CN113201699B - Iron-based alloy material and preparation method and application thereof - Google Patents
Iron-based alloy material and preparation method and application thereof Download PDFInfo
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
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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
- C22C33/06—Making ferrous alloys by melting using master alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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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
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2201/00—Treatment for obtaining particular effects
- C21D2201/03—Amorphous or microcrystalline structure
Abstract
The invention discloses an iron-based alloy material and a preparation method and application thereof, wherein the iron-based alloy material comprises the following components in atomic number percentage: fe:80% -85%, si:2% -3%, B:10% -15%, P:2% -3%, C:0 to 2 percent. The iron-based alloy material has good degradation effect on azo dyes in an amorphous state; annealing the amorphous Fe-based alloy material to form alpha-Fe and Fe with different electromotive forces and concomitant growth 3 B、Fe 2 And in the process of degrading azo dyes, micro batteries are formed among the nano crystal grains with different phases to perform micro battery reaction, so that three-dimensional nano corrosion pits are formed on the surface of the material and are changed into a porous state from a flat state, the increase of the specific surface area of the material reaction in the reaction process is facilitated, and the degradation efficiency is further improved.
Description
Technical Field
The invention relates to the technical field of nano-alloy and wastewater treatment, in particular to an iron-based alloy material and a preparation method and application thereof.
Background
Printing and dyeing wastewater is one of the major sources of water resource pollution. According to statistics, 100 million tons of dye is produced all over the world, wherein the proportion of the azo dye is as high as 67%. Azo dyes, as an important synthetic dye, exhibit a wide variety of colors, can cover substantially the entire visible spectrum, and are widely used for dyeing textiles because of their simple synthesis process, low production cost, and strong dyeing ability. The printing and dyeing industry generates a large amount of waste water during the coloring process, and about 10 percent of waste water directly or indirectly enters the environment during the discharge process. The printing and dyeing wastewater has complex components, contains various dyes of different classes, has the characteristics of deep chromaticity, strong toxicity, difficult degradation, large wastewater amount and the like, and is one of the industrial wastewater difficult to treat.
The current main methods for treating printing and dyeing wastewater comprise a photochemical oxidation method, a flocculation precipitation method, a biological method and the like. The principle of photochemical oxidation is to decompose pollutants by oxidizing agents to generate free radicals with strong oxidizing power under irradiation of light. The method has the problems of narrow ultraviolet light absorption range and low light energy utilization rate. In the wastewater with dark color or the wastewater with more suspended matters, the catalytic effect is seriously influenced because the light can not penetrate through the wastewater and the oxidant can not contact with the light source. The flocculation precipitation process has limited its development because of the large amount of sludge produced after treatment that needs to be treated. In addition, although the biological method has a good effect, for dye wastewater in different environments, enzymes and strains in different proportions need to be proportioned, and the biological method is still in an exploration stage at present.
The traditional method for treating azo dye wastewater has various limitations, such as high cost, serious secondary pollution, complex treatment and the like, which restrict the application. In recent years, researches show that zero-valent iron has excellent degradation performance as a degradation catalytic material, but the environment required by the method for degrading azo dyes is mostly acidic, a large amount of iron mud is generated in the environment, and precipitates are continuously deposited on the zero-valent iron in the degradation process to influence the further proceeding of the degradation process, so that the treatment cost is greatly increased.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the iron-based alloy material provided by the invention has a good degradation effect on azo dye wastewater.
Meanwhile, the invention also provides a preparation method and application of the iron-based alloy material.
Specifically, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides an iron-based alloy material, which comprises the following components in atomic number percentage: fe:80% -85%, si:2% -3%, B:10% -15%, P:2% -3%, C:0 to 2 percent.
The iron-based alloy material according to the first aspect of the invention has at least the following advantageous effects:
the Fe-based alloy material is prepared from Fe, si, B, P and C, wherein the atomic radius difference between Fe, P and C is more than 12%, the Fe-based alloy material has large negative mixing enthalpy and meets Inoue criterion, the obtained Fe-based alloy material has stable amorphous structure, the large atomic radius difference can enable the multi-component amorphous alloy to have a tighter stacking structure, and the tight stacking structure enables atoms to be more difficult to diffuse in a supercooled liquid phase region, namely crystalline phase nucleation is inhibited, and the short-range ordered structure of the amorphous alloy is increased. The inventor finds that the iron-based alloy consisting of Fe, si, B, P and C has good degradation effect on azo dyes.
In some embodiments of the present invention, the iron-based alloy material comprises the following components in atomic number percentage: fe: 81-83%, si:2% -3%, B:10% -15%, P:2% -3%, C:0 to 1.5 percent.
In some embodiments of the present invention, the iron-based alloy material comprises the following components in atomic number percentage: fe:82% -83%, si:2% -3%, B:10% -15%, P:2% -3%, C:0 to 1 percent.
In some embodiments of the present invention, the iron-based alloy material comprises the following components by atomic number percentage: fe:82% -83%, si:2.5%, B:12%, P:2.5%, C:0 to 1 percent.
In some embodiments of the present invention, the iron-based alloy material comprises the following components by atomic number percentage: fe:82%, si:2.5%, B:12%, P:2.5%, C:1% of composition Fe 82 Si 2.5 B 12 P 2.5 C. Under the composition, the iron-based alloy material has the best degradation effect on azo dyes.
In some embodiments of the present invention, the fe-based alloy material is an amorphous alloy or a nanocrystalline alloy.
In some embodiments of the invention, the iron-based alloy material is a nanocrystalline alloy with alpha-Fe, fe 3 B、Fe 2 And (5) phase C. The amorphous alloy can be annealed to obtain the nanocrystalline alloy, and the degradation effect on azo dyes can be further improved.
In some embodiments of the invention, the dimensions of the iron-based alloy material are: the width is 2-5 mm, the thickness is 10-30 μm, and the length is 10-20 mm.
The second aspect of the present invention provides a method for preparing the iron-based alloy material, comprising the following steps:
1) Weighing raw materials of Fe, si, B, fe-C alloy and Fe-P alloy according to the stoichiometric ratio of the iron-based alloy material, and smelting the raw materials into alloy ingots;
2) Preparing the alloy ingot obtained in the step 1) into amorphous alloy;
when the iron-based alloy material contains the nanocrystalline alloy, the preparation method further comprises the following steps:
3) And (3) annealing the amorphous alloy obtained in the step 2) to obtain the nanocrystalline alloy.
The method for preparing the iron-based alloy material according to the second aspect of the invention at least comprises the following steps:
in the preparation process, fe-C alloy, namely carbon steel is used as a carbon source, so that the problem that other carbon sources are difficult to be smelted with other raw materials can be solved. Firstly, preparing amorphous alloy, further annealing the amorphous alloy to obtain nanocrystalline alloy, and forming alpha-Fe and Fe which have different electromotive forces and are concomitantly grown in the annealing process 3 B、Fe 2 C phase of nanocrystalline grains in degradationIn the process of the azo dye, micro batteries are formed among the nano crystal grains with different phases to generate micro battery reaction, so that three-dimensional nano corrosion pits are formed on the surface of the material and are changed into a porous state from a flat state, the increase of the specific surface area of the material reaction in the reaction process is facilitated, and the degradation efficiency is further improved.
In some embodiments of the invention, the mass fraction of C in the Fe-C alloy is between 2% and 3%.
In some embodiments of the invention, the mass fraction of P in the Fe-P alloy is 30% to 35%.
In some embodiments of the invention, the purity of the Fe, the Si and the B is more than or equal to 99.9 percent.
In some embodiments of the invention, in step 1), the smelting is performed under vacuum conditions or in an inert protective gas.
In some embodiments of the present invention, a smelting furnace is used to smelt the raw material, and before smelting, the smelting furnace needs to be subjected to several times of gas washing treatment (for example, 3 times or more than 3 times); in the smelting process, the alloy ingot needs to be overturned and repeatedly smelted for more than several times (such as 6 times or more than 6 times).
In some embodiments of the invention, the temperature of the melting is 2000-3000 ℃, and the time of melting is 30-40 seconds per sample single melting.
In some embodiments of the present invention, in step 2), the alloy ingot of step 1) is made into an amorphous alloy by a strip casting method. The melt spinning method can be carried out in a vacuum melt spinning machine by adopting a single-roller melt spinning method. In the melt-spun process, the rotating speed of a copper roller in the vacuum melt-spun machine is 50-60 m/s.
In some embodiments of the invention, in step 3), the annealing is performed under vacuum conditions or in an inert protective gas. In the specific operation, the amorphous strip in the step 2) can be put into a furnace for annealing treatment after being subjected to vacuum tube sealing.
In some embodiments of the invention, the annealing temperature is 800 to 850 ℃.
In some embodiments of the invention, the annealing time is 3 to 10min.
In some embodiments of the invention, the quenching is performed immediately after the annealing is completed.
The third aspect of the invention provides application of the iron-based alloy material in degradation treatment of azo dye wastewater.
Specifically, the treatment method of the azo dye wastewater comprises the following steps: and (3) adding the iron-based alloy material into the azo dye wastewater, and stirring or standing for a period of time.
In some embodiments of the present invention, the iron-based alloy material is added in an amount of 0.2 to 2g/L in the azo dye wastewater.
In some embodiments of the invention, the rotation speed of the stirring is 200 to 500r/min.
In some embodiments of the present invention, the temperature of the azo dye wastewater is controlled during treatment at 10 to 50 ℃, preferably 20 to 40 ℃, more preferably 35 ℃.
The treatment method can be used for treating azo dye wastewater with the azo dye concentration of 40-100 mg/L, and has good treatment effect in wastewater with other concentrations.
Compared with the prior art, the invention has the following beneficial effects:
the Fe, si, B, P and C are used for preparing the iron-based alloy material, wherein the atomic radius difference among the Fe, the P and the C is more than 12 percent, the iron-based alloy material has large negative mixing enthalpy and meets Inoue criterion, the obtained iron-based alloy material has stable amorphous structure, the large atomic radius difference can enable the multi-element amorphous alloy to have a tighter stacking structure, and the tighter stacking structure enables atoms to be more difficult to diffuse in an overcooled liquid phase region, namely crystalline phase nucleation is inhibited, and the short-range ordered structure of the amorphous alloy is increased.
The iron-based alloy material has good degradation effect on azo dyes in an amorphous state; annealing the amorphous Fe-based alloy material to form alpha-Fe and Fe with different electromotive forces and concomitant growth 3 B、Fe 2 C phase nano crystal grains, and micro battery generation micro generated by the nano crystal grains of different phases in the process of degrading azo dyesThe battery reacts to form three-dimensional nano corrosion pits on the surface of the material, and the material is changed from a flat state to a porous state, so that the specific surface area of the material in the reaction process is increased, and the degradation efficiency is further improved.
In the preparation method, fe-C alloy with extremely low impurity content is used as a carbon source, and can be successfully smelted with other raw materials to successfully prepare the iron-based alloy material. Meanwhile, the preparation raw materials are safe and easy to obtain, the cost is low, the preparation method is simple, and the mass production is easy.
Drawings
FIG. 1 shows the results of X-ray diffraction analysis of C0, C0.5, C1, C1.5, C2, A1 and reduced iron powder;
FIG. 2 is a scanning electron micrograph of A1;
FIG. 3 is a graph (a) of ultraviolet-visible spectrum and a graph (b) of matter of solution of gold orange II degraded by reduced iron powder for different time;
FIG. 4 is a graph (a) of the UV-Vis spectrum and (b) of the solution of C1 versus the degradation of gold orange II solution for different time periods;
FIG. 5 is a graph (a) of the UV-Vis spectrum and (b) of the solution of A1 versus the degradation of gold orange II solution for different time periods;
FIG. 6 is a graph fitted to the kinetics of absorbance at λ =484nm during degradation of orange II solution by C0, C0.5, C1, C1.5, C2, A1 and reduced iron powder (a) and a first kinetic parameter K obs (b)；
FIG. 7 is a scanning electron micrograph of A1 (a, b, C) and C1 (d) at different magnifications after degradation of a solution of Citrus aurantium II;
wherein C0 represents Fe 83 Si 2.5 B 12 P 2.5 Amorphous strip, C0.5 representing Fe 82.5 Si 2.5 B 12 P 2.5 C 0.5 Amorphous ribbon, C1 represents Fe 82 Si 2.5 B 12 P 2.5 Amorphous strip of C, C1.5 representing Fe 81.5 Si 2.5 B 12 P 2.5 C 1.5 Amorphous strip, C2 represents Fe 81 Si 2.5 B 12 P 2.5 C 2 Amorphous strip, A1 represents Fe after C1 has been annealed 82 Si 2.5 B 12 P 2.5 C nanocrystalline strip.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
Example 1
Fe 82 Si 2.5 B 12 P 2.5 The preparation method of the C nanocrystalline strip comprises the following steps:
(1) Selecting high-purity Fe particles (more than or equal to 99.9%), si blocks (more than or equal to 99.9%), B particles (more than or equal to 99.9%), fe-P intermediate alloy blocks (Fe: P =67.5, 32wt.%) and Fe-C intermediate alloy blocks (Fe: C =97, 2.64wt.%) as raw materials, wherein the raw materials are as follows, according to the alloy components, the mass ratio of Fe: si: b: p: c =82:2.5:12:2.5: and 1, converting the required mass for sample preparation.
(2) And (2) putting the raw materials prepared in the step (1) into a vacuum smelting furnace to be smelted to obtain an alloy ingot, repeatedly smelting for at least 6 times in the smelting process to ensure the uniformity of components in the alloy ingot, wherein the smelting temperature is about 2500 ℃, and the smelting time is about 35 seconds for each sample in a single smelting process. Before smelting, argon is used for carrying out gas washing treatment on the smelting furnace for at least three times so as to ensure low oxygen content in the smelting furnace.
(3) And (3) cutting the alloy ingot obtained in the step (2) into small blocks (3-5 g) by using a cutting machine, polishing off oxide skins on the surface of the alloy ingot by using a grinding wheel machine, and then putting the alloy ingot into a quartz tube matched with a single-roller melt-spun machine. The aperture opening at the bottom of the quartz tube is controlled to be 100-500 mu m, and the distance between the bottom of the quartz tube and the copper roller is 2-4 mm. Before starting the strip throwing, argon is used for carrying out argon gas washing treatment on the furnace chamber of the strip throwing machine for at least three times so as to ensure that the oxygen content in the smelting furnace is low. In the process of melt spinning, when the rotation speed of the copper roller reaches a set value of 55m/s, the alloy ingot in the quartz tube is inductively heated, when the alloy ingot is completely melted, the alloy melt in the quartz tube is violently fluctuated and emits dazzling white light to press a blow button of the melt spinning machine, and the molten liquid is sprayed on the copper roller rotating at high speed to obtain Fe with the width of 2-5 mm and the thickness of 10-30 mu m 82 Si 2.5 B 12 P 2.5 C amorphous strip, marked C1.
(4) Part of the Fe prepared in the step (3) 82 Si 2.5 B 12 P 2.5 Cutting the amorphous C strip into small strips with the length of 10-20 mm, and filling the small strips into a quartz tube for vacuum tube sealing treatment. Before vacuum tube sealing, argon is used for carrying out gas washing treatment on the smelting furnace for at least three times so as to ensure low oxygen content in the smelting furnace, and finally a small amount of argon is filled as protective gas.
(5) To sealed Fe 82 Si 2.5 B 12 P 2.5 Annealing the C amorphous strip in a muffle furnace at 850 ℃, timing for 5min, immediately taking out the C amorphous strip after the timing is up, putting the C amorphous strip in water for cooling and quenching to obtain Fe 82 Si 2.5 B 12 P 2.5 C nanocrystalline ribbon, labeled A1.
Adjusting the raw material ratio in the step (1), and mixing the raw materials in percentage by atom as Fe: si: b: p: c =83:2.5:12:2.5:0, preparing a sample, and preparing Fe according to the same preparation method of the steps (2) and (3) 83 Si 2.5 B 12 P 2.5 Amorphous ribbon, marked C0;
or, according to atomic percent Fe: si: b: p: c =82.5:2.5:12:2.5:0.5 preparing a sample, and preparing Fe according to the same preparation method of the steps (2) and (3) 82.5 Si 2.5 B 12 P 2.5 C 0.5 Amorphous ribbon, labeled C0.5;
or, the ratio of Fe: si: b: p: c =81.5:2.5:12:2.5:1.5 preparing Fe by the same preparation method as the steps (2) and (3) 81.5 Si 2.5 B 12 P 2.5 C 1.5 Amorphous ribbon, marked C1.5;
or, according to atomic percent Fe: si: b: p: c =81:2.5:12:2.5:2 preparing Fe by the same preparation method of the steps (2) and (3) 81 Si 2.5 B 12 P 2.5 C 2 Amorphous ribbon, marked C2.
Structural characterization:
the results of X-ray diffraction analysis of C0, C0.5, C1, C1.5, C2 and A1 are shown in FIG. 1, and the results are compared with those of commercially available reduced iron powder. As can be seen from fig. 1, C0, C0.5, C1, C1.5 and C2 have one at 2 θ =45 °Dispersion peaks, which can determine that C0-C2 are all amorphous phases; a1 has obvious diffraction peaks at a plurality of positions, and comparison with PDF card shows that A1 has alpha-Fe and Fe 3 B、Fe 2 The composite structure of C is characterized by a nanocrystalline phase; the reduced iron powder is alpha-Fe phase.
The surface topography of A1 is shown in FIG. 2. As can be seen from FIG. 2, the surface of A1 is smooth and flat as a whole, and fine holes are formed due to the fact that the surface of the copper roller is not smooth enough in the vacuum melt-spinning preparation process. Microscopic morphology observation is carried out on C1, and the surface morphology of C1 is the same as that of A1.
Example 2
The C0, C0.5, C1, C1.5, C2 and A1 prepared in the example and the reduced iron powder are used for treating azo dye wastewater, and the specific method is as follows:
adding C0, C0.5, C1, C1.5, C2, A1 and reduced iron powder into a 40mg/L gold orange II solution at an addition amount of 2g/L, controlling the solution temperature at 30 ℃, and mechanically stirring at a stirring speed of 400r/min. Sampling and observing every 10min and carrying out ultraviolet-visible spectrum testing.
The degradation results of C0, C0.5, C1, C1.5, C2, A1 and reduced iron powder on golden orange II are as follows:
(1) The ultraviolet-visible spectrum and the real solution graph of the degradation of the gold orange II solution by the reduced iron powder, the C1 and the A1 for different time are shown in figures 3 to 5. Fig. 3a, 4a and 5a show that the absorbance at λ =484nm for C1 and A1 decreases with increasing treatment time, while the absorbance at λ =484nm for fine reduced iron hardly changes. And the absorbance at the position of lambda =484nm corresponds to the ultraviolet absorbance of "-N = N-" of the golden orange II molecules, which shows that the two strips of C1 and A1 can effectively perform bond breaking treatment on azo bonds of the golden orange II molecules along with the progress of the reaction, and have obvious degradation effect.
Meanwhile, it can be observed from fig. 3a, 4a and 5a that the absorbance at λ =248nm corresponding to C1 and A1 is also gradually decreased. Due to the fact that the part at lambda =248nm corresponds to the ' -N = N- ' broken bond product ' -NH of the orange II molecule 2 "the amount of the broken bond products should increase as the degradation reaction proceeds, and the absorbance at λ =248nm should increase correspondingly. However, CThe absorbance at λ =248nm corresponding to 1 and A1 is also gradually reduced, which should be due to that C1 and A1 have a certain adsorption effect on degradation products in addition to the bond breaking effect in the degradation process of the aurantium II molecules.
The graphs of the real solutions after the addition of the reduced iron powder, the addition of the C1 and the addition of the A1 to the gold orange II solution and the sampling at intervals of 10min are shown in fig. 3b, 4b and 5b, and it can be seen that the concentration of the gold orange II solution added with the C1 and the addition of the A1 is remarkably reduced as the reaction proceeds, the color of the solution taken out at 70min is almost colorless, and the color of the solution added with the reduced iron powder is almost unchanged.
(2) The first kinetic fit was performed by converting the peak intensity at λ =484nm representing the azo double bond in golden orange II to the corresponding golden orange II concentration according to the lambert-beer law, resulting in C0, C0.5, C1, C1.5, C2, A1, and the absorbance kinetic fit plot at λ =484nm for the reduced iron powder treated 40mg/L golden orange II solution is shown in fig. 6 a. Then by formula C t /C 0 ＝exp(k obs T) fitting calculation to obtain C0, C0.5, C1, C1.5, C2, A1 and the first kinetic parameter K of the reduced iron powder obs To characterize how fast the material degrades efficiently, as shown in fig. 6 b.
As can be seen from fig. 6a and b, C0, C0.5, C1, C1.5, C2 and A1 all have a certain degradation effect on golden orange II; and with the increase of the doping amount of C atoms, the degradation efficiency of the amorphous strip to the golden orange II is increased firstly and then reduced, and when the doping amount of the number of the C atoms is 1 percent, (C1) the degradation efficiency reaches the highest. Wherein, compared with C0 not doped with C, the degradation efficiency of C1 doped with 1% atomic C is improved by 10.4%. Meanwhile, the degradation efficiency of the A1 is improved by 11.82% compared with that of the C1 and is 116 times that of the reduced iron powder, which shows that the efficiency of the amorphous strip for degrading azo dye wastewater can be further improved by carrying out annealing treatment processing on the amorphous strip at high temperature.
As shown in fig. 7, when the microscopic surface morphology of A1 and C1 after degrading the golden orange II (70 min) is observed and compared with fig. 2, it is found that A1 has many nano-pores on the surface during the reaction process, and the nano-pores change from a flat state to a porous state, and the nano-pores increase the reaction specific surface area and accelerate the degradation efficiency; meanwhile, in the process of degrading the golden orange II, the surface of A1 is contacted with oxygen in the solution to form a silicon dioxide layer, and the occurrence of nano holes is favorable for accelerating the falling of the silicon dioxide layer on the surface, so that the contact of Fe atoms on the bottom layer and dye molecules is facilitated; meanwhile, degradation products are also adsorbed on the surface of A1. And C1 is adsorbed with degradation products on the surface, but nano holes do not appear.
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 (5)
1. The application of the iron-based alloy material in the degradation treatment of azo dye wastewater is characterized in that: the application is a method for treating azo dye wastewater, which comprises the following steps: adding the iron-based alloy material into azo dye wastewater, and stirring or standing for a period of time; the iron-based alloy material is a strip material and comprises the following components in atomic number percentage: fe:82% -83%, si:2% -3%, B:10% -15%, P:2% -3%, C:1 percent; the iron-based alloy material is a nanocrystalline alloy with alpha-Fe and Fe 3 B、Fe 2 And C phase.
2. The use as claimed in claim 1, wherein: the preparation method of the iron-based alloy material comprises the following steps:
1) Weighing raw materials Fe, si, B, fe-C alloy and Fe-P alloy according to the stoichiometric ratio of the iron-based alloy material, and smelting into an alloy ingot;
2) Preparing the alloy ingot in the step 1) into amorphous alloy;
when the iron-based alloy material contains the nanocrystalline alloy, the preparation method further comprises the following steps:
3) And (3) annealing the amorphous alloy obtained in the step 2) to prepare the nanocrystalline alloy.
3. The use according to claim 2, wherein the mass fraction of C in the Fe-C alloy is 2-3%.
4. Use according to claim 2, characterized in that: the weight percentage of P in the Fe-P alloy is 30-35%.
5. Use according to claim 2, characterized in that: in the step 3), the annealing temperature is 800-850 ℃.
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