CN109095585A - A method of for degrading azoic dye waste water - Google Patents
A method of for degrading azoic dye waste water Download PDFInfo
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- CN109095585A CN109095585A CN201811154831.9A CN201811154831A CN109095585A CN 109095585 A CN109095585 A CN 109095585A CN 201811154831 A CN201811154831 A CN 201811154831A CN 109095585 A CN109095585 A CN 109095585A
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- waste water
- solution
- based amorphous
- degradation
- band
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- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The present invention relates to a kind of methods for degrading azoic dye waste water, it is characterised in that: it uses Fe68Co10Si8B13AMORPHOUS ALLOY RIBBONS, and H is added2O2The degradation for promoting azo dye wastewater with PS (Na2S2O8), under the action of mechanical stirring, due to H2O2With the synergistic effect of PS, greatly improve the degradation efficiency of azo dyes, its maximum absorbance is detected using ultraviolet-visible spectrophotometer, there is apparent degradation effect to direct blue dye solution, the removal rate that dyestuff is degraded 5 minutes is up to 99% or more.
Description
Technical field
The present invention relates to a kind of methods for sewage of degrading, and belong to new material in sewage treatment application field.
Background technique
Since 1875 for the first time by Perkin synthetic organic dye since, until last century Mo, the annual output of organic dyestuff
Amount is close to 100 tons, and wherein more than half is azo dyes.Azo dyes is a kind of organic compound of azo group both ends connection aryl
Object is fabric clothing most widely used one kind synthetic dyestuffs in dyeing and printing process, for a variety of natural and synthetic fibers
Dyeing and stamp, are also used for the coloring of paint, plastics, rubber etc..According to investigation, there is about 12% dyestuff to flow into waste water every year
In, if not passing through processing appropriate, flows into waste water in rivers and lakes or underground water, ecological environment will be caused greatly
Destruction.
The method of existing frequently-used processing azo dyes mainly active carbon adsorption, biological degradation method, photocatalytic method etc..
Active carbon adsorption is a kind of traditional processing method, but the molecule knot of azo dyes can not be destroyed by being only limitted to physical absorption
Structure, subsequent processing work are still sufficiently complex.Biodegradable rule is often limited to the environmental condition of degradation, needs comparable
Equipment guarantee improves cost, limits its use scope.Photocatalytic method since the price is very expensive, make its promote and apply by
Limitation is arrived.
Amorphous alloy material can be used for azo dyes of degrading, and relative to zeroth order iron powder, the drop of Fe-based amorphous alloy
Solution speed can improve 1000 times of (S.Xie, P.Huang, J.J.Kruzic, X.Zeng and H.Qian, Scientific
Reports, 2016,6,1~10), meanwhile, Fe-based amorphous alloy has ferromagnetism, and band can be recycled and is used for multiple times.However,
Although the effect with individual Fe-based amorphous band for degrading waste water processing has very big advantage compared with reduced iron powder,
It is that its effect can be by adding H2O2Addition with the different proportion of PS significantly improves its degradation efficiency, therefore, by iron-based
Amorphous alloy+H2O2Degradation sewage (non-illuminated conditions) of+PS for printing and dyeing has a good application prospect.
Summary of the invention
The object of the present invention is to provide the methods for degrading azoic dye waste water, by adding different Fe-based amorphous conjunctions
Gold ribbon material, PS, H2O2 match example, use H2SO4Or NaOH solution adjusts pH, improves the speed of its sewage degradation, and by getting rid of band
Method preparation, makes sewage treatment (azo dyes) alloy Cheap highly effective, and amorphous ribbon can be recycled and is used for multiple times, preparation method letter
It is single, easily realize volume production.
The present invention is achieved through the following technical solutions:
1. the ferrum-based amorphous alloy strip of sewage degradation of the present invention exists with strips, in the alloy in alloy
The atomic percent of Fe, Co, Si, B, Sm be Fe68Co10Si8B14。
2. in the present invention, the specification limit of ferrum-based amorphous alloy strip is as follows: 2~6mm of strip width；Beam thickness 20~
100μm；1~20mm of band length.
3. the ferrum-based amorphous alloy strip of the present invention for sewage degradation, includes the following steps:
Carrying device is got rid of for 40m/s using copper roller surface linear velocity, wherein the diameter of test tube is 14mm；The aperture of bottom is straight
Diameter is 1mm；Height of the test tube from copper roller coil is about 1mm；The time of intermediate frequency (IF) smelting is 60 seconds or so.Band is characterized in that:
With complete amorphous feature.
4. Fe-based amorphous alloy item of the present invention is applied to the degradation treatment in dyeing and printing sewage.
5. in preferred experiment method, the weight range of Fe-based amorphous band in 0.25~1.0g/L, preferably 0.5~
0.75g/L；Concentration range of the H2O2 in waste water is 0.06~0.15mM；Preferably 0.06~0.09mM；PS is in waste water
Weight range is in 0~1.0mM；It is preferable over 0.5~0.75mM；
6. Fe-based amorphous band is 0.50g/L in preferred experiment method；H2O2Solution is 0.03mM；PS is
0.50mM.It uses ultraviolet-visible spectrophotometer to detect maximum absorbance, and the removal rate that dyestuff is degraded 5 minutes is high
Up to 95%
7. for the pH of the method 4.0~12, pH value is preferably 6.0~8.0 in preferred experiment method.
8. the churned mechanically revolving speed in step (1) is 200r/min in preferred experiment method；Water bath with thermostatic control control
Temperature be 35 DEG C
Detailed description of the invention
Fig. 1 is Fe of the present invention68Co10Si8B14+H2O2+ PS is under the acid condition of pH=6, to direct before and after reaction 5min
The UV-Vis spectra figure of blue 2B solution.
Fig. 2 is Fe of the present invention68Co10Si8B14+H2O2+ PS is under the weak basic condition of pH=8, to straight before and after reaction 5min
Connect the UV-Vis spectra figure of blue 2B solution.
Fig. 3 is Fe of the present invention68Co10Si8B14+H2O2+ PS is under the alkaline condition of pH=10, to direct before and after reaction 5min
The UV-Vis spectra figure of blue 2B solution.
The present invention compared with the existing technology, have following advantages and effects
(1) compared with individually addition Fe-based amorphous alloy, Fe68Co10Si8B14+H2O2+ PS optimal proportion, use it is ultraviolet-
Visible light photometer detects maximum absorbance, and the removal rate that dyestuff is degraded 5 minutes is up to 95%, than independent
Fe68Co10Si8B14It is only 83.1% in the removal rate that dyestuff is degraded 60 minutes, result greatly shortens degradation time, improves drop
Rate is solved, and is obviously improved raising removal rate；
(2)Fe68Co10Si8B14+H2O2+ PS is suitble to degrade within different pH value ranges, in pH=6.0,
Degradation efficiency is optimal, and removal rate can reach 99% or more；
(3)Fe68Co10Si8B14+H2O2+ PS is under the alkaline environment of pH=10, using the Fe of 0.75g/L68Co10Si8B14
Band, 0.75mM PS, 0.06mM H2O2Optimal proportion, degradation removal rate can reach 83.77%, can be significant
The broad degradation rate under alkaline environment.
Specific embodiment
Specific embodiment is more specifically described in detail the present invention with reference to the accompanying drawings and examples.
Embodiment 1 prepares ferrum-based amorphous alloy strip, fixed azo dyes concentration, and pH=6 determines optimal proportion
1) select commercially available high-purity Fe block, Co block, Si and FeB alloy (Fe:B=79.5:20wt.%) block as raw material,
Pure metal block is first subjected to surface scale disengaging and as in dehydrated alcohol, preventing from aoxidizing.
2) the master alloy raw material 1) prepared the repeats melting 5 times as in the water jacketed copper crucible of vacuum melting furnace, to protect
Demonstrate,prove the uniformity of parent material.
3) master alloy mother's ingot made from 2) step is polished after its surface scale, is put into single roller and gets rid of with machine (WK- II)
Bottom opening diameter is in the quartz test tube of 1mm, and the linear resonance surface velocity of the single roller of adjusting is 42m/s, prepares Fe-based amorphous band.
Using the Fe prepared in example 168Co10Si8B14Fe-based amorphous band carries out the degradation of azo dyes, detailed process
It is as follows:
Using distilled water prepare direct blue 2B solution, solution concentration 100mg/L, for use.
Weigh the Fe in the example 1 of 0.5g68Co10Si8B14Ferrum-based amorphous alloy strip pours into the straight of configured 500mL
Blue 2B solution is connect, at a temperature of 35 DEG C of water bath with thermostatic control, and using the pH=6 of the acid solution of 0.1mM adjusting direct blue 2B solution, is adopted
Solution is stirred with mechanical agitator (Teflon stir bar), the revolving speed of blender is 200r/min.Using difference
The Fe of proportion68Co10Si8B14Band, PS and H2O2 after degradation 5 minutes, extract 4~5mL solution and carry out ultraviolet-visible light light
The comparison of meter is spent, after reaction 5 minutes, when using Fe68Co10Si8B14=0.75g/L, PS=0.75mM and H2O2=0.12mM
Optimal proportion when, dyestuff removal rate reaches 99.5% (as shown in Figure 1).
Embodiment 2 prepares ferrum-based amorphous alloy strip, fixed azo dyes concentration, and pH=8 determines optimal proportion
1) select commercially available high-purity Fe block, Co block, Si and FeB alloy (Fe:B=79.5:20wt.%) block as raw material,
Pure metal block is first subjected to surface scale disengaging and as in dehydrated alcohol, preventing from aoxidizing.
2) the master alloy raw material 1) prepared the repeats melting 5 times as in the water jacketed copper crucible of vacuum melting furnace, to protect
Demonstrate,prove the uniformity of parent material.
3) master alloy mother's ingot made from 2) step is polished after its surface scale, is put into single roller and gets rid of with machine (WK- II)
Bottom opening diameter is in the quartz test tube of 1mm, and the linear resonance surface velocity of the single roller of adjusting is 42m/s, prepares Fe-based amorphous band.
Using the Fe prepared in example 268Co10Si8B14Fe-based amorphous band carries out the degradation of azo dyes, detailed process
It is as follows:
Using distilled water prepare direct blue 2B solution, solution concentration 100mg/L, for use.
Weigh the Fe in the example 1 of 0.5g68Co10Si8B14Ferrum-based amorphous alloy strip pours into the straight of configured 500mL
Blue 2B solution is connect, at a temperature of 35 DEG C of water bath with thermostatic control, and using the pH=of the NaOH solution of 0.1mM adjusting direct blue 2B solution
10, solution is stirred using mechanical agitator (Teflon stir bar), the revolving speed of blender is 200r/min.Using
The Fe of different ratio68Co10Si8B14Band, PS and H2O2, after degradation 5 minutes, extract 4~5mL solution and carry out ultraviolet-visible
The photometric comparison of light, after reaction 5 minutes, when using Fe68Co10Si8B14=1.0g/L, PS=0.5mM and H2O2=
When the optimal proportion of 0.09mM, dyestuff removal rate reaches 99.6% (as shown in Figure 2).
Embodiment 3 prepares ferrum-based amorphous alloy strip, fixed azo dyes concentration, and pH=10 determines optimal proportion
1) select commercially available high-purity Fe block, Co block, Si and FeB alloy (Fe:B=79.5:20wt.%) block as raw material,
Pure metal block is first subjected to surface scale disengaging and as in dehydrated alcohol, preventing from aoxidizing.
2) the master alloy raw material 1) prepared the repeats melting 5 times as in the water jacketed copper crucible of vacuum melting furnace, to protect
Demonstrate,prove the uniformity of parent material.
3) master alloy mother's ingot made from 2) step is polished after its surface scale, is put into single roller and gets rid of with machine (WK- II)
Bottom opening diameter is in the quartz test tube of 1mm, and the linear resonance surface velocity of the single roller of adjusting is 42m/s, prepares Fe-based amorphous band.
Using the Fe prepared in example 368Co10Si8B14Fe-based amorphous band carries out the degradation of azo dyes, detailed process
It is as follows:
Using distilled water prepare direct blue 2B solution, solution concentration 100mg/L, for use.
Weigh the Fe in the example 1 of 0.5g68Co10Si8B14Ferrum-based amorphous alloy strip pours into the straight of configured 500mL
Blue 2B solution is connect, at a temperature of 35 DEG C of water bath with thermostatic control, and uses the pH=8 of the NaOH solution adjusting direct blue 2B solution of 0.1mM,
Solution is stirred using mechanical agitator (Teflon stir bar), the revolving speed of blender is 200r/min.Using not
With the Fe of proportion68Co10Si8B14Band, PS and H2O2, after degradation 5 minutes, extract 4~5mL solution and carry out ultraviolet-visible light
Photometric comparison, after reaction 5 minutes, when using Fe68Co10Si8B14=0.75g/L, PS=0.75mM and H2O2=
When the optimal proportion of 0.06mM, dyestuff removal rate reaches 83.7% (as shown in Figure 3).
Claims (6)
1. a kind of method for degrading azoic dye waste water, it is characterised in that include the following steps；
(1) by azo dye wastewater as in beaker, waste water solution thermostat water bath controls temperature, and using churned mechanically
Method is stirred uniformly solution；
(2) Fe is added in above-mentioned waste water68Co10Si8B13Fe-based amorphous band adjusts weight range of the band in the waste water
In 0.25~1.0g/L；
(3) H is added in above-mentioned waste water2O2With PS (Na2S2O8), H is adjusted2O2Concentration range in the waste water is 0.06~
The weight range of 0.15mM, PS in the waste water is in 0~1.0mM.
2. the method for the directly blue azo dye wastewater of degradation according to claim 1, it is characterised in that: Fe-based amorphous band
Weight range in 0.25~1.0g/L, preferably 0.5~0.75g/L；H2O2Concentration range in waste water is 0.06~
0.15mM；Preferably 0.06~0.09mM；Weight range of the PS in waste water is in 0~1.0mM；It is preferable over 0.5~0.75mM.
3. the method for azo dye wastewater according to claim 2, it is characterised in that: Fe-based amorphous band is 0.50g/L；
H2O2Solution is 0.03mM；PS is 0.50mM.
4. optimal proportion according to claim 3, uses ultraviolet-visible spectrophotometer to examine maximum absorbance
It surveys, the removal rate that dyestuff is degraded 5 minutes is up to 95%.
5. the method for degrading azoic dye waste water according to claim 1-4, it is characterised in that: the method
For pH 4.0~12, pH value is preferably 8.00.
6. the method for degrading azoic dye waste water according to claim 1-5, it is characterised in that: in step (1)
Churned mechanically revolving speed be 200r/min；The temperature of water bath with thermostatic control control is 35 DEG C.
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