CN107670670A - A kind of preparation method and application of visible ray fenton catalyst - Google Patents
A kind of preparation method and application of visible ray fenton catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- -1 tungsten ion Chemical class 0.000 claims abstract description 8
- 238000005119 centrifugation Methods 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 239000010937 tungsten Substances 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 3
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 32
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Substances CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 20
- 230000015556 catabolic process Effects 0.000 claims description 13
- 238000006731 degradation reaction Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002957 persistent organic pollutant Substances 0.000 claims description 9
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical group [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract 3
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 238000004042 decolorization Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 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 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 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 description 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910020350 Na2WO4 Inorganic materials 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910020494 K2WO4 Inorganic materials 0.000 description 2
- 229910007786 Li2WO4 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910005507 FeWO4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 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
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/39—
-
- B01J35/60—
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- 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 present invention provides a kind of preparation method and application of visible ray fenton catalyst, belongs to photochemical catalyst preparing technical field.This method comprises the step of：Soluble ferrite is weighed in molar ratio and soluble lithium salt is added in deionized water；Weigh tungstates M2WO4·2H2O is added in deionized water；The solution of above-mentioned preparation is mixed, the mol ratio for making ferrous ion, lithium ion and tungsten ion is 2:2:1, then adding sodium hydroxide solution makes solution alkaline, and mixed solution is transferred in hydrothermal reaction kettle and reacted；It is centrifuged after the completion of reaction, centrifugation gained precipitation is scrubbed, is dried to obtain visible ray fenton catalyst Li2Fe2WO7Powder.This method is using hydro-thermal method synthesis Li2Fe2WO7, preparation method is simply controllable, and products obtained therefrom has preferable visible light catalysis activity.Processing available for organic wastewater.
Description
【Technical field】
The present invention relates to photochemical catalyst preparing technical field, and in particular to a kind of preparation method of visible ray fenton catalyst
And application.
【Background technology】
The few depollution of environment technology of exploitation green, efficient, economy, secondary pollution is environmental pollution improvement and Prevention Technique one
Individual important research field.Photocatalysis technology realizes organic pollution by using caused hydroxyl radical free radical in course of reaction
Efficient degradation, but conventional photocatalysis technology largely using ultraviolet light be used as excitaton source, cost height, light utilization ratio is relatively low,
And ultraviolet light only accounts in natural sunshine<5%, in recent years, using solar energy photocatalytic handle waste water in difficult degradation it is organic
Pollutant has caused the common concern of domestic and foreign scholars, it will be seen that light is introduced into Fenton's reaction, forms light Fenton's reaction system, can
Further to improve the removal efficiency of organic pollution.
Fenton's reaction is usually used in the processing of persistent organic pollutants in water, has the OH of strong oxidizing property caused by reaction
Living radical can be by persistent organic pollutants degraded removes in water body and mineralising is environmentally safe Li2And H2O, it is
A kind of environment-friendly green catalysis technique.Fenton's reaction is generally in homogeneous lower progress, although catalytic efficiency is higher and reaction is held
It is easy to control, but harsh (generally only just having high catalytic activity in the range of pH2.5-3.5) is required to the pH value of reaction system,
And catalyst also be present and be difficult to the shortcomings of separation causes secondary pollution with recovery, iron ion loss, these problems and disadvantages
In the presence of greatly limit application of the Fenton's reaction in organic pollutants of degrading.Thus, people are increasingly turning to fragrant to out-phase
The research of catalysts.The research of out-phase Fenton's reaction catalyst is concentrated mainly on the catalytic activity of optimization catalyst and sought
Suitable catalyst carrier is looked for or prepares, the optimization of wherein catalyst is mainly by optimizing preparation condition to catalyst activity
Metal form (crystal formation, crystalline size) is regulated and controled in composition, with prepare catalytic efficiency is higher, adaptability more preferably, pH be applicable model
Enclose wider array of efficient composite catalyst.
FeWO4Be one kind in the field such as light, electricity, magnetic, conductor/superconductor, catalysis and biology extensive application prospect
Material, receive much concern in recent years, preparing the tungstate nano material with different-shape by the regulation and control of preparation method is
The study hotspot of researcher, but FeWO made at present4Photocatalysis performance it is poor, applied in visible ray Fenton's reaction
Reactivity deficiency, research finds, by being doped modification to it, can to improve its light Fenton's reaction active.
【The content of the invention】
The goal of the invention of the present invention is：For above-mentioned problem, there is provided a kind of visible ray fenton catalyst
Li2Fe2WO7Preparation method, this method using hydro-thermal method synthesis Li2Fe2WO7, preparation method is simply controllable, and products obtained therefrom has
Preferable visible light catalysis activity.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of preparation method of visible ray fenton catalyst, comprises the following steps：
(1) soluble ferrite and soluble lithium salt are weighed to add in deionized water, makes rubbing for ferrous ion and lithium ion
You are than being 1:1, stirring and dissolving obtains solution A；
(2) tungstates M is weighed2WO4·2H2O is added in deionized water, wherein, M is alkali metal,；Stirring and dissolving obtains
To M2WO4Solution, to M2WO4Isobutanol is added in solution, the addition of isobutanol is per 1mmolM2WO4·2H2O adds 8-
12mL, stir, obtained solution B；
(3) solution A is added slowly to stir in solution B, the mol ratio for making ferrous ion, lithium ion and tungsten ion is
2:2:1, then adding sodium hydroxide solution makes solution alkaline, obtains mixture C, mixture C is transferred in hydrothermal reaction kettle
Sealing, reacts 12-18h at 190-200 DEG C；
(4) after question response kettle natural cooling, the product in reactor is centrifuged, centrifugation gained precipitation distillation
Water washing, then dry, that is, obtain visible ray fenton catalyst Li2Fe2WO7Powder.
Preferably, the soluble ferrous iron is ferrous nitrate, frerrous chloride or ferrous sulfate；The soluble lithium salt is nitre
Sour lithium；The one kind of the M in K, Na or Li.
Preferably, the pH value for making solution alkaline refer to adjust solution in step (3) is 8.5-9.0.
Preferably, the drying described in step (4) is that 3-5h is dried at a temperature of 200-450 DEG C.
The present invention prepares the visible ray fenton catalyst Li of gained2Fe2WO7Answering in organic wastewater is handled can be applied
With.It handles the method for organic wastewater：By the catalyst Li2Fe2WO7It is added in organic wastewater, light is put into after stirring well
In Fenton reactor, the hydrogenperoxide steam generator that volumetric concentration is 25%-30% is then added into light Fenton reactor and forms sweet smell
Reaction system, under the irradiation of visible ray and under stirring action, by organic pollutant degradation.
The made photocatalyst powder of the present invention can be carried on a variety of matrix surfaces, and matrix can be glass, ceramics, work
Property charcoal or quartz sand etc..
In summary, by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
1st, the present invention prepares the Li of gained2Fe2WO7With visible light-responded wide frequency range, light conversion efficiency is high and stably
Property it is good the characteristics of, have the function that under visible light illumination decomposing organic pollutant and sterilization, can be used for the place of organic wastewater
Reason.
2nd, the present invention prepares the Li of gained2Fe2WO7It can effectively be separated in the presence of externally-applied magnetic field, can repeat to follow
Ring uses, and has evaded the problem of homogeneous catalyst is difficult to recycle.
3rd, preparation method of the invention is simple, synthesis temperature is low, and cost is low, is adapted to industrial production and application.Relative to height
Warm solid phase method, present invention gained powder is nutty structure, has bigger specific surface area, is advantageous to catalyst and organic matter
Contact, degraded is fast and degradation rate is high.
【Embodiment】
In order to more clearly express the present invention, below by way of specific embodiment, the invention will be further described.
Embodiment 1
A kind of preparation method of visible ray Fenton composite catalyst, comprises the following steps：
(1) weigh ferrous nitrate and lithium nitrate is added in deionized water, it is 1 to make the mol ratio of ferrous ion and lithium ion:
1, stirring and dissolving obtains solution A；
(2) Li is weighed2WO4·2H2O is added in deionized water, and stirring and dissolving obtains Li2WO4Solution, to Li2WO4In solution
Isobutanol is added, the addition of isobutanol is per 1mmolM2WO4·2H2O adds 8mL, stirs, obtained solution B；
(3) solution A is added slowly to stir in solution B, the mol ratio for making ferrous ion, lithium ion and tungsten ion is
2:2:1, the pH value for then adding sodium hydroxide solution regulation solution B is 8.5, obtains mixture C, mixture C is transferred into hydro-thermal
Sealed in reactor, react 18h at 190 DEG C；
(4) after question response kettle natural cooling, the product in reactor is centrifuged, centrifugation gained precipitation distillation
Water washing, 5h is then dried at a temperature of 200 DEG C, that is, obtains visible ray fenton catalyst Li2Fe2WO7Powder.
The present invention prepares the visible ray fenton catalyst Li of gained2Fe2WO7Answering in organic wastewater is handled can be applied
With.It handles the method for organic wastewater：By the catalyst Li2Fe2WO7It is added in organic wastewater, light is put into after stirring well
In Fenton reactor, the hydrogenperoxide steam generator that volumetric concentration is 25%-30% is then added into light Fenton reactor and forms sweet smell
Reaction system, under the irradiation of visible ray and under stirring action, by organic pollutant degradation.
Embodiment 2
A kind of preparation method of visible ray Fenton composite catalyst, comprises the following steps：
(1) weigh frerrous chloride and lithium nitrate is added in deionized water, it is 1 to make the mol ratio of ferrous ion and lithium ion:
1, stirring and dissolving obtains solution A；
(2) tungstates Na is weighed2WO4·2H2O is added in deionized water, and stirring and dissolving obtains Na2WO4Solution, to Na2WO4
Isobutanol is added in solution, the addition of isobutanol is per 1mmol Na2WO4·2H2O adds 10mL, stirs, and is made molten
Liquid B；
(3) solution A is added slowly to stir in solution B, the mol ratio for making ferrous ion, lithium ion and tungsten ion is
2:2:1, the pH value for then adding sodium hydroxide solution regulation solution B is 8.8, obtains mixture C, mixture C is transferred into hydro-thermal
Sealed in reactor, react 16h at 195 DEG C；
(4) after question response kettle natural cooling, the product in reactor is centrifuged, centrifugation gained precipitation distillation
Water washing, 4h is then dried at a temperature of 300 DEG C, that is, obtains visible ray fenton catalyst Li2Fe2WO7Powder.
Embodiment 3
A kind of preparation method of visible ray Fenton composite catalyst, comprises the following steps：
(1) weigh ferrous sulfate and lithium nitrate is added in deionized water, it is 1 to make the mol ratio of ferrous ion and lithium ion:
1, stirring and dissolving obtains solution A；
(2) tungstates K is weighed2WO4·2H2O is added in deionized water, and stirring and dissolving obtains K2WO4Solution, to K2WO4It is molten
Isobutanol is added in liquid, the addition of isobutanol is per 1mmolK2WO4·2H2O adds 12mL, stirs, obtained solution B；
(3) solution A is added slowly to stir in solution B, the mol ratio for making ferrous ion, lithium ion and tungsten ion is
2:2:1, the pH value for then adding sodium hydroxide solution regulation solution B is 9.0, obtains mixture C, mixture C is transferred into hydro-thermal
Sealed in reactor, react 12h at 200 DEG C；
(4) after question response kettle natural cooling, the product in reactor is centrifuged, centrifugation gained precipitation distillation
Water washing, 3h is then dried at a temperature of 450 DEG C, that is, obtains visible ray fenton catalyst Li2Fe2WO7Powder.
Comparative example 1
This example is using high temperature solid-state method synthesis Li2Fe2WO7, step used is as follows：
(1) by 99.9% analytically pure chemical raw material Li2CO3、Fe2O3And WO3, by Li2Fe2WO7Chemical formula weighs dispensing.
(2) raw material for preparing step (1) mixes, and is put into ball grinder, adds zirconia ball and absolute ethyl alcohol, ball milling 8
Hour, it is mixed and finely ground, takes out drying, crosses 200 mesh sieves.
(3) by the powder that step (2) is well mixed in 750 DEG C of pre-burnings, and 6 hours are incubated, naturally cool to room temperature, then
Crushing means by ball mill makes particle diameter diminish, and less than 2 μm, that is, obtains Li2Fe2WO7Powder.
Degradation property test experiments
The specific method of visible ray fenton catalyst degradation of organic waste water using the present invention is：The visible ray is fragrant
The catalyst that pauses is added in organic wastewater, is put into after stirring well in light Fenton reactor, is then added into light Fenton reactor
The hydrogenperoxide steam generator that volumetric concentration is 25%-30% forms Fenton's reaction system, under the irradiation of visible ray and stirring action
Under, by organic pollutant degradation.
Test 1 smooth Fenton rhodamine B degradation (RhB) organic dyestuff
At room temperature, each embodiments of 100mg and catalyst sample in comparative example and 200mL rhodamine B is taken to have respectively
(concentration of rhodamine B is 100mgL to engine dyeing material-1) mixing be put into 500mL light Fenton reactor, add 30% peroxidating
Hydrogen solution 0.5mL, regulation pH value is 5, is placed on magnetic stirring apparatus and stirs, adjustment rotating speed is 200r/min.In the photograph of visible ray
Penetrate down, persistently stir 2 hours, the situation that observation mixed liquor fades, and test degraded 1h, 2h different time sections solution absorbance
Value, analytical solution absorbance change with time.The percent of decolourization of rhodamine B in each example of test gained the results are shown in Table 1.
Percent of decolourization of the catalyst of table 1 to rhodamine B
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| 1h percent of decolourizations/% | 96.1 | 95.9 | 96.5 | 75.2 | 61.4 |
| 2h percent of decolourizations/% | 99.2 | 99.3 | 99.4 | 91.8 | 87 |
Upper table shows that the catalyst that the present invention synthesizes has the effect of visible light photocatalytic degradation, the place available for organic wastewater
Reason.It can also be seen that pollutant percent of decolourization of the made catalyst of the invention in 1h is significantly better than comparative example from table, degrade
Fast and degradation rate is high.
Test 2 smooth Fenton degradation of methylene blue (MB) organic dyestuff
At room temperature, each embodiments of 100mg and catalyst sample in comparative example and 200mL methylene blue is taken to have respectively
(concentration of methylene blue is 100mgL to engine dyeing material-1) mixing be put into 500mL light Fenton reactor, add 30% peroxidating
Hydrogen solution 0.5mL, regulation pH value is 5, is placed on magnetic stirring apparatus and stirs, adjustment rotating speed is 200r/min.In the photograph of visible ray
Penetrate down, persistently stir 2 hours, the situation that observation mixed liquor fades, and test degraded 1h, 2h different time sections solution absorbance
Value, analytical solution absorbance change with time.The percent of decolourization of methylene blue in each example of test gained the results are shown in Table 2.
Percent of decolourization of the catalyst of table 2 to methylene blue
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| 1h percent of decolourizations/% | 95.6 | 95.8 | 96.0 | 72.2 | 68.7 |
| 2h percent of decolourizations/% | 98.5 | 99.0 | 98.9 | 91.5 | 85.5 |
Upper table shows that the catalyst that the present invention synthesizes has the effect of visible light photocatalytic degradation, the place available for organic wastewater
Reason.It can also be seen that pollutant percent of decolourization of the made catalyst of the invention in 1h is significantly better than comparative example from table, degrade
Fast and degradation rate is high.
Described above is the detailed description for the present invention preferably possible embodiments, but embodiment is not limited to this hair
Bright patent claim, the equal change completed or modification change under the technical spirit suggested by all present invention, all should belong to
Cover the scope of the claims in the present invention.
Claims (8)
1. a kind of preparation method of visible ray fenton catalyst, it is characterised in that comprise the following steps：
(1) weigh soluble ferrite and soluble lithium salt is added in deionized water, make the mol ratio of ferrous ion and lithium ion
For 1:1, stirring and dissolving obtains solution A；
(2) tungstates M is weighed2WO4·2H2O is added in deionized water, wherein, M is alkali metal,；Stirring and dissolving obtains
M2WO4Solution, to M2WO4Isobutanol is added in solution, the addition of isobutanol is per 1mmolM2WO4·2H2O adds 8-12mL,
Stir, obtained solution B；
(3) solution A is added slowly to stir in solution B, the mol ratio for making ferrous ion, lithium ion and tungsten ion is 2:2:
1, then adding sodium hydroxide solution makes solution alkaline, obtains mixture C, mixture C is transferred in hydrothermal reaction kettle and sealed,
12-18h is reacted at 190-200 DEG C；
(4) after question response kettle natural cooling, the product in reactor is centrifuged, the distillation washing of centrifugation gained precipitation
Wash, then dry, that is, obtain visible ray fenton catalyst Li2Fe2WO7Powder.
2. the preparation method of visible ray fenton catalyst according to claim 1, it is characterised in that：It is described soluble ferrous
For ferrous nitrate, frerrous chloride or ferrous sulfate；The soluble lithium salt is lithium nitrate；The M in K, Na or Li one
Kind.
3. the preparation method of visible ray fenton catalyst according to claim 1, it is characterised in that：Make in step (3) molten
The pH value that liquid refers to adjust solution in alkalescence is 8.5-9.0.
4. the preparation method of visible ray fenton catalyst according to claim 1, it is characterised in that：Described in step (4)
Drying be at a temperature of 200-450 DEG C dry 3-5h.
A kind of 5. visible ray fenton catalyst, it is characterised in that：The chemical formula of the visible ray fenton catalyst is Li2Fe2WO7,
It is made of the method any one of claim 1-4.
6. any one of claim 1-5 prepares the application of the visible ray fenton catalyst of gained, it is characterised in that：The application
Refer to the application in organic wastewater is handled.
7. the application of visible ray fenton catalyst according to claim 6, it is characterised in that：The processing organic wastewater
Method is：By the catalyst Li2Fe2WO7It is added in organic wastewater, is put into after stirring well in light Fenton reactor, Ran Houxiang
Hydrogenperoxide steam generator is added in light Fenton reactor and forms Fenton's reaction system, under the irradiation of visible ray and under stirring action,
By organic pollutant degradation.
8. the application of visible ray fenton catalyst according to claim 7, it is characterised in that：The hydrogenperoxide steam generator
Volumetric concentration is 25%-30%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109052547A (en) * | 2018-08-31 | 2018-12-21 | 南京林业大学 | A kind of method of visible light-responded homogeneous light Fenton processing organic wastewater |
| CN113996300A (en) * | 2021-11-26 | 2022-02-01 | 南京大学 | High-activity iron-based bimetallic Fenton catalyst under pH neutral condition and preparation method thereof |
| CN115286088A (en) * | 2022-07-25 | 2022-11-04 | 西南石油大学 | Using composite bimetal FeWO 4 Method for treating waste drilling fluid by activating persulfate |
| CN116618056A (en) * | 2023-04-20 | 2023-08-22 | 陕西科技大学 | Visible light responsive layered ferric silicate photo Fenton catalyst, preparation method and application |
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2017
- 2017-10-23 CN CN201710993365.2A patent/CN107670670A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109052547A (en) * | 2018-08-31 | 2018-12-21 | 南京林业大学 | A kind of method of visible light-responded homogeneous light Fenton processing organic wastewater |
| CN113996300A (en) * | 2021-11-26 | 2022-02-01 | 南京大学 | High-activity iron-based bimetallic Fenton catalyst under pH neutral condition and preparation method thereof |
| CN115286088A (en) * | 2022-07-25 | 2022-11-04 | 西南石油大学 | Using composite bimetal FeWO 4 Method for treating waste drilling fluid by activating persulfate |
| CN115286088B (en) * | 2022-07-25 | 2023-09-26 | 西南石油大学 | By means of composite bimetallic FeWO 4 Method for treating waste drilling fluid by activating persulfate |
| CN116618056A (en) * | 2023-04-20 | 2023-08-22 | 陕西科技大学 | Visible light responsive layered ferric silicate photo Fenton catalyst, preparation method and application |
| CN116618056B (en) * | 2023-04-20 | 2023-12-29 | 陕西科技大学 | Visible light responsive layered ferric silicate photo Fenton catalyst, preparation method and application |
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