CN110252316A - Hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst and the preparation method and application thereof - Google Patents
Hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst and the preparation method and application thereof Download PDFInfo
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- CN110252316A CN110252316A CN201910598488.5A CN201910598488A CN110252316A CN 110252316 A CN110252316 A CN 110252316A CN 201910598488 A CN201910598488 A CN 201910598488A CN 110252316 A CN110252316 A CN 110252316A
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- fenton
- ferrihydrite
- multiphase
- cerium dioxide
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 95
- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006731 degradation reaction Methods 0.000 claims abstract description 74
- 230000015556 catabolic process Effects 0.000 claims abstract description 66
- 230000003197 catalytic effect Effects 0.000 claims abstract description 32
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims abstract description 10
- 239000004098 Tetracycline Substances 0.000 claims description 75
- 229960002180 tetracycline Drugs 0.000 claims description 74
- 229930101283 tetracycline Natural products 0.000 claims description 74
- 235000019364 tetracycline Nutrition 0.000 claims description 74
- 150000003522 tetracyclines Chemical class 0.000 claims description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 46
- 229910001868 water Inorganic materials 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000002351 wastewater Substances 0.000 claims description 39
- 230000003115 biocidal effect Effects 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 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 13
- 229940043267 rhodamine b Drugs 0.000 claims description 13
- 241000235342 Saccharomycetes Species 0.000 claims description 11
- 239000005416 organic matter Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 5
- 239000003205 fragrance Substances 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims description 4
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000005265 energy consumption Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 33
- 239000003344 environmental pollutant Substances 0.000 abstract description 12
- 231100000719 pollutant Toxicity 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 230000004913 activation Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 50
- 229910052742 iron Inorganic materials 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000033558 biomineral tissue development Effects 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 235000014680 Saccharomyces cerevisiae Nutrition 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- -1 hydroxyl radical free radical Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 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 2
- 238000001354 calcination Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011806 microball Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000143437 Aciculosporium take Species 0.000 description 1
- 239000012695 Ce precursor Substances 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000254158 Lampyridae Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910001139 Telluric iron Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011807 nanoball Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000009416 shuttering Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/83—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 rare earths or actinides
-
- B01J35/39—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
- B01J37/36—Biochemical methods
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
-
- 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
- C02F2305/10—Photocatalysts
Abstract
The invention discloses hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalysts and the preparation method and application thereof.The preparation method of the hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst includes being prepared under high temperature environment as biological template with porous cerium dioxide nano microballoon first with S. cervisiae, then so that it is loaded to ferrihydrite surface by way of in-situ deposition.Mesoporous cerium dioxide nano microballoon in the catalyst has light sensitive effect, can responding to visible light generate photo-generated carrier, promote ferrihydrite in Fenton-like system to the activation efficiency of hydrogen peroxide.Generated living radical group has wide spectrum catalytic degradation effect to pollutant, has certain practical application value.
Description
Technical field
The invention belongs to the preparation of multiphase-fenton Fenton material and environment water treatment fields, and in particular to hollow cerium dioxide micro-balloon
Load ferrihydrite multiphase-fenton fenton catalyst and the preparation method and application thereof.
Background technique
In the recent period, the enrichment of emerging pollutant such as antibiotic in surface water will lead to evolution generation and the environment of antibody-resistant bacterium
Pollution.It is reported that the tetracycline as one of four major class antibiotic, is in antibiotic agents in the annual output ranking of China
First.Again since it is with stable aromatic structure and functional group, it is difficult natural degradation in the environment.Traditional physical treatment
Mode can not make this emerging pollutant degrade, thus, advanced oxidation technology, especially with hydrogen peroxide (H2O2) conduct
The Fenton technology of oxidant is paid close attention to by people and is applied to the degradation of such emerging pollutant antibiotic.
Traditional homogeneous Fenton oxidation technology mainly applies Fe2+With H2O2Reaction is generated and can be attacked under acidic conditions
The hydroxyl radical free radical (OH) of organic pollutant makes pollutant gradually degrade or even be mineralized into H2O and CO2Process.But it is traditional
The practical application of homogeneous Fenton oxidation receives the limitation of several aspects, comprising: (1) generation of OH is limited by pH, generally
Only occur in the range that pH is 2.5 to 3.5；(2) Fe in system2+Regeneration rate it is extremely low so that the yield of OH is not high, reaction is lived
Property it is limited；(3) be also easy to produce iron hydroxide sludge settling in reaction process, degrade organic contamination while water quality can be generated it is new
Coloration and impurity pollution.
For the defect for solving conventional homogeneous Fenton, iron-based multiphase Fenton catalyst comes into being, and wherein nature is deposited extensively
Native iron mineral ferrihydrite extensive research concern is received with its unique catalysis and absorption property.Especially it can be with
It is applied in advanced oxidation system as class fenton catalyst, activates H2O2Generation OH, which has no, selectively attacks organic molecule
Make its degradation.But individual ferrihydrite is not high to the catalytic activity of pollutant in Fenton-like.Therefore, ferrihydrite is utilized
As carrier, new and effective class Fenton catalytic composite materials are constructed, the catalytic activity for effectively improving iron-based class Fenton material has
Significance.
Summary of the invention
To solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is that provide hollow ceria micro-
The preparation method of ball load ferrihydrite multiphase-fenton fenton catalyst.This method includes being done in biological template synthesis first with saccharomycete
Empty cerium dioxide nano microballoon, then pass through the surface that the precipitation method are loaded to ferrihydrite.
This method effective use is cheap and the saccharomyces cerevisiae microorganism of abundance, be prepared into active site it is more, with light
It is quick response, can effective activation H2O2The efficient class Fenton composite material (hCeO of iron-based cerium system2/fh)。
Another object of the present invention is to provide hollow cerium dioxide micro-balloons made from the above method to load ferrihydrite multiphase
Class fenton catalyst.
A further object of the present invention is to provide above-mentioned hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton Fenton catalysis
The application of agent refers specifically to the application of the degradable organic pollutant in visible light source/Fenton-like system of low energy consumption.
The object of the invention is achieved through the following technical solutions:
Hollow cerium dioxide micro-balloon loads ferrihydrite (hCeO2/ fh) multiphase-fenton fenton catalyst preparation method, including with
Lower step:
(1) saccharomycete and ceria presoma are added to the water, after mixing, alkaline matter are added and is mixed
Liquid stands aging, washs, dry, and 1~3h is then calcined at 500~700 DEG C, cooling, and it is micro- to obtain hollow cerium dioxide nano
Ball；
(2) hollow cerium dioxide nano microballoon is added to the water, ferrihydrite presoma and alkaline matter is then added, obtains
To mixed liquor, the pH of mixed liquor is adjusted to 6.0~8.0, reacts 2~4h at room temperature, is centrifuged, is washed, it is dry, obtain hCeO2/fh
Multiphase-fenton fenton catalyst；
The mass ratio of the hollow cerium dioxide nano microballoon and ferrihydrite presoma is (0.2~1): 18.16.
Step (1) described saccharomycete is preferably S. cervisiae (Saccharomyces Cerevisiae).
Step (1) described saccharomycete is added preferably in the form of saccharomycete freeze-dried powder, the saccharomycete freeze-dried powder and dioxy
The mass ratio for changing cerium precursor is preferably 0.8~1.2:1.
Step (1) the ceria presoma is preferably Ce (NO3)3·6H2O；The ceria presoma and water
Mass ratio is preferably 1:(20~30).
Concentration of step (1) the described alkaline matter in mixed liquor is preferably 6~8g/L.
Step (1) described alkaline matter is preferably NaOH, and the alkaline matter is added preferably in the form of its aqueous solution,
The mass concentration of aqueous solution is preferably 0.05~0.1g/ml.
Step (1) mixing is preferably ultrasonic mixing, and the time of the ultrasonic mixing is preferably 60~90min.
Step (1) time for standing aging is preferably 12~14h.
Step (1) alkaline matter also needs to carry out oscillation treatment after being added, and the speed of the oscillation is preferably 160~
180rpm, time are 60~90min；Ethyl alcohol and water washing 1~3 time are preferably used in the washing respectively；The condition of the drying
Preferably vacuum, 6~16h is dried at 50~100 DEG C.
Step (1) calcining carries out preferably in Muffle furnace, is warming up to 600 DEG C with the heating rate of 1 DEG C/min.
The mass ratio of step (2) the hollow cerium dioxide nano microballoon and water is preferably (0.2~1): 240.
Step (2) the ferrihydrite presoma is preferably Fe (NO3)3·9H2O。
Step (2) the ferrihydrite presoma and alkaline matter are added preferably in the form of its aqueous solution, wherein water iron
The mass ratio of solute and solvent is preferably 0.227:(1~1.2 in mine precursor water solution), the quality of alkaline substance solution is dense
Degree is preferably 0.05~0.1g/ml.
The ferrihydrite precursor water solution and alkaline substance solution are preferably added in a manner of dropwise addition simultaneously, 5~
It is dripped in 10min.The speed of agitator of the dropwise addition is 160~180rpm.
Concentration of step (2) the described alkaline matter in mixed liquor is preferably 12~14g/L.The alkaline matter is preferably
NaOH。
The oscillation rate of step (2) described reaction is preferably 160~180rmp.
Step (2) described centrifugal condition is preferably 10~15min of centrifugation under 6000~8000rpm；The wash conditions are excellent
Be selected as dispersing product in second alcohol and water respectively and being centrifuged, respectively repeatedly 1~3 time, wherein centrifugal condition be preferably 6000~
8000rpm is centrifuged 10~15min；The drying is preferably freeze-dried, dry 24 at preferably -50~50 DEG C of condition~
36h。
Hollow cerium dioxide micro-balloon made from the above method loads ferrihydrite multiphase-fenton fenton catalyst.
The hCeO2In/fh multiphase-fenton fenton catalyst, the mass ratio of hollow cerium dioxide nano microballoon and ferrihydrite is
(0.05~0.25): 1.
The hollow cerium dioxide micro-balloon loads ferrihydrite multiphase-fenton fenton catalyst, is in nothing using ferrihydrite as carrier
Shape shape, and hollow ceria is in hollow porous micro sphere shape, and is tightly embedded intp ferrihydrite surface.
Above-mentioned hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst is in light-Fenton degradation of organic substances field
In application.
The application is preferably the organic matter removed in waste water.
Organic matter in the removal waste water, comprising the following steps: by hCeO2/ fh multiphase-fenton fenton catalyst and waste water
It is uniformly mixed, absorption is vibrated under the conditions of being protected from light, after reaching adsorption equilibrium, H is added2O2, light-sweet smell is carried out under visible light source
Pause catalytic degradation, completes the degradation treatment to useless Organic substance in water.
The hCeO2Dosage of/fh multiphase-fenton the fenton catalyst in waste water is preferably 0.2~1.2g/L；The H2O2
Concentration in waste water is preferably 20~100mmol/L.
The organic matter is preferably 10~30mg/L in the concentration of waste water；More preferably 10~20mg/L.
The organic matter be preferably antibiotic, tetrabromobisphenol A (TBBPA), rhodamine B (RhB) and 2,4 dichloro phenol (2,
At least one of 4-DCP)；The antibiotic is preferably tetracycline (TC).
The light-Fenton catalytic degradation tetrabromobisphenol A, rhodamine B and 2,4 dichloro phenol is preferably in the pH of waste water itself
(wherein the pH of the waste water containing tetrabromobisphenol A is about 6.43, and the pH of the waste water containing rhodamine B is about 5.62, the chlorophenesic acid containing 2,4-
The pH of waste water be about 7.76) under the conditions of carry out；Light-Fenton catalytic degradation antibiotic is preferably under conditions of the pH of waste water is 4.0
It carries out.
The light-Fenton catalytic degradation preferably carries out under the conditions of the low energy consumption LED lamplight that power is 5W is shone.
The light-Fenton catalytic degradation time is preferably 10-120min.
Compared with prior art, the present invention has the following advantages that and benefit effect:
1, the present invention provides a kind of hollow cerium dioxide micro-balloons to load ferrihydrite (hCeO2/ fh) catalysis of multiphase-fenton Fenton
Agent is made of hollow cerium dioxide nano microballoon and ferrihydrite, wherein hollow cerium dioxide nano microballoon is in cellular, and close
Ground is embedded into unbodied ferrihydrite surface.Ferrihydrite itself is as iron series compound, surface Fe rich in3+And hydroxyl
Free group deactivates H for it as class fenton catalyst2O2It provides potentially possible.Hollow ceria as semiconductor,
It can generate photo-generated carrier under the conditions of visible light source, and photo-generated carrier is transmitted to ferrihydrite surface in close contact therewith
Ferrihydrite can be effectively facilitated in Fenton-like system to H2O2Active rate, to improve the yield and pollutant of active group
Degradation efficiency.Of the invention hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst is degradable different types of to be had
Machine pollutant has the characteristics that degradation rate is fast, removal efficiency is high, easy to operate, low in cost, and does not generate any secondary dirt
Dye has environmental benefit.
2, the present invention is effectively utilized waste microbial matter S. cervisiae as biological template, and makes it in hot environment
Under be gasificated into CO2, so that ceria be promoted to form the nanosphere of porous structure, be conducive to visible absorption and photoproduction current-carrying
The transmission effects of son.Cerium dioxide nano micro-ball load shows its surface also rough porous to ferrihydrite surface
Shape, at the same be also beneficial to pollutant the mass transfer expanding of composite material surface and with the contact action of active group.
3, hollow cerium dioxide micro-balloon of the present invention loads ferrihydrite multiphase-fenton fenton catalyst, using simple high temperature
Calcination method and in situ Precipitation are made, and do not generate secondary pollution in reaction condition easy-regulating, easy to operate, preparation process, have
The advantages that environmentally protective.
4, hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst produced by the present invention can be in low energy consumption
It can produce photohole and light induced electron under LED visible light illumination condition, and be further transferred to ferrihydrite surface, expand water iron
Catalytic applications of the ferro element in Fenton-like in mine, are effectively treated typical environment pollution antibiotic waste water and other are typical
Organic (fire retardant, dyestuff, phenol) pollutant effluents has easy to operate, at low cost, degradation property is excellent, processing is rapid etc.
Characteristic；It is wherein 99.7% to the most degradation efficiency of tetracycline, mineralization rate 71.2%, to the most degradation of tetrabromobisphenol A
Efficiency is 100%, and the most degradation efficiency to rhodamine B is 85.2%, and the most degradation efficiency to 2,4- chlorophenesic acid is
81.8%, and show good stability.Therefore, hCeO of the present invention2/ fh multiphase-fenton fenton catalyst can answer extensively
For the purification and harmless treatment of organic polluting water, while to the catalyst for developing microorganism shuttering supporting, iron-based multiphase
Class fenton catalyst and environmental contaminants processing are of great significance.
Detailed description of the invention
Fig. 1 is that hollow cerium dioxide micro-balloon made from the embodiment of the present invention 1 loads ferrihydrite multiphase-fenton fenton catalyst (5-
hCeO2/fh、15-hCeO2/fh、25-hCeO2/ fh), it is hollow made from pure water iron ore (fh) made from comparative example 1 and embodiment 1
Cerium dioxide nano microballoon (hCeO2) X-ray diffractogram.
Fig. 2 is that hollow cerium dioxide micro-balloon made from the embodiment of the present invention 1 loads ferrihydrite multiphase-fenton fenton catalyst
(25-hCeO2/ fh) scanning electron microscope (SEM) photograph, amplification factor be 4000 times.
Fig. 3 is that the hollow cerium dioxide micro-balloon prepared in embodiment 1 loads ferrihydrite multiphase-fenton fenton catalyst (15-
hCeO2/ fh) the full spectrogram of x-ray photoelectron.
Fig. 4 is hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst obtained in the embodiment of the present invention 1
(5-hCeO2/fh、15-hCeO2/fh、25-hCeO2/ fh), made in pure water iron ore (fh) obtained and embodiment 1 in comparative example 1
The hollow cerium dioxide nano microballoon (hCeO obtained2) ultraviolet-visible light diffusing reflection abosrption spectrogram.
Fig. 5 is that hollow cerium dioxide micro-balloon made from the embodiment of the present invention 1 loads ferrihydrite multiphase-fenton fenton catalyst (5-
hCeO2/fh、10-hCeO2/fh、15-hCeO2/fh、20-hCeO2/fh、25-hCeO2/ fh) and comparative example 1 made from pure water iron
Mine (fh) is in light-Fenton-like system to the degradation effect figure of tetracycline.
Fig. 6 is that the cerium dioxide micro-balloon of different amounts loads the ferrihydrite multiphase-fenton fenton catalyst (15- in embodiment 1
hCeO2/ fh) to light-Fenton catalytic degradation curve graph of tetracycline.
Fig. 7 is cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst (15-hCeO obtained in embodiment 12/
Fh) to the light of tetracycline-Fenton catalytic degradation curve graph under the conditions of different concentration of hydrogen peroxide.
Fig. 8 is cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst (15-hCeO obtained in embodiment 12/
Fh) under condition of different pH in light-Fenton-like system to the degradation curve figure of tetracycline.
Fig. 9 is cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst (15-hCeO obtained in embodiment 12/
Fh) to the light of different type organic pollutant-Fenton catalytic degradation effect curve graph.
Figure 10 is cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst (15- obtained in the embodiment of the present invention 1
hCeO2/ fh) and comparative example 1 made from pure water iron ore during light-Fenton catalytic degradation to the mineralization rate curve of tetracycline
Figure.
Specific embodiment
Below with reference to specific embodiment and Figure of description, the present invention is described in further detail, but not therefore
Limit embodiments of the present invention.
S. cervisiae used in the embodiment of the present invention (Saccharomyces Cerevisiae) purchase is general in China
Logical Culture Collection, deposit number are CGMCC 2.3849.
Embodiment 1
A kind of hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst, the catalyst is by following methods system
It is standby:
(1) 1g S. cervisiae dry bacterium powder and 1g Ce (NO are taken3)3·6H2O is dissolved in 20mL deionized water, room temperature condition
Lower ultrasound 60min, obtains mixed liquor.10mL NaOH aqueous solution (wherein containing 0.2g NaOH) is added dropwise into mixed liquor,
1h is vibrated in 160rpm at room temperature, is collected by centrifugation after static aging 12h at room temperature, and with ethanol washing 1 time, deionization
Water washing 2 times.Obtained sediment takes out after 80 DEG C of vacuum drying 6h, is put into Muffle furnace, is heated up with the rate of 1 DEG C/min
To 600 DEG C, and under 600 DEG C of atmosphere, Temperature fall is cooling after calcining 2h, obtains hollow cerium dioxide nano microballoon (hCeO2)。
(2) the hollow titanium dioxide prepared in 0.025g, 0.05g, 0.075g, 0.1g and 0.125g step (1) is taken respectively
Cerium nanosphere is dissolved in 30mL deionized water, is defined as solution A.Take 2.27g Fe (NO3)3·9H2O grain dissolution is in 10mL
In deionized water, it is defined as B solution.It takes 0.674g NaOH grain dissolution in 10mL deionized water, is defined as C solution.By B
Solution and C solution are added dropwise in solution A simultaneously at 160rpm, and control adds in 5min, and at room temperature will
The pH of mixed solution is adjusted to 7.0+_0.1, later the oscillating reactions 3h then at 160rpm and under room temperature.Then in 4000rpm item
It is centrifugated under part, and after being washed with deionized 2 times, collects sediment, be freeze-dried after 12h under the conditions of -50 DEG C to obtain the final product
Ferrihydrite (hCeO is loaded to hollow cerium dioxide micro-balloon2/ fh) multiphase-fenton fenton catalyst, and according to hollow cerium dioxide nano
The sequence of additional amount 0.025g, 0.05g, 0.075g, 0.1g, 0.125g of microballoon, are denoted as 5-hCeO for product respectively2/fh、
10-hCeO2/fh、15-hCeO2/fh、20-hCeO2/ fh and 25-hCeO2/fh。
Comparative example 1
A kind of preparation of pure water iron ore (fh), comprising the following steps:
By 2.27g Fe (NO3)3·9H2O is dissolved in 10mL deionized water, is defined as B solution, takes 0.674g NaOH
Grain is dissolved in 10mL deionized water, is defined as C solution.C solution is added dropwise in B solution, and at room temperature will
The pH of mixed solution is adjusted to 7.0+_0.1, later the oscillating reactions 3h then at 160rpm and under room temperature.Under the conditions of 4000rpm
Sediment is collected by centrifugation, obtains pure water iron ore (fh) material after 12h is freeze-dried under the conditions of -50 DEG C.
Ferrihydrite multiphase-fenton fenton catalyst (5- is loaded to the hollow cerium dioxide micro-balloon prepared in the embodiment of the present invention 1
hCeO2/fh、15-hCeO2/fh、25-hCeO2/ fh) and hollow cerium dioxide nano microballoon (hCeO2) and comparative example 1 in make
Pure water iron ore (fh) material obtained does X-ray diffraction phenetic analysis, as a result as shown in Figure 1, hCeO2Respectively 2 θ=28.6 °,
There is diffraction maximum in 33.2 °, 47.8 °, 56.3 °, 58.7 °, 69.4 °, 76.7 ° and 88.4 ° of position, respectively corresponds ceria firefly
(111), (200), (220), (311), (222) in stone structure, (400), (331) and (422) crystal face (JCPDS NO.50-
1275).And fh is 35 ° and 63 ° or so in the angle of diffraction and observes diffraction maximum, this is consistent with two wide reflection peaks of ferrihydrite.?
The cerium dioxide micro-balloon of three kinds of different proportions loads ferrihydrite multiphase-fenton fenton catalyst (5-hCeO2/fh、15-hCeO2/fh、
25-hCeO2/ fh) X-ray diffractogram in, contain hCeO2With the diffraction maximum of fh, this illustrates hCeO2Successfully load to water
On iron ore, and hCeO2Incorporation on fh knot be configured without influence.
Ferrihydrite (25-hCeO is loaded to hollow cerium dioxide micro-balloon made from the embodiment of the present invention 12/ fh) multiphase-fenton sweet smell
The catalyst that pauses is scanned electron microscope analysis, as a result as shown in Figure 2.As shown in Figure 2, hollow cerium dioxide micro-balloon prepared by the present invention
Load ferrihydrite (25-hCeO2/ fh) in multiphase-fenton fenton catalyst, surface is presented inhomogenous roughened state, and with being permitted
More gaps, this explanation have the hCeO of many pore structures2The surface fh is successfully loaded to, so that rough porous is presented in its surface
Shape, 25-hCeO2The scanning electron microscope analysis result of/fh is consistent with X-ray diffraction phenetic analysis result.
Ferrihydrite (15-hCeO is loaded to hollow cerium dioxide micro-balloon made from the embodiment of the present invention 12/ fh) multiphase-fenton sweet smell
The catalyst that pauses carries out x-ray photoelectron spectroscopy, as a result as shown in Figure 3.From the figure 3, it may be seen that hollow ceria prepared by the present invention
Micro-ball load ferrihydrite (15-hCeO2/ fh) tetra- kinds of elements of C, Fe, O, Ce in multiphase-fenton fenton catalyst, remove these four elements
Outside, occur without other impurity peaks, illustrate no impurity incorporation.Wherein the region Fe can be divided into Fe 2p1/2 and Fe 2p3/2 again
Two characteristic peaks.Result above shows 15-hCeO2/ fh multiphase-fenton fenton catalyst successfully synthesizes.
Ferrihydrite multiphase-fenton fenton catalyst (5- is loaded to the hollow cerium dioxide micro-balloon prepared in the embodiment of the present invention 1
hCeO2/ fh, 15-hCeO2/ fh, 25-hCeO2/ fh) and hollow cerium dioxide nano microballoon (hCeO2) and comparative example 1 in make
Pure water iron ore (fh) material obtained does ultraviolet-visible light diffusing reflection absorption spectroanalysis, as a result as shown in Figure 4.As shown in Figure 4,
Hollow cerium dioxide nano microballoon (hCeO2) in ultraviolet and visibility region biggish light absorption is shown, the extinction at 470nm
Degree strongly reduces.And pure water iron ore shows apparent adsorption capacity in the area Quan Pu.Compared with fh, hollow cerium dioxide micro-balloon is negative
Carry ferrihydrite multiphase-fenton fenton catalyst (5-hCeO2/ fh, 15-hCeO2/ fh, 25-hCeO2/ fh) visible light region light inhale
Receiving intensity is enhanced, wherein 15-hCeO2/ fh shows best red shift in all samples, illustrates in mineral in load
Empty cerium dioxide nano microballoon can promote its absorption to solar energy.
Embodiment 2
Investigate different hCeO2The hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst of doping is to antibiosis
The influence of the light of plain tetracycline wastewater-Fenton catalytic degradation.
By the hollow cerium dioxide micro-balloon prepared in the embodiment of the present invention 1 load ferrihydrite multiphase-fenton fenton catalyst and
Pure water iron ore (fh) material obtained in comparative example 1 is applied to tetracycline wastewater light-Fenton catalytic degradation processing, and step is such as
Under: tetracycline Stock concentrations are diluted to 20mg/L with deionized water, with the H of 1.0mol/L2SO4Four are adjusted with NaOH solution
Ring element solution initial pH value is 4.0.The 5-hCeO in 20mg embodiment 1 is weighed respectively2/fh、10-hCeO2/fh、15-hCeO2/
fh、20-hCeO2/fh、25-hCeO2It is 50mL, concentration that fh in/fh multiphase-fenton fenton catalyst and comparative example 1, which is added to volume,
First to vibrate 1h under conditions of being protected from light and reaching adsorption equilibrium, add in the tetracycline simulated wastewater solution of 20mg/L
A certain amount of hydrogen peroxide makes its ultimate density 50mmol/L in tetracycline simulated wastewater solution, opens LED light, can
(λ > 420nm) carries out light-Fenton catalytic degradation reaction under light-exposed irradiation condition, reaction time 60min, in reaction process respectively
0.22 μm of filter membrane was sampled in 2min, 5min, 10min, 20min, 40min and 60min to be separated by solid-liquid separation, and utilized ultraviolet spectrometry light
Degree meter measures the concentration of remaining antibiotic tetracycline in filtrate at 357nm, calculates the residual rate of tetracycline.In this embodiment,
It is arranged 1 and tetracycline (the wherein concentration of hydrogen peroxide that any catalyst, volume 50mL, concentration are 20mg/L is not added
The residual rate for measuring and calculating tetracycline as a control group, under the same terms for 50mmol/L), is contrasted for blank.It is different
hCeO2Adulterate than load water body mine multiphase-fenton fenton catalyst in light-Fenton-like system to the degradation curve figure of tetracycline such as
Shown in Fig. 5.As shown in Figure 5, tetracycline degradation rate under conditions of only being shone by visible light and hydrogen peroxide is very low, only faint
Degradation reaction occurs.To the degradation of tetracycline, also remnants 50.83%, degradation efficiency are pure fh in system after 60min
49.17%.Using 5-hCeO2/fh、10-hCeO2/fh、15-hCeO2/fh、20-hCeO2/fh、25-hCeO2/ fh multiphase-fenton is fragrant
Catalyst degrades after 60min to tetracycline in light-Fenton-like system, in system the residual rate of tetracycline be respectively 35.62%,
20.2%, 7.39%, 9.78% and 12.36%；Corresponding tetracycline degradation rate is respectively 64.38%, 79.80%,
92.61%, 90.22 and 87.64%.Illustrate that the doping of hollow cerium dioxide nano microballoon can effectively facilitate ferrihydrite material in light
To the degradation of antibiotic pollution in Fenton-like system.
Embodiment 3
Different hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst dosages are investigated to antibiotic tetracycline
The influence of the light of waste water-Fenton catalytic degradation.
The hollow cerium dioxide micro-balloon prepared in the embodiment of the present invention 1 is loaded into ferrihydrite multiphase-fenton fenton catalyst (15-
hCeO2/ fh) it is applied to tetracycline wastewater light-Fenton catalytic degradation processing, its step are as follows: being stored up tetracycline with deionized water
Standby liquid concentration dilution is to 20mg/L, with the H of 1.0mol/L2SO4Adjusting tetracycline initial pH value with NaOH solution is 4.0.Point
Also known as take the 15-hCeO in 10mg, 20mg, 40mg, 60mg embodiment 12/ fh multiphase-fenton fenton catalyst is added to volume and is
In 50mL, the tetracycline simulated wastewater solution that concentration is 20mg/L, 1h is first vibrated under conditions of being protected from light, and to reach absorption flat
Weighing apparatus, adding a certain amount of hydrogen peroxide makes its ultimate density 50mmol/L in tetracycline simulated wastewater solution, opens
LED light, (λ > 420nm) carries out light-Fenton catalytic degradation reaction, reaction time 60min, reaction under the conditions of can irradiate light
0.22 μm of filter membrane was sampled respectively at 2min, 5min, 10min, 20min, 40min and 60min in the process to be separated by solid-liquid separation, and was utilized
Ultraviolet specrophotometer measures the concentration of remaining antibiotic tetracycline in filtrate at 357nm, calculates the residual rate of tetracycline.No
With the 15-hCeO of catalyst amount2/ fh multiphase-fenton fenton catalyst is as shown in Figure 6 to the degradation curve figure of tetracycline.By Fig. 6
It is found that using the 15-hCeO of 0.2g/L, 0.4g/L, 0.8g/L and 1.2g/L2/ fh multiphase-fenton fenton catalyst is in light-Fenton body
In system to tetracycline degrade 60min after, the residual rate of tetracycline is respectively 15.06%, 7.39%, 2.93% and in system
1.25%；Corresponding tetracycline degradation rate is respectively 84.94%, 92.61%, 97.17% and 98.75%.The degradation of tetracycline
Rate is gradually increased with the increase of catalyst dosage, and usually, catalyst is more, H2O2The active site of decomposition is more, from
And promote the degradation of organic matter.
Embodiment 4
It investigates different concentration of hydrogen peroxide and ferrihydrite multiphase-fenton fenton catalyst light-sweet smell is loaded to hollow cerium dioxide micro-balloon
The influence of catalytic degradation antibiotic tetracycline.
The hollow cerium dioxide micro-balloon prepared in the embodiment of the present invention 1 is loaded into ferrihydrite multiphase-fenton fenton catalyst (15-
hCeO2/ fh) it is applied to tetracycline wastewater light-Fenton catalytic degradation processing, its step are as follows: being stored up tetracycline with deionized water
Standby liquid concentration dilution is to 20mg/L, with the H of 1.0mol/L2SO4Adjusting tetracycline initial pH value with NaOH solution is 4.0.It takes
15-hCeO in 20mg embodiment 12/ fh multiphase-fenton fenton catalyst is added to the Fourth Ring that volume is 50mL, concentration is 20mg/L
In plain simulated wastewater solution, 1h is first vibrated under conditions of being protected from light and reaches adsorption equilibrium, adds a certain amount of peroxidating
Hydrogen make its ultimate density in tetracycline simulated wastewater solution be divided into 20mmol/L, 50mmol/L, 100mmol/L and
150mmol/L opens LED light, and (λ > 420nm) carries out light-Fenton catalytic degradation reaction under the conditions of can irradiate light, when reaction
Between be 60min, sampled 0.22 μm of filter membrane respectively at 2min, 5min, 10min, 20min, 40min and 60min in reaction process
It is separated by solid-liquid separation, and measures the concentration of remaining antibiotic tetracycline in filtrate at 357nm using ultraviolet specrophotometer, calculate four
The residual rate of ring element.15-hCeO under the conditions of different concentration of hydrogen peroxide2Drop of/fh multiphase-fenton the fenton catalyst to tetracycline
Solution curve figure is as shown in Figure 7.As shown in Figure 7, the concentration of hydrogen peroxide be respectively 20mmol/L, 50mmol/L, 100mmol/L and
The tetracycline simulated wastewater solution of 150mmol/L is through 15-hCeO2After/fh light-Fenton catalytic degradation 60min, tetracycline in system
Residual rate be respectively 12.64%, 7.39%, 6.59% and 8.68%.Corresponding tetracycline degradation rate is respectively 87.36%,
92.61%, 93.41% and 91.32%.The degradation rate of tetracycline is first increased with the concentration of hydrogen peroxide to be reduced afterwards, and degradation rate exists
The concentration of hydrogen peroxide reaches maximum when being 100mmol/L.The concentration of hydrogen peroxide is more than or less than 100mmol/L constantly, tetracycline
Degradation efficiency all gradually reduce.
Embodiment 5
Hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst is investigated at different pH to antibiotic Fourth Ring
The influence of the light of plain waste water-Fenton catalytic degradation.
The hollow cerium dioxide micro-balloon prepared in the embodiment of the present invention 1 is loaded into ferrihydrite multiphase-fenton fenton catalyst (15-
hCeO2/ fh) it is applied to tetracycline wastewater light-Fenton catalytic degradation processing, its step are as follows: being stored up tetracycline with deionized water
Standby liquid concentration dilution is to 20mg/L, with the H of 1.0mol/L2SO4Tetracycline initial pH value is divided into NaOH solution and being adjusted to
3.0,4.0,5.0,6.0,7.0,8.0 and 9.0.Take the 15-hCeO in 20mg embodiment 12/ fh multiphase-fenton fenton catalyst is added
Into the tetracycline simulated wastewater solution that volume is 50mL, concentration is 20mg/L, first vibrating 1h under conditions of being protected from light reaches it
To adsorption equilibrium, adding a certain amount of hydrogen peroxide makes its ultimate density in tetracycline simulated wastewater solution
50mmol/L opens LED light, and (λ > 420nm) carries out light-Fenton catalytic degradation reaction under the conditions of can irradiate light, when reaction
Between be 60min, sampled 0.22 μm of filter membrane respectively at 2min, 5min, 10min, 20min, 40min and 60min in reaction process
It is separated by solid-liquid separation, and measures the concentration of remaining antibiotic tetracycline in filtrate at 357nm using ultraviolet specrophotometer, calculate four
The residual rate of ring element.15-hCeO under condition of different pH2The degradation curve figure such as Fig. 8 of/fh multiphase-fenton fenton catalyst to tetracycline
It is shown.As shown in Figure 8, when pH is respectively 3.0,4.0,5.0,6.0,7.0,8.0 and 9.0 in system, 15-hCeO2/ fh exists
Degrade after 60min in light-Fenton-like system to tetracycline, in system the residual rate of tetracycline be respectively 10.62%, 7.39%,
8.62%, 11.26%, 10.91%, 12.39% and 8.61%.Corresponding tetracycline degradation efficiency is respectively 89.38%,
92.61%, 91.38%, 88.74%, 89.09%, 87.61% and 91.39%.The result shows that solution ph is raised to from 3.0
When 4.0, tetracycline degradation rate is improved, but when pH is further increased to neutral and alkalinity, the degradation efficiency of tetracycline is reduced.
Embodiment 6
Investigate the hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst prepared in the embodiment of the present invention 1
(15-hCeO2/ fh) in light-Fenton-like system to the degradation efficiency of different pollutants.
The hollow cerium dioxide micro-balloon prepared in the embodiment of the present invention 1 is loaded into ferrihydrite multiphase-fenton fenton catalyst (15-
hCeO2/ fh) it is applied to waste water light-Fenton degradation treatment of different organic polluting waters, its step are as follows: taking the concentration to be respectively
The rhodamine B of 10mg/L, tetrabromobisphenol A, 2,4- chlorophenesic acid and 20mg/L tetracycline waste water solution, in rhodamine B, tetrabromo
Bisphenol-A, 2,4- chlorophenesic acid waste water solution nature pH under the conditions of and the waste water solution pH of tetracycline be 4.0 under conditions of,
The 15-hCeO in 20mg embodiment 1 is taken respectively2/ fh multiphase-fenton fenton catalyst is added in the above-mentioned four kinds of solution of 50mL, is being kept away
1h is first vibrated under conditions of light, adding a certain amount of hydrogen peroxide makes its ultimate density in four kinds of waste water solutions be
50mmol/L opens LED light, and (λ > 420nm) carries out light-Fenton catalytic degradation reaction under the conditions of can irradiate light, when reaction
Between be 120min, taken respectively at 2min, 5min, 10min, 20min, 40min, 90min, 60min and 120min in reaction process
Sample is crossed 0.22 μm of filter membrane and is separated by solid-liquid separation.Rhodamine B, tetracycline wastewater solution using ultraviolet specrophotometer respectively 567nm,
The concentration of remaining rhodamine B in filtrate, tetracycline is measured at 357nm, 2,4- chlorophenesic acids and tetrabromobisphenol A waste water solution are sharp
The concentration of residue 2,4- chlorophenesic acid and tetrabromobisphenol A in filtrate, liquid chromatogram are detected and calculated with high performance liquid chromatography
Column is C18 (150 4.6 μm of μ ms, 5 μm, Agilent, USA), wherein the testing conditions of 2,4- chlorophenesic acids are Detection wavelength
254nm, 30 DEG C of column temperature, mobile phase is methanol: distilled water=60:40 (v/v), flow velocity 0.8mL/min, 20 μ L of sample volume；Tetrabromo
The testing conditions of bisphenol-A are Detection wavelength 209nm, and 30 DEG C of column temperature, mobile phase is methanol: distilled water=85:15 (v/v), flow velocity
1.0mL/min, 20 μ L of sample volume.The residual rate of each organic pollutant is calculated again.15-hCeO2/ fh multiphase-fenton fenton catalyst pair
The degradation curve figure of different pollutants is as shown in Figure 9.As shown in Figure 9,15-hCeO2/ fh is in light-Fenton-like system to rhodamine
B, tetrabromobisphenol A and 2,4- chlorophenesic acid are degraded after 120min, rhodamine B, tetrabromobisphenol A and 2 in system, 4- chlorophenesic acid
Residual rate is respectively 12.71%, 0% and 18.29%.The degradation of corresponding rhodamine B, tetrabromobisphenol A and 2,4 dichloro phenol
Efficiency is respectively 87.29%, 100% and 81.71%, and the degradation rate of tetrabromobisphenol A just reaches 100% in 20min.As a result table
Bright, the hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst prepared in the embodiment of the present invention 1 is to organic contamination
The degradation of object has broad spectrum activity, and degradation efficiency is higher.
Embodiment 7
Investigate the hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst prepared in the embodiment of the present invention 1
(15-hCeO2/ fh) and comparative example 1 in the pure water iron ore (fh) for preparing in light-Fenton-like system to the mineralization rate of tetracycline.
Probe into the hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst prepared in the embodiment of the present invention 1
(15-hCeO2/ fh) and comparative example 1 in the pure water iron ore (fh) for preparing to the mineralization rate of tetracycline, its step are as follows: spend from
Tetracycline Stock concentrations are diluted to 20mg/L by sub- water, with the H of 1.0mol/L2SO4It is with NaOH solution that tetracycline is initial
PH value is adjusted to 4.0, obtains tetracycline simulated wastewater solution.The 15-hCeO in 20mg embodiment 1 is taken respectively2/ fh multiphase-fenton is fragrant
It is useless that pure water iron ore (fh) in catalyst and comparative example 1 is added to the tetracycline simulation that volume is 50mL, concentration is 20mg/L
In aqueous solution, first vibrate 1h under conditions of being protected from light and reach adsorption equilibrium, add a certain amount of hydrogen peroxide make its
Ultimate density in tetracycline simulated wastewater solution is 50mmol/L, opens LED light, under the conditions of can irradiate light (λ >
420nm) carry out light-Fenton catalytic degradation reaction, reaction time 60min, in reaction process respectively at 2min, 5min,
10min, 20min, 40min and 60min sampled 0.22 μm of filter membrane and were separated by solid-liquid separation, and were detected immediately with total organic carbon analyzer.15-
hCeO2/ fh multiphase-fenton fenton catalyst and pure water iron ore (fh) material are as shown in Figure 10 to the degradation curve figure of tetracycline.By scheming
10 it is found that 15-hCeO2/ fh multiphase-fenton fenton catalyst is apparently higher than pure fh to the mineralization rate of tetracycline, shows the two reactions
Tetracycline can be oxidized to the ability of inorganic carbon, and hCeO by system2Presence can further promote the mineralising of target antibiotic.
In conclusion the present invention efficiently uses cheap and abundance saccharomyces cerevisiae as biological template, successfully synthesize
Hollow cerium dioxide nano microballoon more than active site, and the table of ferrihydrite is further supported on by Situ Hydrothermal method
Face obtains newly synthesized having more active sites, Gao Guangmin response intensity and can effective activation H2O2The efficient class of iron-based cerium system it is fragrant
Pause catalyst.The catalyst preparation process is simple, without secondary pollution, environmental benefit is good.It can effective catalytic degradation antibiotic, dye
The organic pollutants such as material, fire retardant have certain degradation broad spectrum activity, and degradation rate is high, degradation process is easy to operate, it is environmentally friendly not
Generate secondary pollution.The present invention is of great significance to efficient iron-based class Fenton heterogeneous catalyst is developed.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. the preparation method of hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst, which is characterized in that including with
Lower step:
(1) saccharomycete and ceria presoma are added to the water, after mixing, alkaline matter are added and obtains mixed liquor,
Aging is stood, is washed, it is dry, 1~3h is then calcined at 500~700 DEG C, it is cooling, obtain hollow cerium dioxide nano microballoon；
(2) hollow cerium dioxide nano microballoon is added to the water, ferrihydrite presoma and alkaline matter is then added, is mixed
Liquid is closed, the pH of mixed liquor is adjusted to 6.0~8.0, reacts 2~4h at room temperature, is centrifuged, is washed, it is dry, obtain hCeO2/ fh multiphase
Class fenton catalyst；
The mass ratio of ferrihydrite presoma in the hollow cerium dioxide nano microballoon and ferrihydrite precursor solution is (0.2
~1): 18.16.
2. the preparation method of hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst according to claim 1,
It is characterized in that, step (1) saccharomycete is S. cervisiae；The saccharomycete is added in the form of saccharomycete freeze-dried powder,
The mass ratio of the saccharomycete freeze-dried powder and ceria presoma is 0.8~1.2:1.
3. the preparation side of hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst according to claim 1 or claim 2
Method, which is characterized in that concentration of step (1) the described alkaline matter in mixed liquor is 6~8g/L；Step (2) described basic species
Concentration of the matter in mixed liquor is 12~14g/L.
4. the preparation side of hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst according to claim 1 or claim 2
Method, which is characterized in that step (1) the ceria presoma is Ce (NO3)3·6H2O；The ceria presoma and water
Mass ratio be 1:(20~30)；
Step (2) the ferrihydrite presoma is Fe (NO3)3·9H2O；The quality of hollow the cerium dioxide nano microballoon and water
Than for (0.2~1): 240.
5. the preparation method of hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst according to claim 4,
It is characterized in that, step (1) alkaline matter is NaOH, the alkaline matter is added in the form of its aqueous solution, water-soluble
The mass concentration of liquid is 0.05~0.1g/ml；
Step (2) alkaline matter is NaOH；The ferrihydrite presoma and alkaline matter are added in the form of its aqueous solution
Enter, wherein the mass ratio of solute and solvent is 0.227:(1~1.2 in ferrihydrite precursor water solution), alkaline substance solution
Mass concentration be 0.05~0.1g/ml；
The ferrihydrite precursor water solution and alkaline substance solution in a manner of being added dropwise while being added, and drip in 5~10min
It adds.
6. the preparation method of hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst according to claim 3,
It is characterized in that, step (1) time for standing aging is 12~14h；It also needs to be vibrated after the addition alkaline matter
Processing, the speed of the oscillation are 160~180rpm, and the time is 60~90min.
7. the preparation side of hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst according to claim 1 or claim 2
Method, which is characterized in that step (1) is described to be mixed into ultrasonic mixing, and the time of the ultrasonic mixing is 60~90min；It is described to wash
It washs to use ethyl alcohol and water washing 1~3 time respectively；The condition of the drying is vacuum, dries 6~16h at 50~100 DEG C；
The oscillation rate of step (2) described reaction is 160~180rmp；The centrifugal condition is to be centrifuged under 6000~8000rpm
10~15min；The wash conditions are to disperse product in second alcohol and water respectively and be centrifuged, respectively repeatedly 1~3 time, wherein from
Heart condition is that 6000~8000rpm is centrifuged 10~15min；The drying is freeze-drying, and condition is dry at -50~50 DEG C
24~36h.
8. hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton Fenton made from any one of claim 1~7 the method is urged
Agent.
9. hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst described in claim 8 has in light-Fenton degradation
Application in machine object field, which is characterized in that the application is the organic matter removed in waste water.
10. hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst is in light-Fenton drop according to claim 9
Solve the application in organic matter field, which comprises the following steps: by hCeO2/ fh multiphase-fenton fenton catalyst and waste water
It is uniformly mixed, absorption is vibrated under the conditions of being protected from light, after reaching adsorption equilibrium, H is added2O2, light-sweet smell is carried out under visible light source
Pause catalytic degradation, completes the degradation treatment to useless Organic substance in water；
The hCeO2Dosage of/fh multiphase-fenton the fenton catalyst in waste water is 0.2~1.2g/L；The H2O2In waste water
Concentration be 20~100mmol/L；The organic matter is in antibiotic, tetrabromobisphenol A, rhodamine B and 2,4 dichloro phenol
It is at least one；The antibiotic is tetracycline；
The organic matter is 10~30mg/L in the concentration of waste water；The light-Fenton catalytic degradation time is 10~120min；
It is carried out under the conditions of the low energy consumption LED lamplight that power is 5W is shone.
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