CN104785270A - Visible light catalysts used for treatment of methylene blue dye waste water and a preparing method thereof - Google Patents
Visible light catalysts used for treatment of methylene blue dye waste water and a preparing method thereof Download PDFInfo
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- CN104785270A CN104785270A CN201410847202.XA CN201410847202A CN104785270A CN 104785270 A CN104785270 A CN 104785270A CN 201410847202 A CN201410847202 A CN 201410847202A CN 104785270 A CN104785270 A CN 104785270A
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- visible light
- methylene blue
- blue dye
- light catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
Visible light catalysts used for treatment of methylene blue dye waste water and a preparing method thereof are disclosed. The method adopts a soluble metal salt, vanadium pentoxide and hydrogen peroxide as raw materials and includes stirring and dissolving at 0-10 DEG C, heating to 50-62 DEG C, maintaining the temperature, reacting until no bubble is generated and a precipitate is generated at the bottom, filtering, drying to obtain the precipitate, and calcinating to obtain catalyst powder having a general formula of Mex.V2O5, wherein the soluble metal salt is a soluble sodium salt or a copper salt, the Me is sodium or copper, and the x is 0.2-0.4. The prepared catalysts can effectively degrade methylene blue dye in waste water under irradiation of visible light.
Description
Technical field
The invention belongs to inorganic functional material preparing technical field, relate to a kind of visible light catalyst for the treatment of methylene blue dye wastewater and preparation method thereof.
Background technology
Current organic dye waste water has become one of main pollution source of water body.This waste water has that the water yield is large, concentration is high, complicated component, colourity are dark and the feature such as difficult degradation.Most of dyestuff has toxicity, carcinogenicity, teratogenesis and mutagenic effect.Methylene blue is a kind of important organic chemical synthesis dye of positive ion, and commercial Application widely.Such as, can be applicable to fiber crops, silk fabric, the dyeing of paper and the painted of bamboo and wood, be applied to biology, bacterial organisms dyeing and be applied to manufacture ink and color lake etc.Methylene blue extensive use industrially causes containing methylene blue dye wastewater the severe contamination of water body.The processing method of current organic dye waste water mainly contains bioanalysis, Coagulation Method, high-level oxidation technology, photocatalytic method, absorption method and membrane separation process etc.Bioanalysis, by the impact of the factors such as pH value, temperature, salt and kind of dyes, makes the effect of Biochemical method not ideal enough.The operating cost of Coagulation Method is higher, and body refuse amount is large and dehydration is difficult, and the pH value range be suitable for is narrow.High-level oxidation technology cost is high, conventional oxidant also can show oxidability strong, there is the shortcomings such as selective oxidation, and easily introduce impurity in processing procedure and cause secondary pollution.The cost of membrane separation process is higher, and operating pressure is comparatively large, causes the energy consumption of embrane method higher.
In recent years, the poisonous and hazardous pollutant of semi-conducting material photocatalytic degradation is utilized to become important research direction.Not only energy consumption is low, easy and simple to handle, reaction condition is gentle, non-secondary pollution for photocatalysis technology, and effectively organic pollution can be converted into inorganic molecules, reaches completely inorganization object.The more photochemical catalyst of current use is TiO
2, it has, and photocatalytic activity is high, the advantage of good stability.But TiO
2greater band gap, can only absorb the ultraviolet light of λ≤387nm, the utilization rate of solar energy is low.Therefore, exploitation is a kind of replaces TiO
2and the visible light catalyst that simply efficiently can process methylene blue dye wastewater has great importance.
Summary of the invention
In view of the deficiencies in the prior art, the object of the invention is to solve the above-mentioned technical problem existed in prior art, thus visible light catalyst of a kind of simple effectively degradation of methylene blue waste water and its preparation method and application is provided.
To achieve these goals, the present invention obtains following technical scheme after being studied by lot of experiments:
For the treatment of a visible light catalyst for methylene blue dye wastewater, it is Me that described visible light catalyst comprises general formula
xv
2o
5component, wherein Me is sodium element or copper, x=0.2-0.4.
A kind of preparation method of the visible light catalyst for the treatment of methylene blue dye wastewater, the method comprises the steps: with soluble metallic salt, vanadic anhydride and hydrogen peroxide as raw material, stirring and dissolving under the condition of 0-10 DEG C, then insulation reaction after being heated to 50-62 DEG C, to bubble-free produce and bottom have precipitation generate, filter, dry gained precipitation, after calcining, obtain general formula is Me
xv
2o
5catalyst powder; Wherein, described soluble metallic salt is soluble sodium salt or soluble copper salt, and Me is sodium element or copper, x=0.2-0.4.
Preferably, as mentioned above for the treatment of the preparation method of the visible light catalyst of methylene blue dye wastewater, the mol ratio of the sodium element in wherein said soluble metallic salt or copper and vanadic anhydride is 0.2-0.4:1.
Preferably, as mentioned above for the treatment of the preparation method of the visible light catalyst of methylene blue dye wastewater, wherein said raw material is stirring and dissolving under 0 DEG C of ice-water bath.
Further preferably, as mentioned above for the treatment of the preparation method of the visible light catalyst of methylene blue dye wastewater, the raw material after wherein dissolving is insulation reaction under 60 DEG C of constant temperature water bath heating.
Preferably, as mentioned above for the treatment of the preparation method of the visible light catalyst of methylene blue dye wastewater, wherein said drying steps dries under being deposited in normal temperature and air conditions.
Preferably, as mentioned above for the treatment of the preparation method of the visible light catalyst of methylene blue dye wastewater, wherein said calcining step is that the precipitation of drying is put into Muffle furnace, calcines 35 hours at 200 DEG C 500 DEG C.
Preferably, as mentioned above for the treatment of the preparation method of the visible light catalyst of methylene blue dye wastewater, the mass fraction of wherein said hydrogen peroxide is 8-12%.
Methylene blue dye wastewater is introduced in cylindrical quartz photo catalysis reactor by the present invention, the visible light catalyst powder that 0.5 ~ 2g/L prepared as stated above is added according to the concentration of methylene blue dye wastewater, open magnetic stirring apparatus again to stir, catalyst is made to be suspended state, then xenon source is connected, irradiate 30-90 minute, utilize the organic principle in wastewater by photocatalysis.Described xenon lamp is placed in quartzy cold-trap, and this cold-trap is fixed on cylindrical quartz reactor central authorities, is connected with cooling water in the interlayer in cold-trap, by the fuel factor regulating the flow of cooling water to eliminate xenon lamp.Described light source adopts the xenon lamp of simulated solar spectrum, the ultraviolet spectra of optical filter elimination 420 below nm wavelength.Also sunlight can be used in the present invention.It is high that the present invention has catalytic degradation efficiency at normal temperatures and pressures, and technological process is simple, and non-secondary pollution produces, and the feature such as operating cost is low, there is very high actual application value.
Based on above effect, present invention also offers a kind of method utilizing above-mentioned visible light catalyst process methylene blue dye wastewater, wherein the method comprises and is suspended in methylene blue dye wastewater by described visible light catalyst, in the radiation of visible light 30-90 min process of wavelength >=420nm.
Preferably, utilize the method for above-mentioned visible light catalyst process methylene blue dye wastewater as mentioned above, wherein add described visible light catalyst in the ratio of 0.5 ~ 2.0g/L waste water, under agitation process.
Compared with prior art, the method that the present invention relates to process methylene blue dye wastewater has following significant advantage with significant progressive:
(1) visible light catalyst preparation method of the present invention is simple, is easy to suitability for industrialized production.
(2) visible light catalyst activity of the present invention is high, removes pollutant Be very effective, can in the short period of time fast and efficient degradation pollutant.
(3) method of wastewater treatment of the present invention can carry out at normal temperatures and pressures, and technological process is simple and cost is low.
(4) pollutant is finally degraded into inorganic molecules material by method of wastewater treatment of the present invention, thus avoids the generation of secondary pollution.
Detailed description of the invention
The Synthesis and applications of form to visible light catalyst of the present invention is described in further detail again by the following examples, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
Take 0.01mol and 1.81g vanadic anhydride, get 0.43g and 0.003mol anhydrous sodium sulfate again, both are made to be dissolved under ice-water bath condition in the 40mL hydrogen peroxide of 10%, after dissolving completely, mixed solution is placed on water-bath and carries out isothermal reaction in 60 DEG C, after reddish-brown precipitation reaction generated filters, room temperature is dried, and transfers in Muffle furnace and calcine 3h in 300 DEG C after then the sediment dried being positioned over crucible, takes out for subsequent use after cooling.
The methylene blue dye wastewater being 70.0 mg/L by 40 mL concentration adds in cylindrical quartz photo catalysis reactor, add catalyst 40 mg prepared as stated above, magnetic agitation makes photochemical catalyst be in suspended state always, then irradiates (built-in optical filter elimination 420 below nm wave spectrum) with 300 W xenon lamps.After radiation of visible light 60 min of wavelength >=420 nm, the degradation rate of methylene blue is 99.20%.And not having under anhydrous sodium sulfate, the degradation rate of the vanadic anhydride prepared by the present embodiment catalyst method to methylene blue is only 51.14%.
Embodiment 2
Take 0.01mol and 1.81g vanadic anhydride, 0.002mol and 0.483g nitrate trihydrate copper, making both under ice-water bath condition, be dissolved in content is in the 40mL hydrogen peroxide of 10%, after dissolving completely, mixed solution is placed on water-bath and carries out isothermal reaction in 60 DEG C, after reddish-brown precipitation reaction generated filters, room temperature is dried, and transfers in Muffle furnace and calcine 3h in 200 DEG C after then the sediment dried being positioned over crucible, takes out for subsequent use after cooling.
The methylene blue dye wastewater being 70.0 mg/L by 40 mL concentration adds in cylindrical quartz photo catalysis reactor, add catalyst 40 mg prepared as stated above, magnetic agitation makes photochemical catalyst be in suspended state always, then irradiates (built-in optical filter elimination 420 below nm wave spectrum) with 300 W xenon lamps.After radiation of visible light 60 min of wavelength >=420 nm, the degradation rate of methylene blue is 99.17%.And not having under copper nitrate, the degradation rate of the vanadic anhydride prepared by the present embodiment catalyst method to methylene blue is only 51.14%.
Embodiment 3
Take 0.01mol and 1.81g vanadic anhydride, 0.003mol and 0.725g nitrate trihydrate copper, both are made to be dissolved under ice-water bath condition in the 40mL hydrogen peroxide of 10%, after dissolving completely, mixed solution is placed on water-bath and carries out isothermal reaction in 60 DEG C, after reddish-brown precipitation reaction generated filters, room temperature is dried, and transfers in Muffle furnace and calcine 3h in 300 DEG C after then the sediment dried being positioned over crucible, takes out for subsequent use after cooling.
The methylene blue dye wastewater being 70.0 mg/L by 40 mL concentration adds in cylindrical quartz photo catalysis reactor, add catalyst 40 mg prepared as stated above, magnetic agitation makes photochemical catalyst be in suspended state always, then irradiates (built-in optical filter elimination 420 below nm wave spectrum) with 300 W xenon lamps.After radiation of visible light 60 min of wavelength >=420 nm, the degradation rate of methylene blue is 99.50%.
Embodiment 4
Take 0.01mol and 1.81g vanadic anhydride, 0.003mol and 0.967g nitrate trihydrate copper, both are made to be dissolved under ice-water bath condition in the 40mL hydrogen peroxide of 10%, after dissolving completely, mixed solution is placed on water-bath and carries out isothermal reaction in 60 DEG C, after reddish-brown precipitation reaction generated filters, room temperature is dried, and transfers in Muffle furnace and calcine 5h in 500 DEG C after then the sediment dried being positioned over crucible, takes out for subsequent use after cooling.
The methylene blue dye wastewater being 70.0 mg/L by 40 mL concentration adds in cylindrical quartz photo catalysis reactor, add catalyst 40 mg prepared as stated above, magnetic agitation makes photochemical catalyst be in suspended state always, then irradiates (built-in optical filter elimination 420 below nm wave spectrum) with 300 W xenon lamps.After radiation of visible light 60 min of wavelength >=420 nm, the degradation rate of methylene blue is 92.07%.
Claims (10)
1. for the treatment of a visible light catalyst for methylene blue dye wastewater, it is characterized in that: it is Me that described visible light catalyst comprises general formula
xv
2o
5component, wherein Me is sodium element or copper, x=0.2-0.4.
2. the preparation method for the treatment of the visible light catalyst of methylene blue dye wastewater, it is characterized in that the method comprises the steps: with soluble metallic salt, vanadic anhydride and hydrogen peroxide as raw material, stirring and dissolving under the condition of 0-10 DEG C, then insulation reaction after being heated to 50-62 DEG C, to bubble-free produce and bottom have precipitation generate, filter, dry gained precipitation, after calcining, obtain general formula is Me
xv
2o
5catalyst powder; Wherein, described soluble metallic salt is soluble sodium salt or soluble copper salt, and Me is sodium element or copper, x=0.2-0.4.
3. according to claim 2 for the treatment of the preparation method of the visible light catalyst of methylene blue dye wastewater, it is characterized in that: the mol ratio of the sodium element in described soluble metallic salt or copper and vanadic anhydride is 0.2-0.4:1.
4. according to claim 2 for the treatment of the preparation method of the visible light catalyst of methylene blue dye wastewater, it is characterized in that: described raw material is stirring and dissolving under 0 DEG C of ice-water bath.
5. according to claim 4 for the treatment of the preparation method of the visible light catalyst of methylene blue dye wastewater, it is characterized in that: the raw material after dissolving is insulation reaction under 60 DEG C of constant temperature water bath heating.
6. according to claim 2 for the treatment of the preparation method of the visible light catalyst of methylene blue dye wastewater, it is characterized in that: described drying steps dries under being deposited in normal temperature and air conditions.
7. according to claim 2 for the treatment of the preparation method of the visible light catalyst of methylene blue dye wastewater, it is characterized in that: described calcining step is that the precipitation of drying is put into Muffle furnace, calcine 35 hours at 200 DEG C 500 DEG C.
8. according to claim 2 for the treatment of the preparation method of the visible light catalyst of methylene blue dye wastewater, it is characterized in that: the mass fraction of described hydrogen peroxide is 8-12%.
9. one kind utilizes the method for visible light catalyst process methylene blue dye wastewater described in claim 1, it is characterized in that: the method comprises and is suspended in methylene blue dye wastewater by described visible light catalyst, in the radiation of visible light 30-90 min process of wavelength >=420 nm.
10. utilize the method for above-mentioned visible light catalyst process methylene blue dye wastewater according to claim 9, it is characterized in that: add described visible light catalyst in the ratio of 0.5-2.0g/L waste water, under agitation process.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106477706A (en) * | 2016-12-14 | 2017-03-08 | 盐城工学院 | Method and the processing method of waste water from dyestuff that a kind of methylenum careuleum is faded |
| CN106669725A (en) * | 2016-12-09 | 2017-05-17 | 湖北工业大学 | Preparation method of multi-component compound oxide catalyst composition for treating methylene blue wastewater |
| CN106824172A (en) * | 2016-12-09 | 2017-06-13 | 湖北工业大学 | The carbon monoxide-olefin polymeric preparation method and application of low concentration formaldehyde in treatment waste water |
| CN111495398A (en) * | 2020-04-22 | 2020-08-07 | 昆明理工大学 | Nano composite visible light catalyst for degrading organic pollutants and preparation method thereof |
| CN111518399A (en) * | 2019-11-29 | 2020-08-11 | 山东天汇路桥有限公司 | Reaction type self-cleaning pavement cementing material based on photocatalysis and preparation method thereof |
| CN111718071A (en) * | 2020-06-30 | 2020-09-29 | 重庆工商大学 | Methylene blue dye wastewater treatment method based on short-range photocatalysis/algae biodegradation |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669725A (en) * | 2016-12-09 | 2017-05-17 | 湖北工业大学 | Preparation method of multi-component compound oxide catalyst composition for treating methylene blue wastewater |
| CN106824172A (en) * | 2016-12-09 | 2017-06-13 | 湖北工业大学 | The carbon monoxide-olefin polymeric preparation method and application of low concentration formaldehyde in treatment waste water |
| CN106477706A (en) * | 2016-12-14 | 2017-03-08 | 盐城工学院 | Method and the processing method of waste water from dyestuff that a kind of methylenum careuleum is faded |
| CN111518399A (en) * | 2019-11-29 | 2020-08-11 | 山东天汇路桥有限公司 | Reaction type self-cleaning pavement cementing material based on photocatalysis and preparation method thereof |
| CN111495398A (en) * | 2020-04-22 | 2020-08-07 | 昆明理工大学 | Nano composite visible light catalyst for degrading organic pollutants and preparation method thereof |
| CN111718071A (en) * | 2020-06-30 | 2020-09-29 | 重庆工商大学 | Methylene blue dye wastewater treatment method based on short-range photocatalysis/algae biodegradation |
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