CN104944508B - A kind of photocatalytic degradation method of low concentration mixed dye - Google Patents
A kind of photocatalytic degradation method of low concentration mixed dye Download PDFInfo
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- CN104944508B CN104944508B CN201510279684.8A CN201510279684A CN104944508B CN 104944508 B CN104944508 B CN 104944508B CN 201510279684 A CN201510279684 A CN 201510279684A CN 104944508 B CN104944508 B CN 104944508B
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- methylene blue
- methyl orange
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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Abstract
The present invention relates to the processing method of the waste water from dyestuff of printing and dyeing industry discharge, a kind of photocatalytic degradation method of low concentration mixed dye is specifically disclosed, the mixed dye refers to the mixed dye of methyl orange and methylene blue, and methods described is：Zinc-tin binary hydrotalcite is placed in the mixed dye solution of methyl orange and methylene blue, under room temperature, pH neutrallty conditions, 10~15h is irradiated with xenon lamp, stirring makes methyl orange and methylene blue degrade, obtains the dye solution after degradation treatment；Zinc-tin binary hydrotalcite quality consumption is calculated as 0.02~2.0mg/mL with the volume of mixed dye solution；The chemical general formula of zinc-tin binary hydrotalcite is [Zn2+ 1‑xSn4+ x(OH)2](NO3 ‑)2x·mH2O].Zinc-tin binary hydrotalcite is used for photo-catalytic degradation of methyl-orange and methylene blue mixed dye by the present invention, and reaction condition is gentle, and degradation efficiency is high, and significantly, the material after catalytic degradation is easy to be recycled for effect.
Description
(1) technical field
The present invention relates to a kind of photocatalytic degradation method of low concentration mixed dye.
(2) background technology
With the attention of people's environmental pollution, the organic wastewater pollutant of chemical plant emission is increasingly closed by people
Note.Especially the waste water from dyestuff of printing and dyeing industry discharge due to complicated component, colourity is deep, discharge capacity is big the features such as, belong to difficult degradation
Organic pollution, easily causes body eutrophication, problem of environmental pollution.Chemical method, physisorphtion, biological degradation method etc. are conventional
Processing method can produce secondary pollution, and long processing period in processing procedure, price is high, is difficult expanded.And partly lead
Body photocatalysis technology have efficiency high, pollute less, the advantage such as cheap, in terms of water treatment, failure degradation of pesticide
Paid close attention to, be especially increasingly valued by people in terms for the treatment of of dyeing wastewater using by people.
Hydrotalcite (Layered Double Hydroxides, abbreviation LDHs) is the bimetallic that a class has layer structure
Hydroxide, it is by positively charged layers of metal hydroxides plate [M2+ 1-xM3+ x(OH)2]x+With negatively charged interlayer anion
(AN-)x/nConstitute.General structure is [M2+ 1-xM3+ x(OH)2]x+(AN-)x/n·mH2O, wherein M2+And M3+Divalence and three are represented respectively
Valency metal cation, x is the changes of contents of metallic element, An-Represent the tradable anion of interlayer, such as NO3 -、CO3 2-Deng.
LDHs has the characteristics such as crystallite dimension is small, specific surface area is larger, energy gap is smaller, and there is certain photocatalysis to live for its own
Property.LDHs laminate metals have adjustable denaturation simultaneously, and the material for the highlight catalytic active that can adulterate is improved to the sun on laminate
The response of light, has expanded its application in photocatalysis field.
(3) content of the invention
It is an object of the present invention to provide a kind of hydrotalcite catalysis material, and use it for methyl orange and the Asia of degraded low concentration
The application of methyl blue mixed dye.
The technical solution adopted by the present invention is：
A kind of photocatalytic degradation method of low concentration mixed dye, the mixed dye refers to methyl orange and methylene blue
Mixed dye, methods described is：Zinc-tin binary hydrotalcite is placed in the mixed dye solution of methyl orange and methylene blue, room
Under temperature, pH value neutrallty condition, 10~15h is irradiated with xenon lamp, stirring makes methyl orange and methylene blue degrade, obtains degradation treatment
Dye solution afterwards；The zinc-tin binary hydrotalcite quality consumption is calculated as 0.02~2.0mg/ with the volume of mixed dye solution
ML, preferably 1.0mg/mL；
The chemical general formula of the zinc-tin binary hydrotalcite is [Zn2+ 1-xSn4+ x(OH)2](NO3 -)2x·mH2O], wherein x is
Sn4+/[Sn4++Zn2+] mol ratio, 0<x<1, m is crystallization water quantity, preferably 0.2≤x≤0.33.
The zinc-tin binary hydrotalcite chemical general formula is preferably [Zn2+ 0.75Sn4+ 0.25(OH)2](NO3 -)0.5·0.5H2O]。
The present invention uses water-bath temperature control, and the pH value of mixed dye solution is preferably adjusted with NaOH solution and HCl solution.
PH value neutrallty condition of the present invention, the condition as well known to those skilled in the art for referring to that pH value is 7.
The wavelength of the xenon lamp is 380nm~760nm, power preferably 500~1000W, more preferably 500W.
The mass concentration of methyl orange is 0.5~24mg/L in the mixed dye solution, and the mass concentration of methylene blue is 1
~12mg/L.
The higher injected volume of zinc-tin binary hydrotalcite can effectively adsorb dyestuff in material surface, in order to carry out catalysis drop
Solution, the preferred 1.0mg/ml mixed dye solutions of zinc-tin binary hydrotalcite quality consumption of the present invention.
The energy gap and crystallite dimension for the zinc-tin binary hydrotalcite that the present invention is provided are smaller, the energy under suitable illumination
Electron-hole pair is produced, and then generates chemism high OH and O2, OH and O2Can be with absorption in zinc-tin neatly
Redox reaction occurs for the methyl orange and methylene blue of stone, dyestuff is degraded, so as to reach the purpose of purification waste water.
Zinc-tin binary hydrotalcite of the present invention is generally prepared as follows：Take Zn (NO3)2·6H2O and SnCl4·
5H2O is dissolved in CO2Solution A is made in water；Separately NaOH is taken to be dissolved in CO2Solution B is obtained in water, solution A and solution B are dripped simultaneously
It is added to contain and removes CO2In the four round flask of water, constant rate of addition is kept, strong agitation, pH value is maintained between 8~9,
Continue to stir 30~60min after completion of dropping, in 12~48h of crystallization at 65 DEG C, suction filtration, washing to neutrality, 85 DEG C of dryings 12~
72h, grinds to obtain zinc-tin binary hydrotalcite, wherein zinc-tin mol ratio is 3:1, i.e. x are that 0.25, m is 0.5, and chemical general formula is
[Zn2+ 0.75Sn4+ 0.25(OH)2](NO3 -)0.5·0.5H2O]。
Zinc-tin binary hydrotalcite of the present invention is prepared using conventional method, and the water used in preparation process is
CO2Water.The structure of described methyl orange is as shown in formula A, the structure such as formula B of methylene blue：
The zinc-tin binary hydrotalcite of synthesis is placed in ultraviolet-visible spectrophotometer, its spectrogram that diffuses is determined, and
Pass through formula α h ν=K (h ν-Eg)n/2Calculate energy gap.Wherein α, h, ν, K, EgRepresent respectively absorption factor, planck constant,
Light frequency, scale parameter and energy gap, and with (α h ν)2/nH ν are mapped, the intersection point of extrapolation tangent line and abscissa h ν is
Energy gap.Suitable light source is selected according to the energy gap of material, the main peak energy of light source just can be in excitation material valence band
Electron transition to conduction band generate electron-hole pair.
Zinc-tin hydrotalcite material is to methyl orange in reaction system and the total degradation rate D of methylene blue1And D2Public affairs can be used respectively
Formula (1) and (2) are calculated, i.e.,
D1=1-C1/C10Formula (1)
D2=1-C2/C20Formula (2)
In formula (1) (2), C10And C20Respectively after zinc-tin hydrotalcite adsorption-desorption balance in mixed dye methyl orange and
The mass concentration of methylene blue.C1And C2For methyl orange and the matter of methylene blue in mixed dye after light-catalyzed reaction certain time
Measure concentration.C1And C2Value measure by the following method：Every certain reaction time, 3mL solution is taken to filter, filtrate exists respectively
Its absorbance is measured under the maximum absorption wavelength (464nm) of methyl orange and the maximum absorption wavelength (662nm) of methylene blue, then
Corresponding mass concentration is obtained according to the standard curve of methyl orange and methylene blue.
Itself photodissociation rate (being not added with zinc-tin binary hydrotalcite) d of methyl orange and methylene blue1And d2Formula can be used respectively
(3) calculated with (4), i.e.,
d1=1-c1/c10Formula (3)
d2=1-c2/c20Formula (4)
In formula (3) (4), c10And c20Methyl orange and the initial mass concentration of methylene blue respectively in mixed dye.c1
And c2For methyl orange and the mass concentration of methylene blue in mixed dye after illumination certain time.c1And c2Value pass through such as lower section
Method is measured：Every certain reaction time, maximum absorption wavelength (464nm) and methylene of the 3mL solution respectively in methyl orange are taken
Its absorbance is measured under blue maximum absorption wavelength (662nm), is then obtained according to the standard curve of methyl orange and methylene blue
Corresponding mass concentration.
Total degradation rate and dyestuff of the zinc-tin binary hydrotalcite of the present invention to mixed dye (methyl orange and methylene blue)
Itself photodissociation rate is calculated using the above method.The mixed dye of degraded is low concentration, thus methyl orange and methylene blue are in maximum
Absorption value at absorbing wavelength is not superimposed substantially, can be handled by the method for one-component.
Zinc-tin binary hydrotalcite is used for photo-catalytic degradation of methyl-orange and methylene blue mixed dye, reaction condition by the present invention
Gently, degradation efficiency is high, and significantly, the material after catalytic degradation is easy to be recycled for effect.
(4) illustrate
Fig. 1 is the X-ray diffractogram of zinc-tin binary hydrotalcite in embodiment 1.
Fig. 2 is the diffusing reflection spectrogram of zinc-tin binary hydrotalcite in embodiment 2.
Fig. 3 is the degradation rate curve map of methyl orange and methylene blue mixed solution in embodiment 3.
Fig. 4 is the ultraviolet-visible degraded spectrogram of methyl orange and methylene blue mixed solution in embodiment 3.
Fig. 5 is the canonical plotting of the methyl orange of embodiment 4.
Fig. 6 is the canonical plotting of the methylene blue of embodiment 4.
(5) embodiment
The present invention program is described further with specific embodiment below, but protection scope of the present invention is not limited to
This：
The preparation of the zinc-tin binary hydrotalcite of embodiment 1
Take 22.31g (0.075mol) Zn (NO3)2·6H2O and 8.76g (0.025mol) SnCl4·5H2O is dissolved in 100mL's
Remove CO2Solution A is made in water；What the another NaOH for taking 8.0g (0.2mol) was dissolved in 100mL removes CO2Solution B is obtained in water.At 25 DEG C
Under, A and B is added drop-wise to simultaneously and removes CO containing 50mL2In the four round flask of water, 1 drop/sec of rate of addition is kept, is stirred strongly
Mix, pH value is maintained between 8~9, continue to stir 30min after completion of dropping, in crystallization 24h at 65 DEG C, suction filtration is washed into
Property, 85 DEG C of dry 18h, grinding obtains zinc-tin binary hydrotalcite.X-ray diffractogram (XRD) is as shown in figure 1, wherein zinc-tin ratio is
3:1, i.e. x are that 0.25, m is 0.5, and chemical general formula is：
[Zn2+ 0.75Sn4+ 0.25(OH)2](NO3 -)0.5·0.5H2O]
The energy gap of the zinc-tin binary hydrotalcite of embodiment 2
Zinc-tin ratio prepared by the method for Example 1 is 3:1 zinc-tin binary hydrotalcite 2000mg, in UV-vis spectroscopy
Scanning 200~800nm wave-length coverages in photometer (type of Shimadzu -2550), survey the diffusing reflection spectrum of zinc-tin binary hydrotalcite, see figure
2.According to the spectrogram that diffuses of gained, pass through formula α h ν=K (h ν-Eg)n/2Calculate energy gap, wherein α, h, ν, K, EgPoint
Absorption factor, planck constant, light frequency, scale parameter and energy gap are not represented.Take n=1 and with (α h ν)2H ν are made
Figure, the intersection point of extrapolation tangent line and abscissa h ν is energy gap.
Conclusion：The energy gap of zinc-tin binary hydrotalcite is 2.98eV, and optional xenon lamp does excitation source.
The photocatalysis of embodiment 3 is tested
At 25 DEG C, the mixed solution of 50ml methyl oranges (6mg/L) and methylene blue (3mg/L) is taken in crystal reaction tube
In, strong agitation, then weigh the zinc-tin binary hydrotalcite 50mg of the method for embodiment 1 preparation and be put into reaction tube, and control pH=
7,30min is first stirred under dark condition and reaches that adsorption-desorption is balanced, then solution is in 500W xenon lamp (380nm<λ<760nm)
Light-catalyzed reaction is carried out under irradiation and lasting strong agitation.Zinc-tin hydrotalcite material is to methyl orange in reaction system and methylene blue
Total degradation rate D1And D2It can be calculated respectively with formula (1) and (2), i.e.,
D1=1-C1/C10Formula (1)
D2=1-C2/C20Formula (2)
In formula (1) (2), C10And C20Methyl orange and methylene in mixed dye are adsorbed after 30min respectively under dark condition
The blue mass concentration of base.C1And C2It is that methyl orange in mixed dye after light-catalyzed reaction certain time and the quality of methylene blue are dense
Degree.C1And C2Value measure by the following method：Every 60min, 3mL solution is taken to filter, filtrate is inhaled in the maximum of methyl orange respectively
Its absorbance is measured under the maximum absorption wavelength (662nm) for receiving wavelength (464nm) and methylene blue, then according to methyl orange and Asia
The standard curve of methyl blue obtains corresponding mass concentration.
Require that 30min is first adsorbed under dark condition reaches adsorption equilibrium in embodiment, be to be arranged in measurement data
Except absorption is on light-catalysed influence, it is easy to contrast total degradation rate and itself photodissociation rate data.During actual industrial production, it can add
Direct xenon lamp irradiation carries out photodissociation after zinc-tin binary hydrotalcite.
Enter line blank test (being not added with zinc-tin binary hydrotalcite) under the conditions of same 500W Xenon light shining, obtain methyl
Itself photodissociation rate d of orange and methylene blue1And d2, calculated by formula (3) and (4), i.e.,
d1=1-c1/c10Formula (3)
d2=1-c2/c20Formula (4)
In formula (3) (4), c10And c20Methyl orange and the initial mass concentration of methylene blue respectively in mixed dye.c1
And c2For methyl orange and the mass concentration of methylene blue in mixed dye after illumination certain time.c1And c2Value pass through such as lower section
Method is measured：Every 60min, 3mL solution is taken to be inhaled respectively in the maximum absorption wavelength (464nm) of methyl orange and the maximum of methylene blue
Receive and measure its absorbance under wavelength (662nm), corresponding quality is then obtained according to the standard curve of methyl orange and methylene blue
Concentration.The total degradation rate and auto-degradation rate curve of mixed dye (methyl orange and methylene blue) are as shown in Figure 3.
In the photocatalysis experiment of embodiment 3, sample, determine in 200~800nm in illumination 0,1,3,5,7,9h respectively
In the range of mixed dye absorbance, respectively using wavelength as abscissa, the absorbance of mixed dye is ordinate, obtains mixing dye
The ultraviolet-visible degraded spectrogram of material is shown in Fig. 4.As seen from Figure 4, with the increase of light application time, the absorbance of mixed dye
Constantly reducing, illustrating that mixed dye is constantly degraded under catalyst action.464nm and 662nm two peaks are represented respectively
The absorption maximum characteristic peak of methyl orange and methylene blue.
Conclusion：Under xenon lamp irradiation, the total degradation rate of methyl orange and methylene blue is respectively 97.5% and 95.1%, itself
Photodissociation rate is respectively 70.3% and 21.2%, and wherein zinc-tin binary hydrotalcite is to methyl orange and the photocatalytic activity of methylene blue
For 27.2% and 73.9%.
The preparation of the standard curve of embodiment 4
By initial concentration for 100mg/L methyl orange solution based on, compound concentration be 1.00mg/L, 2.00mg/L,
4.00mg/L, 6.00mg/L, 8.00mg/L, 12.00mg/L solution, using deionized water as blank reference, with Shimadzu -2550
Type ultraviolet-visible spectrophotometer determines the absorbance of each solution at 464nm, carries out linear fit and obtains methyl orange solution suction
The standard curve of luminosity A- concentration Cs, as shown in Figure 5.
By initial concentration for 100mg/L methylene blue solution based on, compound concentration be 0.58mg/L, 1.16mg/L,
2.32mg/L, 4.64mg/L, 9.28mg/L, 17.4mg/L solution, using deionized water as blank reference, with Shimadzu -2550
Type ultraviolet-visible spectrophotometer determines the absorbance of each solution at 662nm, carries out linear fit and obtains methylene blue solution
The standard curve of absorbance A-concentration C, as shown in Figure 6.
Claims (4)
1. a kind of photocatalytic degradation method of low concentration mixed dye, the mixed dye refers to the mixed of methyl orange and methylene blue
Close dyestuff, it is characterised in that methods described is：The mixed dye that zinc-tin binary hydrotalcite is placed in into methyl orange and methylene blue is molten
In liquid, under room temperature, pH value neutrallty condition, 10~15h is irradiated with xenon lamp, stirring makes methyl orange and methylene blue degrade, dropped
Dye solution after solution processing；The zinc-tin binary hydrotalcite quality consumption is calculated as 0.02 with the volume of mixed dye solution~
2.0mg/mL；
The chemical general formula of the zinc-tin binary hydrotalcite is [Zn2+ 1-xSn4+ x(OH)2](NO3 -)2x·mH2O], wherein x is Sn4+/
[Sn4++Zn2+] mol ratio, 0<x<1, m is crystallization water quantity；The wavelength of the xenon lamp be 380nm~760nm, power 500~
1000W。
2. the method as described in claim 1, it is characterised in that the zinc-tin binary hydrotalcite chemical general formula is [Zn2+ 0.75Sn4 + 0.25(OH)2](NO3 -)0.5·0.5H2O]。
3. the method as described in claim 1, it is characterised in that the zinc-tin binary hydrotalcite quality consumption is molten with mixed dye
The volume of liquid is calculated as 1.0mg/mL.
4. the method as described in claim 1, it is characterised in that the mass concentration of methyl orange is 0.5 in the mixed dye solution
~24mg/L, the mass concentration of methylene blue is 1~12mg/L.
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Effective date of registration: 20191122 Address after: Room 1,020, Nanxun Science and Technology Pioneering Park, No. 666 Chaoyang Road, Nanxun District, Huzhou City, Zhejiang Province, 313000 Patentee after: Huzhou You Yan Intellectual Property Service Co.,Ltd. Address before: 313000 Room 1403, 14th Floor, Building B, Freeport, Headquarters 1188 District Fulu Road, Wuxing District, Huzhou City, Zhejiang Province Patentee before: Zhejiang creation Intellectual Property Service Co.,Ltd. Effective date of registration: 20191122 Address after: 313000 Room 1403, 14th Floor, Building B, Freeport, Headquarters 1188 District Fulu Road, Wuxing District, Huzhou City, Zhejiang Province Patentee after: Zhejiang creation Intellectual Property Service Co.,Ltd. Address before: The city Zhaohui six districts Chao Wang Road Hangzhou City, Zhejiang province 310014 18 Patentee before: Zhejiang University of Technology |