CN108220824B - Iron-based amorphous alloy strip and application thereof in degradation treatment of printing and dyeing wastewater - Google Patents
Iron-based amorphous alloy strip and application thereof in degradation treatment of printing and dyeing wastewater Download PDFInfo
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- CN108220824B CN108220824B CN201711346001.1A CN201711346001A CN108220824B CN 108220824 B CN108220824 B CN 108220824B CN 201711346001 A CN201711346001 A CN 201711346001A CN 108220824 B CN108220824 B CN 108220824B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/02—Amorphous alloys with iron as the major constituent
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/003—Making ferrous alloys making amorphous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention belongs to the field of sewage treatment materials, and discloses an iron-based amorphous alloy strip and application thereof in degradation treatment of printing and dyeing sewage. The iron-based amorphous alloy strip comprises the following elements in atomic percentage: fe: 68% -78%, Co: 0-10%, Si: 8% -9%, B: 12% -14%, Sm: 0-4%, Gd: 0 to 4 percent. The preparation method of the iron-based amorphous alloy strip is simple, mass production is easy to realize, the sewage degradation speed can be improved by adding different alloy elements, the amorphous strip can be recycled for multiple times, and the iron-based amorphous alloy strip has the advantages of low cost and obvious sewage treatment effect.
Description
Technical Field
The invention belongs to the field of sewage treatment materials, and particularly relates to an iron-based amorphous alloy strip and application thereof in degradation treatment of printing and dyeing sewage.
Background
Since the first synthesis of organic dyes by Perkin in 1875, the annual production of organic dyes by the end of the last century has approached 100 tons, more than half of which are azo dyes. Azo dyes are organic compounds with aryl groups connected with two ends of azo groups, are synthetic dyes which are most widely applied in textile and clothing printing and dyeing processes, are used for dyeing and printing various natural and synthetic fibers, and are also used for coloring paint, plastics, rubber and the like. According to investigations, about 12% of dye flows into wastewater every year, and if the wastewater is not properly treated, the wastewater flows into rivers, lakes or groundwater, causing great damage to the ecological environment.
The currently used methods for treating azo dyes mainly include activated carbon adsorption, biodegradation, photocatalysis, and the like. The activated carbon adsorption method is a traditional treatment method, but is limited to physical adsorption and cannot damage the molecular structure of the azo dye, and the subsequent treatment work is still very complicated. Biodegradation laws are often limited by the environmental conditions of degradation, require considerable equipment safeguards, increase costs, and limit their scope of use. The photocatalytic method is very expensive, so that the popularization and the application of the photocatalytic method are limited.
The amorphous alloy material can be used for degrading azo dyes, the degradation speed of the iron-based amorphous alloy can be improved by 1000 times (S.Xie, P.Huang, J.J.Kruzic, X.Zeng and H.Qian, Scientific reports,2016,6, 1-10) compared with zero-valent iron powder, and meanwhile, the iron-based amorphous alloy has ferromagnetism, and the strip can be recycled for multiple times. Therefore, the iron-based amorphous alloy has good application prospect in degradation sewage (without light condition) of printing and dyeing, but the degradation capability of the iron-based amorphous alloy on printing and dyeing wastewater is still expected to be further improved.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide the iron-based amorphous alloy strip.
The invention also aims to provide a preparation method of the iron-based amorphous alloy strip.
The invention further aims to provide application of the iron-based amorphous alloy strip in degradation treatment of printing and dyeing wastewater.
The purpose of the invention is realized by the following technical scheme:
an iron-based amorphous alloy strip comprises the following elements in atomic percentage: fe: 68% -78%, Co: 0-10%, Si: 8% -9%, B: 12% -14%, Sm: 0-4%, Gd: 0 to 4 percent.
Preferably, the iron-based amorphous alloy strip has the following element atomic percentage composition: fe: 68% -78%, Co: 6-10%, Si: 8% -9%, B: 12% -14%, Sm: 0 to 4%, or Fe: 68% -78%, Si: 8% -9%, B: 12% -14%, Gd: 0 to 4 percent.
The specification range of the iron-based amorphous alloy strip is as follows: the width of the strip is 2-6 mm, the thickness of the strip is 20-100 μm, and the length of the strip is 1-20 mm.
The preparation method of the iron-based amorphous alloy strip comprises the following preparation steps:
(1) according to the proportion of Fe: 68% -78%, Co: 0-10%, Si: 8% -9%, B: 12% -14%, Sm: 0-4%, Gd: proportioning 0-4% of elements, and performing surface pretreatment on the metal raw material;
(2) uniformly smelting the metal raw material pretreated in the step (1) in a vacuum smelting furnace to obtain an alloy mother ingot;
(3) and (3) carrying out surface pretreatment on the alloy mother ingot obtained in the step (2), and then carrying out melt spinning through a melt spinning machine to obtain the iron-based amorphous alloy strip.
Preferably, the surface linear speed of the melt-spun belt in the step (3) is 30-50 m/s.
Preferably, the surface pretreatment described in step (1) and step (3) means surface scale detachment.
Preferably, the iron-based amorphous alloy strip has a fully amorphous state or a composite structural feature of amorphous + alpha-Fe.
The iron-based amorphous alloy strip is applied to degradation treatment of printing and dyeing sewage.
Preferably, in the application process, the concentration of the dye in the printing and dyeing sewage is 20-1000 mg/L, and the adding amount of the iron-based amorphous alloy strip is 0.1-100 g/L.
Preferably, in the application process, the treatment temperature is controlled to be between room temperature and 100 ℃, and the mechanical stirring is 0 to 1000 r/min.
The iron-based amorphous alloy strip obtained by the invention has the following advantages and beneficial effects:
the preparation method of the iron-based amorphous alloy strip is simple, mass production is easy to realize, and the degradation speed of sewage can be improved by adding different alloy elements, so that the degradation capability of the iron-based amorphous alloy strip on printing and dyeing wastewater is further improved; and the amorphous strip can be recycled for multiple times, the dye removal rate of 60 minutes after continuous degradation for 5 times reaches 63.9%, and the method has the advantages of low cost and remarkable sewage treatment effect.
Drawings
FIG. 1 isFe in example 1 of the invention68Co10-xSi8B14SmxXRD pattern of (x ═ 0,2,4) fe-based amorphous alloy ribbon.
FIG. 2 shows (Fe) in example 2 of the present invention78Si9B13)1-0.01xGdxXRD pattern of (x ═ 0,2,4) fe-based amorphous alloy ribbon.
FIGS. 3 and 4 are Fe in example 1 of the present invention68Co10Si8B14、Fe68Co6Si8B14Sm4Ultraviolet-visible spectrum of the iron-based amorphous alloy strip for direct blue 2B solution under different treatment times.
FIGS. 5 and 6 are Fe in example 2 of the present invention78Si9B13、(Fe78Si9B13)0.96Gd4Ultraviolet-visible spectrum of the iron-based amorphous alloy strip for direct blue 2B solution under different treatment times.
FIG. 7 shows Fe in example 1 of the present invention68Co10Si8B14The iron-based amorphous alloy strip was repeatedly degraded five times with the change of the concentration of the dye with time.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
This example Fe68Co10-xSi8B14Smx(x ═ 0,2,4) preparation of fe-based amorphous alloy ribbon:
(1) commercially available high-purity Fe blocks, Co blocks, Si blocks, Sm blocks, and FeB master alloy (Fe: B: 79.5:20 wt.%) blocks were selected as raw materials, and the metal blocks were first surface-scale-removed and placed in absolute ethanol to prevent oxidation.
(2) And (3) repeatedly smelting the mother alloy raw material prepared in the step (1) in a water-cooled copper crucible of a vacuum smelting furnace for 5 times to ensure the uniformity of the mother material and obtain the iron-based amorphous alloy mother ingot.
(3) Prepared by the step (2)Polishing oxide skin on the surface of an alloy mother ingot, putting the alloy mother ingot into a quartz test tube with the bottom opening diameter of 1mm of a single-roller melt-spun machine (WK-II), melting the alloy mother ingot uniformly by using a medium-frequency induction furnace in an inert atmosphere, adjusting the surface linear velocity of a single-roller to be 42m/s, spraying molten metal onto a copper roller under the protection of inert gas for melt-spinning to obtain Fe with the width of about 3mm, the thickness of about 40 mu m and the length of about 5mm68Co10-xSi8B14SmxAn iron-based amorphous alloy strip.
Fe obtained in this example68Co10-xSi8B14SmxThe XRD test pattern of the (x ═ 0,2,4) fe-based amorphous alloy strip is shown in fig. 1. The XRD pattern shown in FIG. 1 shows Fe68Co10Si8B14Has the characteristic of full amorphous state; fe68Co8Si8B14Sm2Has the composite structural characteristics of amorphous state and alpha-Fe; fe68Co6Si8B14Sm4Has the composite structure characteristic of amorphous state + alpha-Fe.
Fe obtained in this example68Co10Si8B14、Fe68Co6Si8B14Sm4The application of the iron-based amorphous alloy strip in the degradation treatment of the sewage containing azo dyes comprises the following specific processes:
(1) and (3) preparing a direct blue 2B solution by using distilled water, wherein the concentration of the direct blue 2B dye in the solution is 100mg/L for later use.
(2) 0.5g of Fe obtained in this example was weighed out separately68Co10Si8B14、Fe68Co6Si8B14Sm4Pouring 500mL of prepared direct blue 2B solution into the iron-based amorphous alloy strip, stirring the solution by adopting a mechanical stirrer at the temperature of 35 ℃ in a thermostatic water bath, extracting 4-5 mL of solution at intervals at the rotating speed of 350r/min, and comparing by using an ultraviolet-visible spectrophotometer, wherein the results are respectively shown in fig. 3 and fig. 4. Calculated from the results of FIG. 3, Fe68Co10Si8B14After 60 minutes of reaction, the dyeThe removal rate reaches 83.1 percent; calculated from the results of FIG. 4, Fe68Co6Si8B14Sm4After 60 minutes of reaction, the dye removal reached 78.9%.
(3) Taking out Fe after 60 minutes of degradation68Co10Si8B14Cleaning iron-based amorphous strip with ultrasonic wave for 10min, performing secondary degradation experiment, reconfiguring direct blue 2B solution required in the above steps, performing secondary degradation with cleaned iron-based strip, and continuously repeating the above degradation experiment for 5 times to obtain Fe68Co10Si8B14The concentration of the dye over time for the iron-based amorphous strip was repeatedly degraded 5 times as shown in fig. 7. As can be seen from fig. 7, the removal rates of the degradation experiments of 1 st, 3 rd and 5 th are 83.1%, 73.5% and 63.9%, respectively.
Example 2
This example (Fe)78Si9B13)1-0.01xGdx(x ═ 0,2,4) preparation of fe-based amorphous alloy ribbon:
(1) commercially available high-purity Fe, Si, Gd and FeB master alloy (Fe: B: 79.5:20 wt.%) blocks were selected as raw materials, and the metal blocks were first surface-scale-detached and placed in absolute ethanol to prevent oxidation.
(2) And (3) repeatedly smelting the mother alloy raw material prepared in the step (1) in a water-cooled copper crucible of a vacuum smelting furnace for 5 times to ensure the uniformity of the mother material and obtain the iron-based amorphous alloy mother ingot.
(3) Polishing the oxide skin on the surface of the alloy mother ingot prepared in the step (2), putting the alloy mother ingot into a quartz test tube with the bottom opening diameter of 1mm of a single-roller melt-spun machine (WK-II), melting the alloy mother ingot uniformly in an inert atmosphere by using a medium-frequency induction furnace, adjusting the surface linear velocity of a single-roller to be 42m/s, spraying the molten metal liquid onto a copper roller under the protection of inert gas for melt-spinning to prepare the alloy mother ingot (Fe) with the width of about 2mm, the thickness of about 40 mu m and the length of about 5mm78Si9B13)1-0.01xGdx(x ═ 0,2,4) fe-based amorphous alloy ribbon.
Obtained in this example (Fe)78Si9B13)1-0.01xGdxThe XRD test pattern of the (x ═ 0,2,4) fe-based amorphous alloy strip is shown in fig. 2. The XRD pattern shown in FIG. 2 shows Fe78Si9B13Has the characteristic of full amorphous state; (Fe)78Si9B13)0.98Gd2Has the composite structural characteristics of amorphous state and alpha-Fe; (Fe)78Si9B13)0.96Gd4Has the composite structure characteristic of amorphous state + alpha-Fe.
Fe obtained in this example78Si9B13、(Fe78Si9B13)0.96Gd4The application of the iron-based amorphous alloy strip in the degradation treatment of the sewage containing azo dyes comprises the following specific processes:
(1) and (3) preparing a direct blue 2B solution by using distilled water, wherein the concentration of the direct blue 2B dye in the solution is 100mg/L for later use.
(2) 0.5g of Fe obtained in this example was weighed out separately78Si9B13、(Fe78Si9B13)0.96Gd4Pouring 500mL of prepared direct blue 2B solution into the iron-based amorphous alloy strip, stirring the solution by adopting a mechanical stirrer at the temperature of 35 ℃ in a thermostatic water bath, extracting 4-5 mL of solution at intervals at the rotating speed of 350r/min, and comparing by using an ultraviolet-visible spectrophotometer, wherein the results are respectively shown in fig. 5 and fig. 6. Calculated from the results of FIG. 5, Fe78Si9B13After reacting for 60 minutes, the dye removal rate reaches 62.0 percent; calculated from the results of FIG. 6, (Fe)78Si9B13)0.96Gd4After 60 minutes of reaction, the dye removal rate reached 75.7%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. An iron-based amorphous alloy strip is characterized in that the iron-based amorphous alloy strip comprises the following elements in atomic percentage: fe: 68% -78%, Co: 6-10%, Si: 8% -9%, B: 12% -14%, Sm: 2-4%; the specification range of the iron-based amorphous alloy strip is as follows: the width of the strip is 2-6 mm, the thickness of the strip is 20-100 μm, and the length of the strip is 1-20 mm.
2. The fe-based amorphous alloy ribbon according to claim 1, wherein said fe-based amorphous alloy ribbon comprises the following elements in atomic percent: fe: 68% -78%, Si: 8% -9%, B: 12% -14%, Gd: 2-4%.
3. The method for preparing the iron-based amorphous alloy strip of any one of claims 1-2, characterized by comprising the following preparation steps:
(1) proportioning according to the element percentage of claim 1 or 2, and carrying out surface pretreatment on a metal raw material;
(2) uniformly smelting the metal raw material pretreated in the step (1) in a vacuum smelting furnace to obtain an alloy mother ingot;
(3) and (3) carrying out surface pretreatment on the alloy mother ingot obtained in the step (2), and then carrying out melt spinning through a melt spinning machine to obtain the iron-based amorphous alloy strip.
4. The method for preparing the Fe-based amorphous alloy strip according to claim 3, wherein: and (4) the surface linear velocity of the melt-spun belt in the step (3) is 30-50 m/s.
5. The method for preparing the Fe-based amorphous alloy strip according to claim 3, wherein: the surface pretreatment described in step (1) and step (3) means surface scale detachment.
6. The method for preparing the Fe-based amorphous alloy strip according to claim 3, wherein: the iron-based amorphous alloy strip has the composite structural characteristic of amorphous state + alpha-Fe.
7. The application of the iron-based amorphous alloy strip of any one of claims 1-2 in degradation treatment of printing and dyeing wastewater.
8. The application of the iron-based amorphous alloy strip in the degradation treatment of printing and dyeing wastewater according to claim 7: the method is characterized in that in the application process, the concentration of dye in the printing and dyeing sewage is 20-1000 mg/L, the adding amount of the iron-based amorphous alloy strip is 0.1-100 g/L, the treatment temperature is controlled to be room temperature-100 ℃, and the mechanical stirring is 0-1000 r/min.
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| CN109095585A (en) * | 2018-09-30 | 2018-12-28 | 湘潭大学 | A method of for degrading azoic dye waste water |
| CN109434120B (en) * | 2018-11-14 | 2021-09-03 | 东南大学 | Iron-based amorphous alloy powder for degrading dye waste liquid and preparation method and application thereof |
| CN109811278A (en) * | 2019-02-28 | 2019-05-28 | 华南理工大学 | A kind of Fe-Si-B amorphous alloy strips and its preparation and the application in azo dye wastewater degradation |
| CN110918911B (en) * | 2019-11-19 | 2022-04-22 | 华南理工大学 | Iron-based series amorphous alloy strip, preparation method thereof and application thereof in degradation of azo dye wastewater |
| CN111041519A (en) * | 2019-11-21 | 2020-04-21 | 中国科学院金属研究所 | Non-noble metal amorphous electrolyzed water anode material and in-situ growth preparation method |
| CN112973691B (en) * | 2021-02-25 | 2023-12-26 | 深圳大学 | Strip amorphous alloy catalyst with nano structure and preparation method and application thereof |
| CN113201699B (en) * | 2021-04-13 | 2022-11-18 | 华南理工大学 | Iron-based alloy material and preparation method and application thereof |
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