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is: the organic contaminant is Methylene Blue (MB).
Example 5
The method for degrading organic pollutants in water, which is an embodiment of the invention, comprises the following steps:
(1) adding 0.1g of the catalyst prepared in the example 1 into 100mL of 10mg/L bisphenol A solution, keeping the temperature at 25 ℃, and continuously stirring for 10min to ensure that the pollutants and the catalyst reach adsorption equilibrium;
(2) 0.307g (1mmol) of potassium persulfate was added thereto and mixed well.
(3) After reacting for 30 minutes, separating the catalyst in the solution, washing and filtering the catalyst by using ultrapure water, and drying the catalyst;
(4) and (3) repeating the steps (1), (2) and (3).
Comparative example 1
A method of degrading organic contaminants in water as a comparative example of the present invention, the method comprising the steps of:
(1) adding 0.1g of the catalyst prepared in the example 1 into 100mL of 10mg/L bisphenol A solution, keeping the temperature at 25 ℃, and continuously stirring for 10min to ensure that the pollutants and the catalyst reach adsorption equilibrium;
(2) the reaction was carried out for 30 minutes.
Samples were taken at different time points to determine bisphenol A concentration.
Comparative example 2
A method of degrading organic contaminants in water as a comparative example of the present invention, the method comprising the steps of:
(1) adding 0.307g of potassium persulfate into 100mL of 10mg/L bisphenol A solution, keeping the temperature at 25 ℃, and continuously stirring for 10min to ensure that the pollutants and the catalyst reach adsorption balance;
(2) the reaction was carried out for 30 minutes.
Samples were taken at different time points to determine bisphenol A concentration.
The experimental results are as follows:
as shown in fig. 5, the degradation results of example 2, comparative example 1 and comparative example 2 are shown. Comparative examples 1 andcomparative example 2 shows that the degradation effect on BPA is less than 8%, the degradation effect in example 2 is obvious, the removal rate of BPA is 83% when the reaction is carried out for 10min, and the activated persulfate magnetic solid-phase catalyst (ZnFe) prepared in example 1 is describedxCo2-xO4) After being mixed with persulfate, the composite material has good degradation effect on organic pollutants.
As shown in fig. 6, the degradation results of example 2, example 3, and example 4 are shown. Persulfate and ZnFexCo2- xO4The degradation rate of bisphenol A, 2-chlorophenol and methylene blue is high, the degradation rate is high, the removal rate of 3 pollutants is higher than 60% when the reaction is started for 5min, and the removal rate of 3 pollutants is higher than 90% when the reaction is started for 10 min.
As shown in fig. 7, the degradation results of example 5 are shown. ZnFe in quadruplicatexCo2-xO4All show higher catalytic activity, ZnFe in the fourth repeated testxCo2-xO4The removal rate of BPA is still higher than 85 percent, which shows that ZnFexCo2-xO4The stability in a reaction system is good, and the catalyst can be repeatedly utilized.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of an activated persulfate magnetic solid-phase catalyst is characterized by comprising the following steps:
(1) dissolving zinc acetate, cobalt acetate and ferric nitrate in a nitric acid solution, and uniformly mixing to obtain a mixed solution A, wherein the dosage of the zinc acetate, the cobalt acetate and the ferric nitrate is as follows: the molar quantity ratio of Zn, Co and Fe elements is 1: 2-x: x, wherein 0 is less than 2;
(2) adding citric acid into the mixed solution A, stirring and heating at 60-100 ℃ until the solution is brown sol, wherein the molar quantity ratio of the citric acid to Zn element is (2-9) to 1;
(3) heating the brown sol to 100-220 ℃ in the air, and keeping for 6-15 hours to obtain a solid substance;
(4) grinding the solid substance obtained in the step (3), roasting at the temperature of 400-1000 ℃, and keeping for 2-20 hours;
(5) and naturally cooling the roasted solid, washing with inorganic acid and water successively, and drying.
2. The method of claim 1, wherein the zinc acetate, cobalt acetate and ferric nitrate are used in the following amounts: x is 1.4.
3. The method of claim 1, wherein in step (2), the solution is heated with stirring at 90 ℃ until the solution is a tan sol, and the stirring and heating time is 4-6 hours.
4. The method of claim 1, wherein the tan sol is heated to 170 ℃ in air for 12 hours in step (3).
5. The method as claimed in claim 1, wherein the calcination temperature in the step (4) is 600 ℃ and the calcination time is 6 hours.
6. The method according to claim 1, wherein the heating in step (3) is performed at a heating rate of less than 20 ℃/min, the heating rate for the calcination in step (4) is 5-10 ℃/min, the inorganic acid in step (5) is a hydrochloric acid solution, and the pH of the hydrochloric acid solution is 2-3.
7. The method according to claim 1, wherein the mass fraction of the nitric acid solution in the step (1) is 3 to 13.7%.
8. An activated persulfate magnetic solid-phase catalyst prepared according to the method of any one of claims 1 to 7.
9. A method for degrading organic pollutants in water, adding the catalyst of claim 8 and persulfate to the water, and mixing uniformly.
10. The method of claim 9, wherein the organic contaminants comprise at least one of bisphenol a, phenytoin, 2-chlorophenol, 2, 4-dichlorophenoxyacetic acid, rhodamine B, methylene blue.
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