CN108046402A - A kind of method using cu-based amorphous alloys degradation pigment wastewater - Google Patents
A kind of method using cu-based amorphous alloys degradation pigment wastewater Download PDFInfo
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- CN108046402A CN108046402A CN201711258823.4A CN201711258823A CN108046402A CN 108046402 A CN108046402 A CN 108046402A CN 201711258823 A CN201711258823 A CN 201711258823A CN 108046402 A CN108046402 A CN 108046402A
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- alloy
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- waste water
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/001—Amorphous alloys with Cu as the major constituent
-
- 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
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
A kind of method using cu-based amorphous alloys degradation pigment wastewater is related to a kind of wastewater treatment method, and the cu-based amorphous alloys that the method uses are Cu46Zr44.5Al7.5Y2 AMORPHOUS ALLOY RIBBONSs, and ingredient and atomic percent are：46%Cu, 44.5%Zr, 7.5%Al, 2%Y；Cu46Zr44.5Al7.5Y2 AMORPHOUS ALLOY RIBBONSs are prepared first, then add in Cu46Zr44.5Al7.5Y2 AMORPHOUS ALLOY RIBBONSs and permonosulphuric acid potassium solution in waste water from dyestuff, the potentiometric titrations oxidative degradation waste water from dyestuff generated using activation；The present invention both had higher chemism using cu-based amorphous alloys surface, while also had excellent degradation property and stability using cu-based amorphous alloys.This method equipment is simple, easily-controllable, and catalyst cu-based amorphous alloys prepare fairly simple, are easily recycled.
Description
Technical field
It is specially a kind of to be dropped using cu-based amorphous alloys activation peroxy-monosulfate the present invention relates to a kind of wastewater treatment method
The method for solving waste water from dyestuff.
Background technology
Water resource is precious resources for the survival of mankind, and with China's rapid development of economy, Development of China's Urbanization adds
It is fast etc., shortage of water resources and water pollution in the whole country oneself through becoming the problem of sternness that our people faces.Print
Dye industry is both the rich and influential family of water resources consumption, while is also important water pollution source, and to be dyeing commonly use azo dyes
Dyestuff produces waste water difficult for biological degradation and with toxicity.
To mitigate the harmful effect caused by water pollution, it is necessary to greatly develop techniques of Dyeing Wastewater Treatment.Currently in order to control
The dye discoloration of water body, world industry developed country generally uses compares the promising biotechnology of tool, but its flow is complicated,
Capital cost is high, takes up a large area, operating cost height, while little to the decolorization of many organic pollutions.Therefore, to have
Effect ground solves pollution problem caused by dyeing waste water, and research and development are not only efficient, energy saving but also practicable processing new technology, oneself into
The new direction studied for wastewater processing technology in the world today.In recent years, since high-level oxidation technology is to poisonous and harmful, difficult drop
The relatively low organic pollution of solution, biodegradability has good degradation effect, and receives significant attention.Wherein by activating persulfuric acid
Salt generates potentiometric titrations degradable organic pollutant and is considered as a kind of advanced oxidation technology.Potentiometric titrations have compared with
High oxidation-reduction potential and longer half-life period, when degradable organic pollutant, are influenced smaller by pH, are 4-9 models in pH
Good degradation can be all obtained in enclosing.Pass through heat, ultrasonic wave, ultraviolet light, transition metal (Co2 +、Fe2 + 、Mn2 +Deng), metal
Oxide (Co3O4、Fe3O4 、Mn2O3Deng), activated carbon the methods of activation persulfate can generate potentiometric titrations.Its
In with transition metal ions and its oxide most activation efficiency, but there is also metal ion loss, cause secondary dye, do not have weight
The limitations such as multiple usability.
The study found that use three-dimensional dimension for the nano transition metal or oxidate powder of nanometer scale be improve degradation efficiency
One of effective means.But high production cost, bio-toxicity and due to high-specific surface area bring it is easy reunite with it is oxidizable
The problems such as cause the catalyst of nanometer scale preserve, transport and using process all there are it is certain the problem of.How to keep
Make it that there can be high reactivity and with good stability in the case of the advantages such as catalyst itself low cost, and
No biotoxicity becomes a research direction.
The content of the invention
It is an object of the invention to provide a kind of peroxy-monosulfate degradation of dye waste water is activated using cu-based amorphous alloys
Method both had higher chemism using cu-based amorphous alloys surface, while also using cu-based amorphous alloys with excellent
Degradation property and stability.This method equipment is simple, easily-controllable, and catalyst cu-based amorphous alloys prepare fairly simple, are easily recycled
It recycles.
The technical scheme is that：
A kind of method using cu-based amorphous alloys degradation pigment wastewater, the cu-based amorphous alloys that the method uses are
Cu46Zr44.5Al7.5Y2AMORPHOUS ALLOY RIBBONS, ingredient and atomic percent are：46%Cu, 44.5%Zr, 7.5%Al, 2%Y；First
Prepare Cu46Zr44.5Al7.5Y2AMORPHOUS ALLOY RIBBONS, then by Cu46Zr44.5Al7.5Y2AMORPHOUS ALLOY RIBBONS and permonosulphuric acid potassium are molten
Liquid is added in waste water from dyestuff, the potentiometric titrations oxidative degradation waste water from dyestuff generated using activation；
It is as follows：
1）Cu46Zr44.5Al7.5Y2It is prepared by AMORPHOUS ALLOY RIBBONS
A. dispensing：Simple substance raw material used in experiment is not less than 99.9 % using purity（Mass percent）Cu, Zr, Al and Y；Profit
The quality of above-mentioned simple substance raw material is weighed up with precision electronic balance, the gross mass of above-mentioned simple substance raw material is 100 grams；Then petroleum ether is used
Ultrasonic cleaning is carried out to above-mentioned simple substance raw material with absolute ethyl alcohol, finally above-mentioned simple substance raw material is mixed and is put into tungsten electrode magnetic control
Inside electric arc furnaces；
B. master alloy melting：Tungsten electrode magnetic control arc stove working chamber is evacuated to 7 × 10-4Pa, then be passed through purity and be
99.99%（Mass percent）High-purity argon gas, Titanium is melted, by Titanium at high temperature strong oxidation reaction with
The partial pressure of oxygen in working chamber is further reduced, then the above-mentioned simple substance raw material of melting again, becomes mother alloy ingot；
C. single roller gets rid of band：After above-mentioned melted master alloy ingot descale, fritter is crushed to；Then 50 grams of fritter is closed
Ingot is put into below with aperture（1-1.5 millimeters of diameter）Quartz ampoule in after, then the quartz ampoule equipped with fritter alloy put into
In induction furnace, treat working chamber vacuum to 2 × 10-3Pa, then induction melting is carried out, form Cu46Zr44.5Al7.5Y2Non-crystaline amorphous metal item
Band；
2）It is accurate to weigh 5-10 grams of permonosulphuric acid potassium and be dissolved in deionized water, transfer in 1000 milliliters of volumetric flasks and spend from
Sub- water is diluted to volumetric flask groove, prepares permonosulphuric acid potassium solution；
3）The degradation process of waste water from dyestuff：Above-mentioned solution is added in into waste water from dyestuff, adds 2-6 grams
Cu46Zr44.5Al7.5Y2 AMORPHOUS ALLOY RIBBONSs carry out the degradation of waste water from dyestuff.
A kind of method using cu-based amorphous alloys degradation pigment wastewater, the mother alloy ingot melting at least need
It turns refining 5 times, after the completion of melting, mother alloy ingot is cooled to room temperature with tungsten electrode magnetic control arc stove, then opens tungsten electrode magnetic control electricity
Arc stove takes out mother alloy ingot.
A kind of described method using cu-based amorphous alloys degradation pigment wastewater during the induction melting, treats that fritter closes
After gold becomes alloy melt by solid, and the temperature of alloy melt reaches preset temperature, immediately with high-purity argon gas by quartz ampoule
Interior alloy melt is sprayed onto high-speed rotating copper roller surface, forms Cu46Zr44.5Al7.5Y2 AMORPHOUS ALLOY RIBBONSs.
A kind of method using cu-based amorphous alloys degradation pigment wastewater, the degradation of the waste water from dyestuff use
500 milliliters of beakers are reactor, and degradation object is 150 milliliters of the simulation orange beta-naphthol waste water dissolving that concentration is 5-15 mg/litres, and
Reactor is placed on magnetic stirring apparatus, tune pH value is 2-7, and magnetic stirring apparatus rotating speed is 200 revs/min, solution temperature 25-
50℃。
The present invention has the following advantages：
1st, Cu prepared by the present invention46Zr44.5Al7.5Y2AMORPHOUS ALLOY RIBBONS had both had higher using cu-based amorphous alloys surface
Chemism, while also there is excellent degradation property and stability using cu-based amorphous alloys.
2nd, cu-based amorphous alloys Forming ability of the present invention is strong, and reusable, production cost is low, technology maturation, without big
The fund of amount, industrialization are easier to.
3rd, simplification of flowsheet of the present invention, it is easy to operate, reduce cost of water treatment.
Description of the drawings
Fig. 1 is the Cu for preparing under the conditions of present example 146Zr44.5Al7.5Y2AMORPHOUS ALLOY RIBBONS photomacrograph；
Fig. 2 is the Cu for preparing under the conditions of present example 146Zr44.5Al7.5Y2AMORPHOUS ALLOY RIBBONS activation permonosulphuric acid potassium degradation
Contrast on effect digital photograph after orange beta-naphthol different time.
Specific embodiment
The present invention is described in detail by the following examples.
Embodiment 1
1、Cu46Zr44.5Al7.5Y2It is prepared by AMORPHOUS ALLOY RIBBONS
（1）Dispensing：Simple substance raw material used in experiment is not less than 99.9 % using purity（Mass percent）Cu, Zr, Al and Y.
The quality of above-mentioned simple substance raw material is weighed up using precision electronic balance, the gross mass of above-mentioned simple substance raw material is 100 grams.Then oil is used
Ether and absolute ethyl alcohol carry out ultrasonic cleaning to above-mentioned simple substance raw material, and finally above-mentioned simple substance raw material is mixed and is put into tungsten electrode magnetic
It controls inside electric arc furnaces.
（2）Master alloy melting：Tungsten electrode magnetic control arc stove working chamber is evacuated to 7 × 10-4Pa, then be passed through purity and be
99.99%（Mass percent）High-purity argon gas.Titanium is melted, by Titanium at high temperature strong oxidation reaction with
The partial pressure of oxygen in working chamber is further reduced, then the above-mentioned simple substance raw material of melting again, becomes mother alloy ingot.It is female to ensure
The chemical composition uniformity of alloy cast ingot, mother alloy ingot at least need to turn refining 5 times.After the completion of melting, mother alloy ingot is with tungsten
Pole magnetic control arc stove is cooled to room temperature, and is then opened tungsten electrode magnetic control arc stove and is taken out mother alloy ingot.
（3）Single roller gets rid of band：After above-mentioned melted master alloy ingot descale, fritter is crushed to；Then by 50 grams
Fritter alloy pig is put into below with aperture（1.5 millimeters of diameter）Quartz ampoule in after, then the quartz ampoule equipped with fritter alloy
It puts induction furnace into, treats working chamber vacuum to 2 × 10-3Pa, then carry out induction melting；Treat that fritter alloy becomes alloy by solid and melts
Body, and after the temperature of alloy melt reaches preset temperature, the alloy melt in quartz ampoule is sprayed onto height with high-purity argon gas immediately
The copper roller surface of speed rotation, forms Cu46Zr44.5Al7.5Y2AMORPHOUS ALLOY RIBBONS.
2nd, 6 grams of permonosulphuric acid potassium accurately are weighed to be dissolved in deionized water, transfers in 1000 milliliters of volumetric flasks and spend
Ionized water is diluted to volumetric flask groove, prepares permonosulphuric acid potassium solution.
3rd, the degradation process of waste water from dyestuff：Above-mentioned solution is added in into waste water from dyestuff, adds 3 grams
Cu46Zr44.5Al7.5Y2AMORPHOUS ALLOY RIBBONS carries out the degradation of waste water from dyestuff.500 milliliters of beakers are used as reactor, degradation pair
As if concentration dissolves 150 milliliters for the simulation orange beta-naphthol waste water of 10 mg/litres, and reactor is placed on magnetic stirring apparatus, it adjusts
PH value is 6.5, and magnetic stirring apparatus rotating speed is 200 revs/min, and solution temperature is 25 DEG C.
Fig. 1 is the Cu prepared46Zr44.5Al7.5Y2AMORPHOUS ALLOY RIBBONS photomacrograph.As can be seen from Figure 2 with the time
Extend, the color of orange beta-naphthol gradually becomes colourless, illustrates that orange beta-naphthol has been removed.
Embodiment 2
1、Cu46Zr44.5Al7.5Y2It is prepared by AMORPHOUS ALLOY RIBBONS
（1）Dispensing：Simple substance raw material used in experiment is not less than 99.9 % using purity（Mass percent）Cu, Zr, Al and Y.
The quality of above-mentioned simple substance raw material is weighed up using precision electronic balance, the gross mass of above-mentioned simple substance raw material is 100 grams.Then oil is used
Ether and absolute ethyl alcohol carry out ultrasonic cleaning to above-mentioned simple substance raw material, and finally above-mentioned simple substance raw material is mixed and is put into tungsten electrode magnetic
It controls inside electric arc furnaces.
（2）Master alloy melting：Tungsten electrode magnetic control arc stove working chamber is evacuated to 7 × 10-4Pa, then be passed through purity and be
99.99%（Mass percent）High-purity argon gas.Titanium is melted, by Titanium at high temperature strong oxidation reaction with
The partial pressure of oxygen in working chamber is further reduced, then the above-mentioned simple substance raw material of melting again, becomes mother alloy ingot.It is female to ensure
The chemical composition uniformity of alloy cast ingot, mother alloy ingot at least need to turn refining 5 times.After the completion of melting, mother alloy ingot is with tungsten
Pole magnetic control arc stove is cooled to room temperature, and is then opened tungsten electrode magnetic control arc stove and is taken out mother alloy ingot.
（3）Single roller gets rid of band：After above-mentioned melted master alloy ingot descale, fritter is crushed to；Then by 50 grams
Fritter alloy pig is put into below with aperture（1.5 millimeters of diameter）Quartz ampoule in after, then the quartz ampoule equipped with fritter alloy
It puts induction furnace into, treats working chamber vacuum to 2 × 10-3Pa, then carry out induction melting；Treat that fritter alloy becomes alloy by solid and melts
Body, and after the temperature of alloy melt reaches preset temperature, the alloy melt in quartz ampoule is sprayed onto height with high-purity argon gas immediately
The copper roller surface of speed rotation, forms Cu46Zr44.5Al7.5Y2AMORPHOUS ALLOY RIBBONS.
2nd, 10 grams of permonosulphuric acid potassium accurately are weighed to be dissolved in deionized water, transfers in 1000 milliliters of volumetric flasks and spend
Ionized water is diluted to volumetric flask groove, prepares permonosulphuric acid potassium solution.
3rd, the degradation process of waste water from dyestuff：Above-mentioned solution is added in into waste water from dyestuff, adds 2 grams
Cu46Zr44.5Al7.5Y2AMORPHOUS ALLOY RIBBONS carries out the degradation of waste water from dyestuff.500 milliliters of beakers are used as reactor, degradation pair
As if concentration dissolves 150 milliliters for the simulation orange beta-naphthol waste water of 15 mg/litres, and reactor is placed on magnetic stirring apparatus, it adjusts
PH value is 6.5, and magnetic stirring apparatus rotating speed is 200 revs/min, and solution temperature is 25 DEG C.
Embodiment 3
1、Cu46Zr44.5Al7.5Y2It is prepared by AMORPHOUS ALLOY RIBBONS
（1）Dispensing：Simple substance raw material used in experiment is not less than 99.9 % using purity（Mass percent）Cu, Zr, Al and Y.
The quality of above-mentioned simple substance raw material is weighed up using precision electronic balance, the gross mass of above-mentioned simple substance raw material is 100 grams.Then oil is used
Ether and absolute ethyl alcohol carry out ultrasonic cleaning to above-mentioned simple substance raw material, and finally above-mentioned simple substance raw material is mixed and is put into tungsten electrode magnetic
It controls inside electric arc furnaces.
（2）Master alloy melting：Tungsten electrode magnetic control arc stove working chamber is evacuated to 7 × 10-4Pa, then be passed through purity and be
99.99%（Mass percent）High-purity argon gas.Titanium is melted, by Titanium at high temperature strong oxidation reaction with
The partial pressure of oxygen in working chamber is further reduced, then the above-mentioned simple substance raw material of melting again, becomes mother alloy ingot.It is female to ensure
The chemical composition uniformity of alloy cast ingot, mother alloy ingot at least need to turn refining 5 times.After the completion of melting, mother alloy ingot is with tungsten
Pole magnetic control arc stove is cooled to room temperature, and is then opened tungsten electrode magnetic control arc stove and is taken out mother alloy ingot.
（3）Single roller gets rid of band：After above-mentioned melted master alloy ingot descale, fritter is crushed to；Then by 50 grams
Fritter alloy pig is put into below with aperture（1 millimeter of diameter）Quartz ampoule in after, then the quartz ampoule equipped with fritter alloy put
Into in induction furnace, treat working chamber vacuum to 2 × 10-3Pa, then carry out induction melting；Treat that fritter alloy becomes alloy by solid and melts
Body, and after the temperature of alloy melt reaches preset temperature, the alloy melt in quartz ampoule is sprayed onto height with high-purity argon gas immediately
The copper roller surface of speed rotation, forms Cu46Zr44.5Al7.5Y2AMORPHOUS ALLOY RIBBONS.
2nd, 5 grams of permonosulphuric acid potassium accurately are weighed to be dissolved in deionized water, transfers in 1000 milliliters of volumetric flasks and spend
Ionized water is diluted to volumetric flask groove, prepares permonosulphuric acid potassium solution.
3rd, the degradation process of waste water from dyestuff：Above-mentioned solution is added in into waste water from dyestuff, adds 6 grams
Cu46Zr44.5Al7.5Y2AMORPHOUS ALLOY RIBBONS carries out the degradation of waste water from dyestuff.500 milliliters of beakers are used as reactor, degradation pair
As if concentration dissolves 150 milliliters for the simulation orange beta-naphthol waste water of 15 mg/litres, and reactor is placed on magnetic stirring apparatus, it adjusts
PH value is 6.5, and magnetic stirring apparatus rotating speed is 200 revs/min, and solution temperature is 25 DEG C.
Claims (4)
- A kind of 1. method using cu-based amorphous alloys degradation pigment wastewater, which is characterized in that the method uses copper-based non- Peritectic alloy is Cu46Zr44.5Al7.5Y2AMORPHOUS ALLOY RIBBONS, ingredient and atomic percent are：46%Cu, 44.5%Zr, 7.5%Al, 2%Y；Cu is prepared first46Zr44.5Al7.5Y2AMORPHOUS ALLOY RIBBONS, then by Cu46Zr44.5Al7.5Y2AMORPHOUS ALLOY RIBBONS and excessively one Potassium sulfate solution is added in waste water from dyestuff, the potentiometric titrations oxidative degradation waste water from dyestuff generated using activation；It is as follows：1）Cu46Zr44.5Al7.5Y2It is prepared by AMORPHOUS ALLOY RIBBONSA. dispensing：Simple substance raw material used in experiment is not less than 99.9 % using purity（Mass percent）Cu, Zr, Al and Y；Profit The quality of above-mentioned simple substance raw material is weighed up with precision electronic balance, the gross mass of above-mentioned simple substance raw material is 100 grams；Then petroleum ether is used Ultrasonic cleaning is carried out to above-mentioned simple substance raw material with absolute ethyl alcohol, finally above-mentioned simple substance raw material is mixed and is put into tungsten electrode magnetic control Inside electric arc furnaces；B. master alloy melting：Tungsten electrode magnetic control arc stove working chamber is evacuated to 7 × 10-4Pa, then purity is passed through as 99.99% （Mass percent）High-purity argon gas, Titanium is melted, by Titanium at high temperature strong oxidation reaction with further The partial pressure of oxygen in working chamber is reduced, then the above-mentioned simple substance raw material of melting again, become mother alloy ingot；C. single roller gets rid of band：After above-mentioned melted master alloy ingot descale, fritter is crushed to；Then 50 grams of fritter is closed Ingot is put into below with aperture（1-1.5 millimeters of diameter）Quartz ampoule in after, then the quartz ampoule equipped with fritter alloy put into In induction furnace, treat working chamber vacuum to 2 × 10-3Pa, then induction melting is carried out, form Cu46Zr44.5Al7.5Y2Non-crystaline amorphous metal item Band；2）It is accurate to weigh 5-10 grams of permonosulphuric acid potassium and be dissolved in deionized water, transfer in 1000 milliliters of volumetric flasks and spend from Sub- water is diluted to volumetric flask groove, prepares permonosulphuric acid potassium solution；3）The degradation process of waste water from dyestuff：Above-mentioned solution is added in into waste water from dyestuff, adds 2-6 grams Cu46Zr44.5Al7.5Y2 AMORPHOUS ALLOY RIBBONSs carry out the degradation of waste water from dyestuff.
- A kind of 2. method using cu-based amorphous alloys degradation pigment wastewater according to claim 1, which is characterized in that institute Stating mother alloy ingot melting at least needs to turn refining 5 times, and after the completion of melting, mother alloy ingot is cooled to room with tungsten electrode magnetic control arc stove Then temperature opens tungsten electrode magnetic control arc stove and takes out mother alloy ingot.
- A kind of 3. method using cu-based amorphous alloys degradation pigment wastewater according to claim 1, which is characterized in that institute When stating induction melting, after treating that fritter alloy becomes alloy melt by solid, and the temperature of alloy melt reaches preset temperature, stand The alloy melt in quartz ampoule is sprayed onto high-speed rotating copper roller surface with high-purity argon gas, forms Cu46Zr44.5Al7.5Y2 AMORPHOUS ALLOY RIBBONS.
- A kind of 4. method using cu-based amorphous alloys degradation pigment wastewater according to claim 1, which is characterized in that institute The degradation for stating waste water from dyestuff uses 500 milliliters of beakers as reactor, and degradation object is that the simulation that concentration is 5-15 mg/litres is orange II waste water dissolves 150 milliliters, and reactor is placed on magnetic stirring apparatus, and tune pH value is 2-7, and magnetic stirring apparatus rotating speed is 200 Rev/min, solution temperature is 25-50 DEG C.
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| CN110499480A (en) * | 2019-09-30 | 2019-11-26 | 大连理工大学 | A kind of Cu-M-O amorphous alloy and preparation method thereof |
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| CN111389407A (en) * | 2020-05-12 | 2020-07-10 | 辽宁大学 | Copper-based amorphous alloy catalyst and preparation method and application thereof |
| CN113005460A (en) * | 2021-03-12 | 2021-06-22 | 沈阳大学 | Method for improving electrocatalytic oxidation performance of amorphous alloy |
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