CN109434120B - Iron-based amorphous alloy powder for degrading dye waste liquid and preparation method and application thereof - Google Patents
Iron-based amorphous alloy powder for degrading dye waste liquid and preparation method and application thereof Download PDFInfo
- Publication number
- CN109434120B CN109434120B CN201811352972.1A CN201811352972A CN109434120B CN 109434120 B CN109434120 B CN 109434120B CN 201811352972 A CN201811352972 A CN 201811352972A CN 109434120 B CN109434120 B CN 109434120B
- Authority
- CN
- China
- Prior art keywords
- iron
- based amorphous
- amorphous alloy
- alloy powder
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
-
- 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
- C02F2101/40—Organic compounds containing sulfur
Abstract
The invention discloses a method for preparing iron-based amorphous alloy powder for degrading dyes, which is obtained by carrying out ultrasonic treatment on the iron-based amorphous alloy powder by combining the existing process conditions in actual production on the premise of meeting the market application requirements. The invention also discloses application of the amorphous powder after ultrasonic treatment in degradation of dye waste liquid, and optimal degradation treatment conditions are finally obtained by respectively considering different ultrasonic energy and powder usage in the degradation process. The method realizes degradation of the dye waste liquid, realizes effective utilization of industrial waste iron-based amorphous powder, has good application prospect in the aspect of sewage treatment, and has important significance for environmental protection and sustainable development.
Description
Technical Field
The invention belongs to the field of sewage treatment, and particularly relates to iron-based amorphous alloy powder for degrading waste liquid dye, and a preparation method and application thereof.
Background
With the rapid development of industry, a large amount of dye waste liquid is discharged, and the waste liquid poses serious threats to the sustainable development of human health and ecological environment. At present, the dye waste liquid treatment technologies which are applied more frequently comprise a physical adsorption method, a chemical flocculation method, a membrane separation method, a chemical oxidation method, a biodegradation method and the like. However, due to the inherent defects of the technology, most of the dye waste liquid treatment technologies cannot meet the requirement of completely and effectively degrading the dye waste liquid; the activated carbon shows good dye adsorption performance, but is difficult to be put into use on a large scale due to complex preparation process, complex subsequent treatment work, high cost and secondary pollution; biodegradation processes exhibit green, pollution-free degradation, but the scope of application is greatly limited by the stringent environmental requirements of the process.
Amorphous alloy as a novel metal material has a very wide potential application due to the characteristics of long-range disorder and short-range order in the structure, and is greatly concerned in the field of materials. The iron-based amorphous alloy is used as a novel functional material for dye sewage treatment due to the unique atomic structure and the special physical and chemical properties. On one hand, the amorphous alloy is in a metastable state, the component atoms are far away from an equilibrium state, the energy of the amorphous alloy is higher than that of the corresponding crystalline alloy in thermodynamics, and the amorphous alloy shows lower reaction activation energy; on the other hand, the nano-scale uniform microstructure of the amorphous alloy has the characteristics of no crystal boundary and the like, so that the amorphous alloy has excellent corrosion resistance. In addition, the iron-based amorphous alloy has low cost, good environmental compatibility and sustainability and easy recycling, so the iron-based amorphous alloy has great application potential in the degradation of dye waste liquid.
However, the preparation process of the quenched iron-based amorphous alloy ribbon is complex and strict in requirements, the specific surface area is relatively small, and the production cost is high, so that the quenched iron-based amorphous alloy ribbon is not beneficial to large-scale popularization and application. The iron-based amorphous alloy powder can effectively increase the specific surface area of a sample and improve the degradation efficiency. Meanwhile, the degradation performance of the amorphous alloy can be obviously improved in two aspects by ultrasonic treatment, on one hand, the energy of an iron-based amorphous alloy powder system can be increased, and more high activation points can be obtained, so that the activation energy required by the reaction is reduced, and the improvement of the degradation performance is promoted; on the other hand, the ultrasonic oscillation can effectively remove the oxide layer on the surface of the amorphous alloy, has a self-cleaning effect, and provides more reaction sites, thereby improving the degradation performance of the iron-based amorphous alloy powder. In addition, the catalyst for degrading the dye waste liquid can be prepared by selecting industrial waste iron-based amorphous alloy powder for ultrasonic treatment, so that the production process is effectively simplified, and the production cost is reduced.
Chinese patent application CN108220824A discloses an iron-based amorphous alloy strip and application thereof in degradation treatment of printing and dyeing sewage. The method is used for increasing the degradation speed of the catalytic dye waste liquid by adding different alloy elements to prepare the iron-based amorphous alloy strip serving as a catalyst. However, rare earth elements Sm and Gd are added to improve the amorphous degradation capability, and the addition amount of the iron-based amorphous alloy strip required by the patent is relatively large, so that the application cost is high. The maximum degradation rate of the sewage of the amorphous alloy prepared by the method is 83.1 percent in 60 minutes, the degradation speed is low, and the degradation rate is low.
Chinese patent CN108187687A discloses a method for preparing a photo-fenton catalyst. The method firstly prepares alpha-Fe2O3@ C, then on the alpha-Fe prepared2O3@ C surface-treated with Na2WO4·2H2O、Bi(NO3)3·5H2And mixing O and sodium citrate, and carrying out hydrothermal reaction to obtain the catalyst. The catalyst can promote photo-generated charge separation, can remarkably enhance the adsorption of the catalyst on dye molecules, and has a remarkable degradation effect on rhodamine B. However, the dosage of hydrogen peroxide in the patent is high, and the catalyst preparation is complex and needs to be carried outA light source is added.
Therefore, on the basis of keeping excellent degradation waste liquid dye of the amorphous alloy, the catalytic degradation rate and the degradation rate of the iron-based amorphous alloy are improved, the required dosage of the catalyst is reduced, the environmental requirement of catalysis on degradation of the dye waste liquid is reduced, the preparation process is simplified, the production cost is reduced, and the method is of great importance for the research on the catalytic degradation of the iron-based amorphous alloy.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the existing defects, the invention provides a brand-new process for preparing the iron-based amorphous alloy powder for degrading the waste liquid dye, and the amorphous powder prepared by the process can effectively avoid the defects of complex preparation process, high cost, slow degradation rate, low degradation rate and the like of the dye degradation catalyst.
The technical scheme is as follows: the preparation method of the iron-based amorphous alloy powder for degrading the dye waste liquid comprises the following steps:
(1) preparing iron-based amorphous alloy powder: preparing raw materials from alloy component elements Fe, Si and B, smelting the raw materials into uniform master alloy, remelting the smelted master alloy into alloy solution, spray-casting the alloy solution onto the surface of a rapidly rotating copper roller to obtain iron-based amorphous alloy strips with uniform components, and putting the iron-based amorphous alloy strips into a ball mill for high-speed ball milling to obtain iron-based amorphous alloy powder;
(2) ultrasonic treatment of iron-based amorphous alloy powder: and (2) carrying out ultrasonic treatment on the iron-based amorphous alloy powder prepared in the step (1) to obtain the iron-based amorphous alloy powder for degrading dye waste liquid.
Further, the step (1) includes the steps of:
1) preparing raw materials by taking industrial pure Fe, Si and B elements, putting the raw materials into an arc melting furnace or an induction melting furnace, melting the raw materials uniformly, and cooling to obtain a master alloy ingot with uniform components;
2) remelting the master alloy ingot obtained in the step 1), and spraying the remelted alloy liquid onto the surface of a rapidly rotating copper roller by using a single-roller melt rapid quenching method to prepare an iron-based amorphous alloy strip;
3) and 2) carrying out high-speed ball milling on the iron-based amorphous alloy strip prepared in the step 2) in an inert atmosphere or air to prepare iron-based amorphous alloy powder.
Wherein, in the step 1), when the master alloy is prepared by adopting an induction smelting furnace, the temperature is kept for 10-30min after the raw materials are completely melted; when the electric arc melting furnace is adopted to prepare the master alloy, the smelting is repeated for 3 to 6 times, and the aim is to ensure the uniformity of the components of the master alloy.
In the step 2), the surface linear velocity of the rapidly rotating copper roller is 20-40 m/s; the thickness of the prepared iron-based amorphous alloy strip is 18-35 mu m.
In the step 3), ball milling is carried out until the particle size of the powder is 1-50 μm. The ball milling conditions are ball milling in air (protected with inert gas for particularly easily oxidizable systems) for 1 to 36 hours.
Preferably, in the step (2), the ultrasonic treatment is: the energy of the ultrasonic wave is 100-. The purpose of ultrasonic treatment is to obtain iron-based amorphous alloy powder in different energy states.
As shown in fig. 1 and 2, the iron-based amorphous alloy powder is repeatedly oscillated at a certain speed through a cylindrical ultrasonic pressure head under a certain force, so that the energy of an iron-based amorphous alloy powder system can be remarkably increased, more high activation points are obtained, the activation energy required by the reaction is reduced, and the improvement of the degradation performance is promoted. Meanwhile, the oxide layer on the surface of the amorphous alloy can be effectively removed through ultrasonic oscillation, the self-cleaning effect is achieved, more reaction sites are provided, and therefore the degradation performance of the iron-based amorphous alloy powder is improved.
Most preferably, the ultrasonic wave has a treatment energy of 750J, a trigger pressure of 100N, an amplitude of 100% and a working air pressure of 500 KPa.
Further preferably, in step (1), the elements Fe, Si, B are according to the formula Fe78Si9B13Preparing raw materials.
The iron-based amorphous alloy powder for degrading the dye waste liquid prepared by the method is also within the protection scope of the invention.
The invention discloses application of iron-based amorphous alloy powder for degrading dye waste liquid in degrading dye waste liquid. Specifically, the application comprises the following steps: adding hydrogen peroxide into the dye waste liquid solution to be treated in a constant-temperature water bath environment, and adjusting the pH value of the mixed solution; and then adding the iron-based amorphous alloy powder for degrading the dye waste liquid into the mixed solution, and mechanically stirring to ensure that the dye waste liquid solution to be treated fully contacts the iron-based amorphous alloy powder, thereby realizing the uniform degradation of the dye solution.
Preferably, the temperature of the constant-temperature water bath is 25-65 ℃; the concentration of the hydrogen peroxide is 0.5-10 mM.
Preferably, the pH value of the mixed solution is adjusted to 2-4.
Preferably, the dosage of the amorphous alloy powder is 0.1-0.5 g/L; the mechanical stirring speed is 350-450 r/min.
The most preferable degradation treatment scheme is that the pH value of the mixed solution is 3, the using amount of the iron-based amorphous alloy powder is 0.4g/L, and the concentration of hydrogen peroxide is 1 mM.
The method of the invention is adopted to degrade the dye waste liquid, and the degradation rate of the sewage dye is obviously improved.
Has the advantages that: compared with the prior art, the preparation method of the iron-based amorphous alloy powder for degrading the dye waste liquid is simple and easy to obtain, and the prepared iron-based amorphous alloy has the following advantages when used for degrading the dye waste liquid: (1) the catalyst has the advantages of high catalytic degradation reaction rate, high degradation rate, good effect and small dosage; (2) the used iron-based amorphous powder can also adopt industrial waste powder, so that on one hand, the secondary utilization of waste raw materials is realized, and on the other hand, the cost is reduced; (3) has good application prospect in the aspect of sewage treatment and has important significance for environmental protection and sustainable development.
Drawings
FIG. 1 is a schematic view of an ultrasonic treatment device for iron-based amorphous alloy powder;
FIG. 2 is a schematic diagram of an ultrasonic treatment of Fe-based amorphous alloy powder;
FIG. 3 shows industrial Fe treated with 750J ultrasonic energy in example 1 of the present invention78Si9B13Ultraviolet light absorption of amorphous powder catalytic degradation methylene blueA spectrogram;
FIG. 4 shows the industrial Fe after different ultrasonic energy treatments in example 1 of the present invention78Si9B13The change curve of the concentration of the dye for catalyzing and degrading the methylene blue by the amorphous powder along with the degradation time;
FIG. 5 shows industrial Fe in example 2 of the present invention78Si9B13The change curve of the concentration of the dye for catalyzing and degrading the methylene blue by the amorphous powder at different solution pH values along with the degradation time;
FIG. 6 shows different industrial Fe in example 3 of the present invention78Si9B13The change curve of the concentration of the dye for catalyzing and degrading the methylene blue by using the amorphous powder along with the degradation time;
FIG. 7 shows industrial Fe in example 4 of the present invention78Si9B13The change curve of the concentration of the dye for catalyzing and degrading the methylene blue of the amorphous powder under different water bath temperature environments along with the degradation time.
Detailed Description
The present application will be described in detail with reference to specific examples.
The invention provides a method for preparing industrial iron-based amorphous powder for degrading waste liquid dye, wherein the iron-based amorphous alloy powder is industrial iron-based amorphous powder, and the method is characterized by comprising the following three stages:
the first stage is as follows: preparation of amorphous powder: preparing raw materials of industrial pure Fe, Si and B elements according to a molecular formula, smelting the raw materials into uniform master alloy in an inert atmosphere by using an electric arc furnace, and spray-casting the smelted master alloy on a rapidly rotating copper roller in the inert atmosphere to obtain an iron-based amorphous alloy strip with uniform components; and putting the prepared industrial amorphous strip into a ball mill, and carrying out high-speed ball milling for 1-36 hours under the protection of air or inert gas to prepare the industrial iron-based amorphous alloy powder with the particle size distribution of 1-50 mu m.
And a second stage: as shown in FIG. 1, a proper amount of industrial iron-based amorphous powder is placed into an ultrasonic mold to carry out ultrasonic treatment with the triggering pressure of 22-1000N, the amplitude of 50-100% and the working air pressure of 100-600KPa and the energy of 250-2000J; preferably, the ultrasonic trigger pressure is 100N, the amplitude is 100%, the working air pressure is 500KPa, and the energy is 750J, so as to obtain industrial iron-based amorphous powder in different energy states;
and a third stage: adding 0.5-10mM hydrogen peroxide into the dye solution in a constant-temperature water bath environment with a water bath temperature of 25-65 ℃, and adjusting the pH of the mixed solution to 2-4, wherein the preferable concentration of the hydrogen peroxide is 1Mm, and the pH of the solution is 3, so as to degrade the dye sewage in different environments; adding the industrial iron-based amorphous powder subjected to ultrasonic treatment into a dye solution according to the dosage of 0.1-0.5 g/L, and mechanically stirring at the speed of 350-450 r/min to ensure that the dye solution fully contacts the industrial iron-based amorphous powder to realize uniform degradation of the dye, wherein the preferred dosage of the industrial iron-based amorphous powder is 0.4 g/L.
Changing the size of ultrasonic treatment energy in the industrial iron-based amorphous powder sample, setting and preferably selecting different energies (400-2000J), analyzing and comparing the capacity of the powder sample for degrading the dye waste liquid under different ultrasonic energy conditions, and obviously improving the capacity of the amorphous powder sample for degrading the dye waste liquid after ultrasonic treatment.
Example 1
This example investigated the use of sonicated industrial Fe78Si9B13The ability of iron-based amorphous powder to degrade methylene blue.
Step 1: industrial pure Fe, Si and B elements are Fe according to the molecular formula78Si9B13Preparing raw materials, smelting the raw materials into uniform master alloy by using an electric arc furnace, remelting the smelted master alloy into alloy liquid, and spray-casting the alloy liquid onto the surface of a copper roller rotating at a high speed of 30m/s to obtain an iron-based amorphous alloy strip with uniform components; putting the prepared industrial amorphous strip into a ball mill (air atmosphere) for high-speed ball milling for 24 hours to prepare Fe with the particle size distribution of 1-50 mu m78Si9B13Industrial iron-based amorphous alloy powder.
Step 2: industrial Fe78Si9B13The amorphous powder is subjected to ultrasonic treatment under the ultrasonic energy with the ultrasonic trigger pressure of 100N, the amplitude of 100 percent and the working air pressure of 500KPa and 250-2000J.
And step 3: adding 250mL of methylene blue solution with the concentration of 100mg/L into a beaker with the capacity of 500mL, putting the beaker into a constant-temperature water bath kettle with the temperature of 25 ℃ for heat preservation, adding hydrogen peroxide after the temperature of the solution is stable, adjusting the concentration of the hydrogen peroxide to be 1mM, and adjusting the pH value of the solution to be 3.
And 4, step 4: and (3) weighing the iron-based amorphous powder subjected to ultrasonic treatment in the step (2) according to the dosage of the methylene blue solution and the dosage of 0.5g/L, and then putting the iron-based amorphous powder into the beaker solution in the step (3). Mechanically stirring the solution by using a mechanical stirring device to ensure that the industrial Fe78Si9B13The amorphous powder is uniformly contacted with methylene blue, so that the dye is fully degraded.
And 5: in the degradation process, 2.5mL of solution is extracted by an injector at regular intervals, the obtained solution is filtered by a disposable filter membrane with the aperture of 0.22 mu m, the filtered solution is immediately put into an ultraviolet/visible spectrophotometer to be tested, an ultraviolet absorption spectrogram is obtained, and the change of the solution concentration is obtained according to the change trend of the absorbance at the maximum absorption peak.
Fig. 3 is an ultraviolet absorption spectrum of catalytic degradation of methylene blue of 750J ultrasonically treated FeSiB iron-based amorphous powder measured by a UVmini-1280 ultraviolet/visible spectrophotometer, and it can be seen that the intensity of the absorption peak gradually decreases with the progress of the degradation reaction, and after 14 minutes, the characteristic peak in the ultraviolet absorption spectrum of the solution disappears, i.e. the methylene blue in the solution is completely degraded.
The concentration C of methylene blue in the solution at the moment t can be obtained according to the ultraviolet absorption spectrogramtWith initial dye concentration C0Ratio of the two, using a quasi-first order kinetic model Ct＝C0exp (-kt) describes the catalytic degradation process of amorphous alloys.
FIG. 4 shows C obtained by degrading methylene blue with FeSiB amorphous powder after ultrasonic treatment with different energiest/C0Time diagram, it can be seen that the 500J, 750J, 1000J treated powders have been substantially completely degraded at 14 minutes.
Comparative example 1
The following comparative example 1 is a comparative example of the above example 1. The powder composition used in comparative example 1 was identical to the powder composition described in example 1, whereas comparative example 1 was a solution of degraded methylene blue using the original amorphous powder without sonication.
The powders of comparative example 1 were tested for their degradability in exactly the same manner as described in example 1, and the results are given in table 1.
TABLE 1 comparison of the degradation behavior of the amorphous alloy powders in example 1
In the above table, the amorphous alloys are all industrial Fe with the same composition and the same dosage78Si9B13Amorphous powder. From the comparison of the performance data in table 1 and fig. 4, it can be seen that the ability of the iron-based amorphous powder in example 1 of the present invention to degrade methylene blue is significantly improved compared to that in comparative example 1.
Example 2
This example investigated the pH of the solution versus industrial Fe78Si9B13Influence of the ability of amorphous powder to catalyze degradation of methylene blue.
Step 1: the industrial powder was sonicated at 500KPa, 750J ultrasonic energy.
Step 2: adding 250mL of methylene blue solution with the concentration of 100mg/L into a beaker with the capacity of 500mL, putting the beaker into a constant-temperature water bath kettle with the temperature of 25 ℃ for heat preservation, adding hydrogen peroxide after the temperature of the solution is stable, adjusting the concentration of the hydrogen peroxide to be 1mM, and adjusting the pH value of the solution to be 2, 3, 4, 5 and 9.
And step 3: weighing the iron-based amorphous powder prepared in the step 1 according to the dosage of the methylene blue solution and then putting the iron-based amorphous powder into a beaker according to the dosage of 0.4 g/L. Mechanically stirring the solution by using a mechanical stirring device to ensure that the industrial Fe78Si9B13The amorphous powder is uniformly contacted with methylene blue, so that the dye is fully degraded.
And 4, step 4: in the degradation process, 2.5mL of solution is extracted by an injector at regular intervals, the obtained solution is filtered by a disposable filter membrane with the aperture of 0.22 mu m, and the filtered solution is immediately put into an ultraviolet/visible spectrophotometer for testing to obtain an ultraviolet absorption spectrum.
Comparative example 2
The following comparative example 2 is a comparative example of the above example 2. The amorphous alloy powder used in comparative example 2 was identical to the amorphous alloy powder described in example 2, and in comparative example 2, a methylene blue solution was degraded using the amorphous powder under a solution environment of pH 7.
The methylene blue of comparative example 2 was tested for its ability to degrade, in exactly the same manner as described in example 2.
FIG. 5 shows industrial Fe78Si9B13Amorphous powder for catalyzing and degrading methylene blue C under different solution pH valuest/C0vs. time plot. From comparison of various performance data in fig. 5, it can be seen that the degradation rate is faster when the pH is adjusted to 2-4, wherein the degradation rate is fastest when the pH is 3, and methylene blue can be completely degraded.
Example 3
This example explores the industrial Fe in solution78Si9B13Influence of the amount of amorphous powder on the ability of catalyzing and degrading methylene blue.
Step 1: the industrial powder was sonicated at 500KPa, 750J ultrasonic energy.
Step 2: adding 250mL of methylene blue solution with the concentration of 100mg/L into a beaker with the capacity of 500mL, putting the beaker into a constant-temperature water bath kettle with the temperature of 25 ℃ for heat preservation, adding hydrogen peroxide after the temperature of the solution is stable, adjusting the concentration of the hydrogen peroxide to be 1mM, and adjusting the pH value of the solution to be 3.
And step 3: weighing the iron-based amorphous powder prepared in the step 1 according to the dosage of methylene blue solution, and then putting the iron-based amorphous powder into a beaker according to the dosage of 0.1g/L, 0.2g/L, 0.3g/L, 0.4g/L and 0.5 g/L. Mechanically stirring the solution by using a mechanical stirring device to ensure that the industrial Fe78Si9B13Amorphous powder with methyleneThe blue is uniformly contacted, so that the dye is fully degraded.
And 4, step 4: in the degradation process, 2.5mL of solution is extracted by an injector at regular intervals, the obtained solution is filtered by a disposable filter membrane with the aperture of 0.22 mu m, and the filtered solution is immediately put into an ultraviolet/visible spectrophotometer for testing to obtain an ultraviolet absorption spectrum.
FIG. 6 shows industrial Fe78Si9B13C for catalyzing and degrading methylene blue by amorphous powder under different amorphous alloy powder dosagest/C0vs. time plot. As can be seen from the figure, the degradation rate is firstly improved along with the increase of the dosage of the amorphous powder, and then is basically kept unchanged; when in industrial Fe78Si9B13When the using amount of the amorphous powder is 0.3-0.4 g/L, a relatively good degradation rate can be achieved, and therefore the method has a relatively low demand on the FeSiB amorphous powder and can remarkably reduce the sewage treatment cost.
Example 4
This example explores the temperature in solution versus industrial Fe78Si9B13Influence of the ability of amorphous powder to catalyze degradation of methylene blue.
Step 1: the industrial powder was sonicated at 500KPa, 750J ultrasonic energy.
Step 2: adding 250mL of methylene blue solution with the concentration of 100mg/L into a beaker with the capacity of 500mL, putting the beaker into a constant-temperature water bath kettle with the temperature of 45 ℃ and the temperature of 65 ℃ for heat preservation, adding hydrogen peroxide after the solution temperature is stable, adjusting the concentration of the hydrogen peroxide to be 1mM, and adjusting the pH value of the solution to be 3.
And step 3: weighing the iron-based amorphous powder prepared in the step 1 according to the dosage of the methylene blue solution and then putting the iron-based amorphous powder into a beaker according to the dosage of 0.4 g/L. Mechanically stirring the solution by using a mechanical stirring device to ensure that the industrial Fe78Si9B13The amorphous powder is uniformly contacted with methylene blue, so that the dye is fully degraded.
And 4, step 4: in the degradation process, 2.5mL of solution is extracted by an injector at regular intervals, the obtained solution is filtered by a disposable filter membrane with the aperture of 0.22 mu m, and the filtered solution is immediately put into an ultraviolet/visible spectrophotometer for testing to obtain an ultraviolet absorption spectrum.
Comparative example 3
Comparative example 3 is a comparative example to example 4 above. The powder composition used in comparative example 3 was identical to the powder composition described in example 4, whereas comparative example 3 was a methylene blue solution degraded with the original amorphous powder at room temperature and a bath temperature of 25 ℃.
The methylene blue of comparative example 3 was tested for its ability to degrade, in exactly the same manner as described in example 4.
FIG. 7 shows industrial Fe78Si9B13Catalyzing and degrading methylene blue C by amorphous powder at different water bath temperaturest/C0vs. time plot. As can be seen from the figure, industrial Fe in the present invention78Si9B13The capability of the amorphous powder for degrading methylene blue is obviously improved along with the increase of temperature; moreover, when the temperature of the solution is 45 ℃, the amorphous alloy powder can achieve higher degradation capability, so that the requirement on energy is lower in the invention, and the energy loss can be effectively reduced.
Claims (6)
1. A preparation method of iron-based amorphous alloy powder for degrading dye waste liquid is characterized by comprising the following steps:
(1) preparing iron-based amorphous alloy powder:
1) preparing raw materials by taking industrial pure Fe, Si and B elements, putting the raw materials into an arc melting furnace or an induction melting furnace, melting the raw materials uniformly, and cooling to obtain a master alloy ingot with uniform components;
2) remelting the master alloy ingot obtained in the step 1), and spraying the remelted alloy liquid onto the surface of a rapidly rotating copper roller by using a single-roller melt rapid quenching method to prepare an iron-based amorphous alloy strip;
3) carrying out high-speed ball milling on the iron-based amorphous alloy strip prepared in the step 2) in air to prepare iron-based amorphous alloy powder with the particle size distribution of 1-50 mu m;
(2) ultrasonic treatment of iron-based amorphous alloy powder: carrying out ultrasonic treatment on the iron-based amorphous alloy powder prepared in the step (1) to obtain iron-based amorphous alloy powder for degrading dye waste liquid;
in the step (1), the elements Fe, Si and B are Fe according to the molecular formula78Si9B13Preparing raw materials;
in the step (2), the ultrasonic treatment means: the energy of the ultrasonic wave is 100-.
2. The preparation method according to claim 1, wherein in the step 2), the surface linear speed of the rapidly rotating copper roller is 20-40 m/s; the thickness of the prepared iron-based amorphous alloy strip is 18-35 mu m.
3. The iron-based amorphous alloy powder prepared according to claim 1 or 2.
4. The application of the iron-based amorphous alloy powder in degrading dye waste liquid in claim 3 is characterized by comprising the following steps: adding hydrogen peroxide into the dye waste liquid solution to be treated in a constant-temperature water bath environment, and adjusting the pH value of the mixed solution; and then adding the iron-based amorphous alloy powder for degrading the dye waste liquid into the mixed solution, and mechanically stirring to ensure that the dye to be treated fully contacts the iron-based amorphous alloy powder, thereby realizing the uniform degradation of the dye solution.
5. The use according to claim 4, wherein the thermostated water bath temperature is 25-65 ℃; the concentration of the hydrogen peroxide is 0.5-10mM, and the pH value of the mixed solution is 2-4.
6. The use according to claim 4, wherein the amorphous alloy powder is used in an amount of 0.1 to 0.5 g/L; the mechanical stirring speed is 350-450 r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811352972.1A CN109434120B (en) | 2018-11-14 | 2018-11-14 | Iron-based amorphous alloy powder for degrading dye waste liquid and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811352972.1A CN109434120B (en) | 2018-11-14 | 2018-11-14 | Iron-based amorphous alloy powder for degrading dye waste liquid and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109434120A CN109434120A (en) | 2019-03-08 |
| CN109434120B true CN109434120B (en) | 2021-09-03 |
Family
ID=65552832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811352972.1A Active CN109434120B (en) | 2018-11-14 | 2018-11-14 | Iron-based amorphous alloy powder for degrading dye waste liquid and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109434120B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110237854B (en) * | 2019-06-20 | 2022-02-18 | 山东大学 | Method for Fenton catalytic degradation of methylene blue sewage by FeBC amorphous alloy |
| CN110498497B (en) * | 2019-07-29 | 2022-03-15 | 上海黄浦建设工程质量检测有限公司 | MnBi alloy powder for degrading azo-containing chemical bond dye and preparation method thereof |
| CN110759533A (en) * | 2019-11-08 | 2020-02-07 | 上海置信电气非晶有限公司 | Method for treating printing and dyeing wastewater by using amorphous powder |
| CN111170414B (en) * | 2020-01-03 | 2022-06-03 | 东南大学 | Method for degrading dye wastewater by iron-based amorphous alloy strip |
| CN111172380B (en) * | 2020-01-16 | 2022-04-15 | 暨南大学 | Method for improving catalytic activity of Fe-based amorphous alloy for electrolytic water hydrogen evolution by mechanical ultrasonic treatment |
| CN111495412B (en) * | 2020-05-06 | 2022-03-29 | 东南大学 | Iron-based amorphous alloy/g-C3N4Composite photocatalyst and preparation method and application thereof |
| CN111620389A (en) * | 2020-05-19 | 2020-09-04 | 中国科学院金属研究所 | Application of amorphous alloy in catalytic degradation of antibiotic pollutants |
| CN112048658B (en) * | 2020-08-17 | 2021-08-24 | 东南大学 | Preparation method of iron-based amorphous alloy capable of efficiently degrading dye |
| CN113912174A (en) * | 2021-10-29 | 2022-01-11 | 华中科技大学 | Method for improving performance of sewage treatment catalyst, product and application |
| CN114988551B (en) * | 2022-07-05 | 2023-04-21 | 河海大学 | Method for efficiently degrading azo dye by using ultrasonic-assisted iron-based amorphous coating |
| CN117051429B (en) * | 2023-08-29 | 2024-04-19 | 深圳大学 | Platinum-based amorphous alloy electrolyzed water bifunctional catalyst and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1985013A (en) * | 2004-04-29 | 2007-06-20 | U.I.T.有限责任公司 | Method for modifying or producing materials and joints with specific properties by generating and applying adaptive impulses, normalizing energy thereof and pauses therebetween |
| CN101736213A (en) * | 2010-01-05 | 2010-06-16 | 北京航空航天大学 | Method to toughen and malleableize the amorphous alloy by ultrasonic processing |
| CN102070236A (en) * | 2009-11-20 | 2011-05-25 | 中国科学院金属研究所 | Ferrum-based amorphous alloy strip for treating printing and dyeing wastewater and preparation method thereof |
| CN103880149A (en) * | 2014-03-20 | 2014-06-25 | 上海理工大学 | Method of degrading dye wastewater by iron-based amorphous alloy/hydrogen peroxide Fenton-like system |
| CN105314726A (en) * | 2014-07-01 | 2016-02-10 | 中国科学院宁波材料技术与工程研究所 | Printing and dyeing wastewater treatment method |
| CN107326159A (en) * | 2017-06-20 | 2017-11-07 | 清华大学 | It is a kind of to be used for the iron-base nanometer crystal alloy methods for making and using same and device of the processing containing azo dye printing and dyeing wastewater |
| KR20170125192A (en) * | 2016-05-04 | 2017-11-14 | (주) 가이환경에너지 | Method and apparatus for treatment of treating of non-disintegrating organic waste water using the catalyst |
| CN108220824A (en) * | 2017-12-15 | 2018-06-29 | 华南理工大学 | A kind of ferrum-based amorphous alloy strip and its application in dyeing and printing sewage degradation treatment |
| CN108525688A (en) * | 2018-04-28 | 2018-09-14 | 东南大学 | A kind of Fe-based amorphous alloy is used for the application of degradation of dye waste water Methylene Blue |
-
2018
- 2018-11-14 CN CN201811352972.1A patent/CN109434120B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1985013A (en) * | 2004-04-29 | 2007-06-20 | U.I.T.有限责任公司 | Method for modifying or producing materials and joints with specific properties by generating and applying adaptive impulses, normalizing energy thereof and pauses therebetween |
| CN102070236A (en) * | 2009-11-20 | 2011-05-25 | 中国科学院金属研究所 | Ferrum-based amorphous alloy strip for treating printing and dyeing wastewater and preparation method thereof |
| CN101736213A (en) * | 2010-01-05 | 2010-06-16 | 北京航空航天大学 | Method to toughen and malleableize the amorphous alloy by ultrasonic processing |
| CN103880149A (en) * | 2014-03-20 | 2014-06-25 | 上海理工大学 | Method of degrading dye wastewater by iron-based amorphous alloy/hydrogen peroxide Fenton-like system |
| CN105314726A (en) * | 2014-07-01 | 2016-02-10 | 中国科学院宁波材料技术与工程研究所 | Printing and dyeing wastewater treatment method |
| KR20170125192A (en) * | 2016-05-04 | 2017-11-14 | (주) 가이환경에너지 | Method and apparatus for treatment of treating of non-disintegrating organic waste water using the catalyst |
| CN107326159A (en) * | 2017-06-20 | 2017-11-07 | 清华大学 | It is a kind of to be used for the iron-base nanometer crystal alloy methods for making and using same and device of the processing containing azo dye printing and dyeing wastewater |
| CN108220824A (en) * | 2017-12-15 | 2018-06-29 | 华南理工大学 | A kind of ferrum-based amorphous alloy strip and its application in dyeing and printing sewage degradation treatment |
| CN108525688A (en) * | 2018-04-28 | 2018-09-14 | 东南大学 | A kind of Fe-based amorphous alloy is used for the application of degradation of dye waste water Methylene Blue |
Non-Patent Citations (1)
| Title |
|---|
| Fe-Si-B系非晶合金表面微纳米化与催化性能的研究 第3章铁基非晶合金表面微纳米多孔制备工艺的研究;倪兵莹;《中国优秀硕士学位论文全文数据库（电子期刊）》;20180215;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109434120A (en) | 2019-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109434120B (en) | Iron-based amorphous alloy powder for degrading dye waste liquid and preparation method and application thereof | |
| Wang et al. | Investigation of FePC amorphous alloys with self-renewing behaviour for highly efficient decolorization of methylene blue | |
| CN110975872B (en) | Cobalt-based amorphous alloy catalyst and preparation method and application thereof | |
| CN105314726B (en) | A kind of processing method of dyeing and printing sewage | |
| US11027992B2 (en) | Iron-based amorphous electrode material for wastewater treatment and use thereof | |
| Wu et al. | Azo dye degradation behavior of AlFeMnTiM (M= Cr, Co, Ni) high-entropy alloys | |
| US20120285899A1 (en) | Nanopolymetalic reducing agent filler | |
| CN109402369A (en) | A kind of iron-based porous material and preparation method thereof for azo dyes of degrading | |
| Li et al. | Cu-based metallic glass with robust activity and sustainability for wastewater treatment | |
| Qin et al. | Fenton-like degradation of coke wastewater using Fe78Si8B14 and Fe73. 5Nb3Cu1Si13. 5B9 metallic glasses | |
| Ma et al. | Influence of surface morphology of Fe-based amorphous alloys on degradation of azo dye | |
| CN113201699B (en) | Iron-based alloy material and preparation method and application thereof | |
| Dai et al. | Efficient degradation of azo dye by dual-doped photo-enhanced Fenton-like catalysts in magnetic suspension reactor | |
| Luo et al. | Synergistic effect of various elements in Fe41Co7Cr15Mo14C15B6Y2 amorphous alloy hollow ball on catalytic degradation of methylene blue | |
| CN108190883B (en) | A kind of method of purification of diamond | |
| Wu et al. | Rapid decoloration of azo dye Direct Blue 6 by AlCrFeMn high entropy alloy | |
| Chen et al. | Nanostructured metallic glass contributing to efficient catalytic degradation of dye wastewater | |
| CN113680313A (en) | Preparation method of easily-regenerated methylene blue adsorbent | |
| CN111545211B (en) | Graphene oxide-lanthanum oxide-cobalt hydroxide composite material, and synthesis method and application thereof | |
| Pei et al. | Application of Fe-based amorphous alloy in industrial wastewater treatment: a review | |
| CN109399765A (en) | Utilize the method for amorphous alloy electrochemical degradation azo dyes | |
| CN109847751A (en) | It is a kind of to utilize metallurgical dust beam system for polynary magnetic iron base composite material, method and application | |
| Lassoued et al. | Preparation, characterization and application of Fe 72 Cu 1 Co 5 Si 9 B 13 metallic glass catalyst in degradation of azo dyes | |
| Qi et al. | Light activated methylene blue degradation by magnetic Fe80PxC20-x (x= 0, 4, 7 and 13) glassy ribbons | |
| CN107988568B (en) | A kind of amorphous alloy strips and preparation method thereof and the application in dye wastewater treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |