CN109225344A - Complex light fenton catalyst and its preparation method and application for dyeing waste water of degrading - Google Patents
Complex light fenton catalyst and its preparation method and application for dyeing waste water of degrading Download PDFInfo
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- CN109225344A CN109225344A CN201811242818.9A CN201811242818A CN109225344A CN 109225344 A CN109225344 A CN 109225344A CN 201811242818 A CN201811242818 A CN 201811242818A CN 109225344 A CN109225344 A CN 109225344A
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- waste water
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- dyeing waste
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000004043 dyeing Methods 0.000 title claims abstract description 34
- 239000002351 wastewater Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000000593 degrading effect Effects 0.000 title claims abstract description 20
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 230000015556 catabolic process Effects 0.000 claims abstract description 9
- 238000006731 degradation reaction Methods 0.000 claims abstract description 9
- 230000008901 benefit Effects 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 25
- 239000002077 nanosphere Substances 0.000 claims description 24
- 239000013049 sediment Substances 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 238000005516 engineering process Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 12
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 claims description 10
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 239000010410 layer Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000004005 microsphere Substances 0.000 claims description 7
- 150000002823 nitrates Chemical class 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 5
- 239000000975 dye Substances 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- -1 Ethyl alcohol Chemical compound 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- VHKFFPOTSWQHPK-UHFFFAOYSA-N C(C)O.C1(=CC(=CC(=C1)C(=O)O)C(=O)O)C(=O)O Chemical compound C(C)O.C1(=CC(=CC(=C1)C(=O)O)C(=O)O)C(=O)O VHKFFPOTSWQHPK-UHFFFAOYSA-N 0.000 claims 1
- 239000011258 core-shell material Substances 0.000 claims 1
- BHCKXCJXVYHWBT-UHFFFAOYSA-L [O-]C(C1=CC(S([O-])(=O)=O)=CC=C1O)=O.[Fe+3] Chemical compound [O-]C(C1=CC(S([O-])(=O)=O)=CC=C1O)=O.[Fe+3] BHCKXCJXVYHWBT-UHFFFAOYSA-L 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000005286 illumination Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 34
- 239000002957 persistent organic pollutant Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000052 vinegar Substances 0.000 description 4
- 235000021419 vinegar Nutrition 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- GJROJDDFCYSVGK-UHFFFAOYSA-N C(C)O.C(C)(=S)O Chemical compound C(C)O.C(C)(=S)O GJROJDDFCYSVGK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- 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
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- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The present invention discloses a kind of complex light fenton catalyst and its preparation method and application for dyeing waste water of degrading, and complex light fenton catalyst includes core/shell type Fe3O4@MOF magnetic carrier and core/shell type Fe3O45-sulphosalicylic acid iron (III) layer loaded on@MOF magnetic carrier.Compared with prior art, the light fenton catalyst for the degradation dyeing waste water that the present invention is prepared has visible light-responded wide frequency range, light conversion efficiency is high, the pH value of solution scope of application is wide, selectivity is good, strong antijamming capability and the advantages such as reusable, can rapidly and efficiently degrade dyeing waste water under visible light illumination, and quickly catalyst can be separated from solution by external magnetic field, to realize the recycling and reusing of catalyst, greatly reduce cost for wastewater treatment, preparation process is simple, reaction condition is mild, low energy consumption, synthetic method is simple, it is at low cost, it is easy to realize industrial production.
Description
Technical field
The present invention relates to photocatalysis technology field, in particular to a kind of complex light Fenton for dyeing waste water of degrading is catalyzed
Agent and its preparation method and application.
Background technique
China is textile printing and dyeing industry big country, and not only water consumption is huge for textile printing and dyeing industry, and wastewater discharge is not also small.According to statistics
Average every production 1kg product need to consume 0.2~0.5m3Water, the total emission volumn of China's dyeing waste water accounts for about entire Industry Waste at present
The 35% of water.More intractable dyeing waste water is because the water quality such as its, coloration sufficiently complex with ingredient, content of organics height are special
Point in addition a variety of dyestuffs, auxiliary agent etc. used in dyeing process have very strong toxicity, and then is difficult to be bioavailable degradation.
In recent years, as the rapid development of dyeing, new dye and dyeing auxiliaries are by a large amount of exploitation and application, so that dyeing waste water
Processing difficulty also constantly increasing.
Processing for such waste water, biochemical method treatment effect is unsatisfactory, is generally extremely difficult to the requirement of relevant criterion,
Active carbon adsorption is to organic matter removal significant effect, but activated carbon adsorption capacity is limited, and difficulty is regenerated after adsorption saturation, is caused
Operating cost is higher；Photocatalysis technology has efficient, stable, without secondary pollution and to be applicable in all kinds of organic pollutant degradations etc. prominent
Advantage out is one of technology very promising in advanced oxidation processes, but previous photocatalysis technology is largely using ultraviolet
Light is as excitaton source, and at high cost, light utilization ratio is lower, and ultraviolet light only accounts for < 5% in natural sunlight, utilizes solar energy
Organic pollutant difficult to degrade has caused the common concern of domestic and foreign scholars in photocatalysis treatment of waste water；Fenton's reaction is usually used in water
The processing of middle persistent organic pollutants will have using the hydroxyl radical free radical that ferrous ion and hydrogen peroxide generate strong oxidizing property
Machine molecule exhaustive oxidation is a kind of environmental-friendly green catalysis technique.But Fenton's reaction usually carries out under homogeneous, but to anti-
Answer the pH value of system to require harsh, and be difficult to separate and recycle there is also catalyst, iron ion loss causes secondary pollution etc.
The presence of disadvantage, these problems and disadvantage greatly limits application of the Fenton's reaction in degradation organic pollutants；If will
Photocatalysis technology is coupled with class Fenton technology, that is, light class Fenton technology, can effectively solve the problem that the defect of class Fenton technology, and
It can show higher catalytic activity.
Summary of the invention
In order to solve the above technical problems, the present invention mention a kind of complex light fenton catalyst for dyeing waste water of degrading and its
Preparation method and application solve the catalytic activity with preferable visible light, and dyeing waste water of quickly and efficiently degrading is prepared simultaneously
The problems such as method is simple and environmentally protective.
The technical solution adopted by the invention is as follows: a kind of preparation of the complex light fenton catalyst for dyeing waste water of degrading
Method, it is characterised in that the following steps are included:
Step 1: preparing sulfhydrylation Fe3O4Nanosphere: by FeCl3It is placed in ethylene glycol, anhydrous vinegar is added after stirring and dissolving
Sour sodium continues stirring to after being completely dissolved, and system temperature is risen to 170-300 DEG C, reaction 5-12h will be precipitated after reaction
Object separation, washing, drying, obtain magnetic Nano microsphere, and it is 0.02-0.1mol/L's that mass concentration, which is added, in magnetic Nano microsphere
In the ethanol solution of thioacetic acid, the microwave reaction 0.5-2h at 25 DEG C by sediment separation, washing, is done after reaction
It is dry to get arrive the sulfhydrylation Fe3O4Nanosphere；
Step 2: preparing core/shell type Fe3O4@MOF: the sulfhydrylation Fe that step 1 is obtained3O4FeCl is added in nanosphere3's
Ethanol solution, ultrasonic disperse 2-10min are stirred to react 10-30min, reaction terminates then under the conditions of 65~80 DEG C of water-bath
Afterwards, by after sediment separation, ethanol washing, the ethanol solution of trimesic acid, ultrasonic disperse 2-10min, then in water is added
Under the conditions of 65~80 DEG C of bath, it is stirred to react 10-30min, after reaction, after sediment separation, ethanol washing, sulfhydrylation
Fe3O4Nanosphere is coated with single layer MOF, repeatedly, until sulfhydrylation Fe3O4Nanosphere is coated with multilayer MOF, is formed
The core/shell type Fe3O4@MOF；
Step 3: preparation complex light fenton catalyst: nine water ferric nitrates being dissolved in dust technology and obtains mass concentration and is
Then at room temperature 5-sulphosalicylic acid is stirred and is added in iron nitrate solution by the iron nitrate solution of 0.02-0.1mol/L, adjust
Solution is saved in the core/shell type Fe that after acid, step 2 is obtained3O4In@MOF addition system, it is stirred to react 18-30h at room temperature,
After reaction, it is dried in vacuo by sediment separation, washing, at 25 DEG C, obtains the complex light fenton catalyst.
Preferably, FeCl described in step 13, anhydrous sodium acetate and ethylene glycol mass volume ratio be (1-5) g:(5-
12) g:100ml.
Preferably, FeCl described in step 23The mass concentration of ethanol solution is 0.5-5mol/L, the trimesic acid
The mass concentration of ethanol solution is 0.5-5mol/L.
Preferably, described in the step 2 MOF layers be 10-40 layers.
Preferably, the molar ratio of nine water ferric nitrates and 5-sulphosalicylic acid described in step 3 is 1:(1.5-2.5).
Preferably, the nine water ferric nitrate and core/shell type Fe3O4The molal weight ratio of@MOF is (0.02-0.1) mmol:
(0.8-1.5)g。
Preferably, solution refers to that the pH value for adjusting solution is 3.0-5.0 in acidity in step 3.
A kind of complex light fenton catalyst for dyeing waste water of degrading, key are: the smooth fenton catalyst is by weighing
Benefit requires the described in any item methods of 1-7 to be prepared, including core/shell type Fe3O4@MOF magnetic carrier and core/shell type Fe3O4@
5-sulphosalicylic acid iron (III) layer loaded on MOF magnetic carrier.
A kind of application of smooth fenton catalyst according to any one of claims 8, key are: by the complex light fenton catalyst
It is added in dyeing waste water, is put into after stirring evenly in light Fenton reactor, it is molten that hydrogen peroxide is then added into light Fenton reactor
Liquid, under the irradiation of visible light and stirring action, by degradation of organic dyes.
The utility model has the advantages that compared with prior art, the light fenton catalyst for the degradation dyeing waste water that the present invention is prepared will
Fe3O4On successively wrap up MOF and 5-sulphosalicylic acid iron (III) from inside to outside, 5-sulphosalicylic acid iron (III) swashs in visible light
It gives, is excited to form transition state, Fe2+Dissociate into aqueous solution rapidly, the OH of strong oxidizing property is generated with hydrogen peroxide, generation
Fe3+It again with ligand complex, recycles again, class hydroquinone structure can be according to the spirit of each stage of iron ion catalytic cycle
Ground switch iron living two it is alternate walk so that the OH generated is in water phase, and Fe3+Action is but limited in solid phase, has non-
Often high H2O2Utilization rate；MOF is coated on Fe3O4Upper formation core/shell type magnetic carrier, have high-specific surface area, and with sun
There is strong electrostatic interaction between ion organic dyestuff, the two synergistic effect can be by organic pollutant quick adsorption in catalyst
Surface, and pass through a series of chain conveyer process between catalyst surface-solution, one side directly degradation catalyst adsorption
Organic pollutant, while a part of OH desorption catalyzing agent surface carries out oxidative degradation to the organic pollutant in waste water, effectively
Reaction efficiency is improved, oxidant consumption is saved；Catalyst preparation process of the present invention is simple, will can quickly be urged by external magnetic field
Agent is separated from solution, to realize the recycling and reusing of catalyst, greatly reduces cost for wastewater treatment；It is independent with tradition
Ozonation technology is compared, and the present invention significantly improves the removal rate of Cationic organic dyes, and lesser catalyst amounts can
To obtain good catalysis ozone effect.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, below with reference to subordinate list and specific embodiment party
Formula elaborates to the present invention.
One, preparation of the embodiment 1 for the complex light fenton catalyst I for dyeing waste water of degrading
Step 1: preparing sulfhydrylation Fe3O4Nanosphere: by FeCl3It is placed in ethylene glycol, anhydrous vinegar is added after stirring and dissolving
Sour sodium, the FeCl3, anhydrous sodium acetate and ethylene glycol mass volume ratio be 1g:5g:100ml, continue stirring to being completely dissolved
Afterwards, system temperature is risen to 170 DEG C, reacts 5h, after reaction, by sediment separation, washing, drying, obtain magnetic Nano
Microballoon magnetic Nano microsphere is added in the ethanol solution for the thioacetic acid that mass concentration is 0.02mol/L, the microwave at 25 DEG C
0.5h is reacted, after reaction, the sulfhydrylation Fe is arrived into sediment separation, washing, drying3O4Nanosphere；
Step 2: preparing core/shell type Fe3O4@MOF carrier: the sulfhydrylation Fe that step 1 is obtained3O4Matter is added in nanosphere
Measure the FeCl that concentration is 0.5mol/L3Ethanol solution, ultrasonic disperse 2min are stirred to react then under the conditions of 65 DEG C of water-bath
After sediment separation, ethanol washing, the trimesic acid that mass concentration is 0.5mol/L is added after reaction in 10min
Ethanol solution, ultrasonic disperse 2min is stirred to react 10min then under the conditions of 65 DEG C of water-bath, after reaction, by sediment
After separation, ethanol washing, sulfhydrylation Fe3O4Nanosphere is coated with single layer MOF, repeatedly, until sulfhydrylation Fe3O4Nanometer
Ball is coated with 10 layers of MOF, forms the core/shell type Fe3O4@MOF；
Step 3: preparation complex light fenton catalyst: nine water ferric nitrates being dissolved in dust technology and obtains mass concentration and is
Then at room temperature 5-sulphosalicylic acid is stirred and is added in iron nitrate solution by the iron nitrate solution of 0.02mol/L, nine water nitre
The molar ratio of sour iron and 5-sulphosalicylic acid is 1:1.5, and the pH value for adjusting solution is 3.0, the core/shell type that step 2 is obtained
Fe3O4In@MOF addition system, the nine water ferric nitrate and core/shell type Fe3O4The molal weight ratio of@MOF is 0.02mmol:
0.8g is stirred to react 18h at room temperature, after reaction, is dried in vacuo, obtains described by sediment separation, washing, at 25 DEG C
Complex light fenton catalyst I.
Preparation of the embodiment 2 for the complex light fenton catalyst II for dyeing waste water of degrading
Step 1: preparing sulfhydrylation Fe3O4Nanosphere: by FeCl3It is placed in ethylene glycol, anhydrous vinegar is added after stirring and dissolving
Sour sodium, the FeCl3, anhydrous sodium acetate and ethylene glycol mass volume ratio be 5g:12g:100ml, continue stirring to completely molten
System temperature is risen to 300 DEG C, reacts 5-12h by Xie Hou, after reaction, by sediment separation, washing, drying, obtains magnetism
Nanosphere magnetic Nano microsphere is added in the ethanol solution for the thioacetic acid that mass concentration is 0.1mol/L, at 25 DEG C
Sediment separation, washing, drying are arrived the sulfhydrylation Fe after reaction by microwave reaction 2h3O4Nanosphere；
Step 2: preparing core/shell type Fe3O4@MOF carrier: the sulfhydrylation Fe that step 1 is obtained3O4Matter is added in nanosphere
Measure the FeCl that concentration is 5mol/L3Ethanol solution, ultrasonic disperse 10min are stirred to react then under the conditions of 80 DEG C of water-bath
After sediment separation, ethanol washing, the second for the trimesic acid that mass concentration is 5mol/L is added after reaction in 30min
Alcoholic solution, ultrasonic disperse 10min are stirred to react 30min then under the conditions of 80 DEG C of water-bath, after reaction, by sediment point
From after, ethanol washing, sulfhydrylation Fe3O4Nanosphere is coated with single layer MOF, repeatedly, until sulfhydrylation Fe3O4Nanosphere
20 layers of MOF are coated with, the core/shell type Fe is formed3O4@MOF；
Step 3: preparation complex light fenton catalyst: nine water ferric nitrates being dissolved in dust technology and obtains mass concentration and is
Then at room temperature 5-sulphosalicylic acid is stirred and is added in iron nitrate solution by the iron nitrate solution of 0.1mol/L, nine water nitric acid
The molar ratio of iron and 5-sulphosalicylic acid is 1:2.5, and the pH value for adjusting solution is 5.0, the core/shell type that step 2 is obtained
Fe3O4In@MOF addition system, the nine water ferric nitrate and core/shell type Fe3O4The molal weight ratio of@MOF is 0.1mmol:
1.5g is stirred to react 30h at room temperature, after reaction, is dried in vacuo, obtains described by sediment separation, washing, at 25 DEG C
Complex light fenton catalyst II.
Preparation of the embodiment 3 for the complex light fenton catalyst III for dyeing waste water of degrading
Step 1: preparing sulfhydrylation Fe3O4Nanosphere: by FeCl3It is placed in ethylene glycol, anhydrous vinegar is added after stirring and dissolving
Sour sodium, the FeCl3, anhydrous sodium acetate and ethylene glycol mass volume ratio be 1.56g:5.75g:100ml, continue stirring to complete
After fully dissolved, system temperature is risen to 200 DEG C, reacts 8h, after reaction, by sediment separation, washing, drying, obtains magnetic
Property nanosphere, by magnetic Nano microsphere be added mass concentration be 0.013mol/L thioacetic acid ethanol solution in, 25
Sediment separation, washing, drying are arrived the sulfhydrylation Fe after reaction by microwave reaction 1h at DEG C3O4Nanosphere；
Step 2: preparing core/shell type Fe3O4@MOF carrier: the sulfhydrylation Fe that step 1 is obtained3O4Matter is added in nanosphere
Measure the FeCl that concentration is 1.6mol/L3Ethanol solution, ultrasonic disperse 4min are stirred to react then under the conditions of 70 DEG C of water-bath
After sediment separation, ethanol washing, the trimesic acid that mass concentration is 1.6mol/L is added after reaction in 15min
Ethanol solution, ultrasonic disperse 3min is stirred to react 20min then under the conditions of 70 DEG C of water-bath, after reaction, by sediment
After separation, ethanol washing, sulfhydrylation Fe3O4Nanosphere is coated with single layer MOF, repeatedly, until sulfhydrylation Fe3O4Nanometer
Ball is coated with 40 layers of MOF, forms the core/shell type Fe3O4@MOF；
Step 3: preparation complex light fenton catalyst: nine water ferric nitrates being dissolved in dust technology and obtains mass concentration and is
Then at room temperature 5-sulphosalicylic acid is stirred and is added in iron nitrate solution by the iron nitrate solution of 0.07mol/L, nine water nitre
The molar ratio of sour iron and 5-sulphosalicylic acid is 1:2, and the pH value for adjusting solution is 4.0, the core/shell type that step 2 is obtained
Fe3O4In@MOF addition system, the nine water ferric nitrate and core/shell type Fe3O4The molal weight ratio of@MOF is 0.07mmol:1g,
It is stirred to react at room temperature for 24 hours, after reaction, is dried in vacuo, obtains described compound by sediment separation, washing, at 25 DEG C
Light fenton catalyst II.
Two, the complex light fenton catalyst I-III prepared by the present invention for dyeing waste water of degrading is tested as follows:
The methylene blue solution that 50mL concentration is 50mg/L is added in the complex light fenton catalyst I-III of 0.1g respectively
In, it is 4.0 that 60min, which is sufficiently stirred, and adjusts solution ph respectively, then mixed solution is respectively charged into vial, dark ring
Respective dark reaction 0.5h in border investigates purification of the different time catalyst to dyeing waste water then under the xenon lamp irradiation of 500W
Degree, test result is referring to the following table 1:
Degradation property of the smooth fenton catalyst I-III of table 1 to methylene blue
Finally it is to be appreciated that foregoing description is merely a preferred embodiment of the present invention, those skilled in the art is in the present invention
Enlightenment under, without prejudice to the purpose of the present invention and the claims, multiple similar expressions, such change can be made
It changes and falls within the scope of protection of the present invention.
Claims (9)
1. a kind of preparation method of the complex light fenton catalyst for dyeing waste water of degrading, it is characterised in that including following step
It is rapid:
Step 1: preparing sulfhydrylation Fe3O4Nanosphere: by FeCl3It is placed in ethylene glycol, anhydrous sodium acetate is added after stirring and dissolving,
Continue stirring to after being completely dissolved, system temperature is risen to 170-300 DEG C, reacts 5-12h, after reaction, by sediment point
From, washing, dry, magnetic Nano microsphere is obtained, the sulfydryl that mass concentration is 0.02-0.1mol/L is added in magnetic Nano microsphere
In the ethanol solution of acetic acid, the microwave reaction 0.5-2h at 25 DEG C, after reaction, by sediment separation, washing, drying, i.e.,
Obtain the sulfhydrylation Fe3O4Nanosphere；
Step 2: preparing core/shell type Fe3O4@MOF: the sulfhydrylation Fe that step 1 is obtained3O4FeCl is added in nanosphere3Ethyl alcohol
Solution, ultrasonic disperse 2-10min are stirred to react 10-30min then under the conditions of 65~80 DEG C of water-bath, after reaction, will
After ethanol washing, the ethanol solution of trimesic acid is added in sediment separation, ultrasonic disperse 2-10min, then water-bath 65~
Under the conditions of 80 DEG C, it is stirred to react 10-30min, after reaction, after sediment separation, ethanol washing, sulfhydrylation Fe3O4Nanometer
Ball is coated with single layer MOF, repeatedly, until sulfhydrylation Fe3O4Nanosphere is coated with multilayer MOF, forms the core shell
Type Fe3O4@MOF；
Step 3: preparation complex light fenton catalyst: it is 0.02- that nine water ferric nitrates, which are dissolved in dust technology, and obtain mass concentration
Then at room temperature 5-sulphosalicylic acid is stirred and is added in iron nitrate solution by the iron nitrate solution of 0.1mol/L, adjust solution
After acidity, core/shell type that step 2 is obtained
Fe3O4In@MOF addition system, it is stirred to react 18-30h at room temperature, after reaction, by sediment separation, washing, 25
It is dried in vacuo at DEG C, obtains the complex light fenton catalyst.
2. the preparation method of the complex light fenton catalyst according to claim 1 for dyeing waste water of degrading, feature
It is FeCl described in step 13, anhydrous sodium acetate and ethylene glycol mass volume ratio be (1-5) g:(5-12) g:100ml.
3. the preparation method of the complex light fenton catalyst according to claim 1 or 2 for dyeing waste water of degrading, special
Sign is FeCl described in step 23The mass concentration of ethanol solution is 0.5-5mol/L, the trimesic acid ethanol solution
Mass concentration be 0.5-5mol/L.
4. the preparation method of the complex light fenton catalyst according to claim 3 for dyeing waste water of degrading, feature
It is that MOF described in the step 2 layers is 10-40 layers.
5. the preparation method of the complex light fenton catalyst according to claim 3 for dyeing waste water of degrading, feature
It is that the molar ratio of nine water ferric nitrates and 5-sulphosalicylic acid described in step 3 is 1:(1.5-2.5).
6. the according to claim 1, system of the described in any item complex light fenton catalysts for dyeing waste water of degrading in 2,4 or 5
Preparation Method, it is characterised in that: the nine water ferric nitrate and core/shell type Fe3O4The molal weight ratio of@MOF is (0.02-0.1)
Mmol:(0.8-1.5) g.
7. the preparation method of the complex light fenton catalyst according to claim 6 for dyeing waste water of degrading, feature
It is in step 3 that solution refers to that the pH value for adjusting solution is 3.0-5.0 in acidity.
8. a kind of complex light fenton catalyst for dyeing waste water of degrading, it is characterised in that: the smooth fenton catalyst is by weighing
Benefit requires the described in any item methods of 1-7 to be prepared, including core/shell type Fe3O4@MOF magnetic carrier and core/shell type Fe3O4@
5-sulphosalicylic acid iron (III) layer loaded on MOF magnetic carrier.
9. a kind of application of smooth fenton catalyst according to any one of claims 8, it is characterised in that: by the complex light fenton catalyst
It is added in dyeing waste water, is put into after stirring evenly in light Fenton reactor, it is molten that hydrogen peroxide is then added into light Fenton reactor
Liquid, under the irradiation of visible light and stirring action, by degradation of organic dyes.
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| CN115970693A (en) * | 2022-11-30 | 2023-04-18 | 重庆化工职业学院 | Microalgae modified iron oxide photo-Fenton catalyst and preparation method and application thereof |
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