An iron-based amorphous alloy material, its preparation method and application in wastewater treatment

Abstract

The present invention discloses an iron-based amorphous alloy material, a preparation method thereof, and an application in wastewater treatment. In terms of atomic ratio, the chemical formula of the iron-based amorphous alloy material is Fe 83 Si2B 15 . This amorphous alloy material can achieve the co-removal of heavy metal ions (Cu, Sb) and antibiotics in wastewater, has strong anti-interference ability and good stability. Moreover, it does not require external conditions such as oxidants, light, and electricity, and has broad application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical fields of iron-based amorphous alloys and wastewater treatment, and more specifically, relates to an iron-based amorphous alloy material, a preparation method thereof, and an application thereof in wastewater treatment. Background Art

[0002] Livestock wastewater has become one of the main sources of global environmental and water pollution. One of the reasons is the continuous expansion of aquaculture and agriculture, and the usage of feed, antibiotics, and industrial fertilizers has also increased accordingly. Florfenicol (FF) is one of the most commonly used chloramphenicol antibiotics in veterinary drugs, and its residues are often detected in animal feed. At the same time, heavy metals such as copper, lead, and cadmium are also added to animal feed as trace elements to meet the physiological needs of animals. Therefore, FF and copper often coexist in the agricultural environment. Chloramphenicol antibiotics can form coordination complexes with copper through the hydroxyl or carbonyl group of the amide group. It has been found that the combined exposure of FF and Cu(II) can lead to changes in the intestinal microbiota and metabolome of lactating Spragg-Dowley rats, posing potential health risks. Therefore, the efficient co-removal of FF and Cu(II) is of great significance.

[0003] Methods such as adsorption, photocatalysis, advanced oxidation, and electrochemical technology have been applied to the co-removal of heavy metals and antibiotics. However, simple adsorption methods cannot achieve the deep removal of antibiotic wastewater. Photocatalysis or advanced oxidation processes can generate reactive oxygen species to promote the degradation of antibiotics, usually requiring external light irradiation or the addition of advanced oxidants. Excessive use of advanced oxidants may lead to secondary pollution and a significant increase in treatment costs.

[0004] In recent years, the use of abundant iron-based materials to degrade antibiotics has become a research hotspot. As a special ZVI material, iron-based amorphous alloys have the characteristics of corrosion resistance, high catalytic activity, environmental protection, and low cost, and are widely used in water treatment. For example, the literature "Q.Chen,et.Insight into fast catalytic degradation of neutralreactive red 195solution by FePC glassy alloy:Fe release and OH generation,J.Mol.Liq.,364(2022)120058." reported the use of Fe 75 P 15 C 10Amorphous alloys efficiently degrade reactive red 195 (RR195) through photocatalytic Fenton-like reaction. The literature "L. Zhang, et. Insight into efficient degradation of 3,5-dichlorosalicylic acid by Fe-Si-B amorphous ribbon under neutral condition, Appl. Catal., B, 294 (2021)." reported the activation of H2O2 by FeSiB amorphous ribbon for the effective degradation of 3,5-dichlorosalicylic acid. FeSiB amorphous alloy materials (FeSiB AR ) are usually applied to the treatment of printing and dyeing wastewater, such as Chinese patents CN113201699A and CN102070239A. Currently, there is no report on the simultaneous removal of antibiotics and heavy metals using iron-based amorphous alloys. In particular, there are few studies on the simultaneous removal of Cu(II) and degradation of FF using self-generated reactive oxygen species (ROSs) without external assistance. Summary of the Invention

[0005] The object of the present invention is to provide an iron-based amorphous alloy material, its preparation method and application in wastewater treatment, which can achieve the co-removal of two pollutants, namely antibiotics (FF) and heavy metals (Cu(II) / Sb(V)), by using FeSiB AR

[0006] The present invention provides an iron-based amorphous alloy material. In terms of atomic ratio, the chemical formula of the iron-based amorphous alloy material is Fe 83 Si2B 15 .

[0007] Preferably, the iron-based amorphous alloy material is an alloy ribbon.

[0008] The present invention also provides a preparation method of the above-mentioned iron-based amorphous alloy material, which includes the following steps:

[0009] (1) Weigh Fe, Si, and FeB alloys according to the atomic ratio and melt them in a vacuum induction furnace to make Fe 83 Si2B 15 alloy;

[0010] (2) Use a melt spinning device to inductively melt the alloy ingot in an inert atmosphere or vacuum using an intermediate frequency power supply, and spray the molten metal onto the roller through an instantaneous pressure difference to obtain an amorphous alloy ribbon by melt spinning.

[0011] Preferably, the vacuum induction melting is specifically: evacuate the induction furnace cavity to 5.0×10 -3 ​Below Pa, then fill with high-purity argon until the vacuum reaches 400 - 600 Pa for protection. After washing the gas 2 - 4 times repeatedly, synthesize Fe by induction heating. 83 Si2B 15 Alloy ingot.

[0012] Preferably, the step (2) specifically includes:

[0013] Put the master alloy ingot into a quartz tube. When the vacuum degree of the spinning machine decreases to below 5 Pa, introduce high-purity argon until the vacuum degree of the spinning machine cavity reaches 800 - 1000 Pa. Then make the copper roller rotate and keep the rotation speed at 30 - 40 m / s. Next, turn on the induction coil to heat the master alloy ingot in the quartz tube. After the ingot melts, introduce argon into the quartz tube and use the pressure difference to spray the liquid metal onto the high-speed rotating copper roller, thereby preparing an amorphous alloy strip.

[0014] Preferably, the width of the amorphous alloy strip is 0.8 - 1.2 μm, and the thickness is 25 - 30 μm.

[0015] The present invention further provides the application of the above-mentioned iron-based amorphous alloy material in the co-removal of heavy metal ions and antibiotics in wastewater.

[0016] Preferably, the variable-valence metal ions are Cu and / or Sb.

[0017] Preferably, the antibiotic is a chloramphenicol antibiotic.

[0018] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0019] The iron-based amorphous alloy material of the present invention can realize the co-removal of heavy metal ions (Cu, Sb) and antibiotics in wastewater, with strong anti-interference ability and good stability. Moreover, without relying on external conditions such as oxidants, light, and electricity, the co-removal of heavy metal ions and antibiotics can be achieved, having broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 Fe 83 Si2B 15 AR XRD, SEM, and XPS spectra of;

[0021] Among them, (a) XRD, (b) SEM, (c) Fe 2p spectrum, (d) Si 2p spectrum, (e) B 1s spectrum.

[0022] Figure 2 For Fe 83 Si2B 15 ARRemoval effects of FF(a) and Cu(II)(b) in single and binary systems; Experimental conditions: pH0 = 3, dosage 0.5 g / L, [FF]0 = 30 mg / L, [Cu(II)]0 = 100 mg / L.

[0023] Figure 3 Effect of different influencing factors on Fe in binary system 83 Si2B 15 AR Effect on the removal of FF(a) and Cu(II)(b).

[0024] Among them, (a) Effect of pH on Fe 83 Si2B 15 AR Effect on the removal of FF; (b) Effect of pH on Fe 83 Si2B 15 AR Effect on the removal of Cu(II); (c) Effect of Fe 83 Si2B 15 AR Dosage on the removal of FF in binary system; (d) Effect of Fe 83 Si2B 15 AR Dosage on the removal of Cu(II) in binary system; (e) Removal of FF at different Cu(II) concentrations; (f) Removal of Cu(II) at different Cu(II) concentrations.

[0025] Figure 4 Effect of environmental factors on Fe 83 Si2B 15 AR Effect on the removal of FF and Cu(II);

[0026] Among them, (a) Effect of different anions (10 mM) on Fe 83 Si2B 15 AR Effect on the removal of FF; (b) Effect on Fe 83 Si2B 15 AR Effect on the removal of Cu(II); (c) Effect of different H2PO4 2- Concentration on the removal rate of FF; (d) Effect of different H2PO4 - Concentration on the removal rate of Cu(II); (e) Removal rate of Fe 83 Si2B 15 AR On FF in three cycles; (f) Removal rate of Fe 83 Si2B 15 AR On Cu(II) in three cycles.

[0027] Figure 5 For different H2PO4 - pH change during the co-removal process at the initial concentration.

[0028] Figure 6 For Fe 83 Si2B 15 AR Co-removal effect on FF(a) and Cu(II)(b) in different water bodies.

[0029] Figure 7 For Fe 83 Si2B 15 AR XRD spectra before and after the reaction.

[0030] Figure 8 Co-removal rates of different iron-based materials for Cu(II)(a) and FF(b).

[0031] Figure 9 Co-removal rates of heavy metals(a) and FF(b) in different composite systems.

[0032] Experimental conditions: pH0 = 3, dosage 0.5g / L, [FF]0 = 30mg / L, [Sb(V)]0 = 100mg / L. Specific implementation manner

[0033] Many specific details are set forth in the following description in order to provide a thorough understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific implementations disclosed below.

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which this invention belongs. The terms used in the description of the present invention herein are for the purpose of describing specific embodiments only and are not intended to limit the present invention. It should be noted that the reagents used in this embodiment are all ordinary commercially available products.

[0035] Example 1

[0036] Weigh Fe, Si, and FeB alloy according to the atomic ratio, and put the prepared raw materials into an Al2O3 crucible and melt them using a vacuum induction melting furnace: First, perform gas washing. The induction furnace cavity is evacuated to below 5.0×10 -3 Pa, and then filled with high-purity argon until the vacuum reaches 400 - 600 Pa for protection. After washing the gas 3 times repeatedly, synthesize Fe 83 Si2B 15(at.%) master alloy ingot. Then, an alloy strip was prepared using a vacuum melt-spinning machine: First, the master alloy ingot was placed in a special quartz tube with an opening of 0.8 mm. When the vacuum of the melt-spinning machine was reduced to below 5 Pa, high-purity argon was introduced until the vacuum of the melt-spinning machine cavity reached 800 - 1000 Pa. Subsequently, the copper roller was rotated and the rotation speed was maintained at 35 m / s. Then, the induction coil was turned on to heat the master alloy ingot in the quartz tube. After the ingot melted, argon with a pressure of 30 Pa was introduced into the quartz tube, and the liquid metal was sprayed onto the high-speed rotating copper roller using the pressure difference, thereby preparing an alloy strip with a width of approximately 1 micron and a thickness of approximately 27 microns.

[0037] Performance test

[0038] Fe 83 Si2B 15 AR The XRD analysis of is as Figure 1 shown in a. For Fe 83 Si2B 15 AR there is only one typical broad scattering peak at around 45 degrees, indicating that the prepared energy band has an amorphous nature. For Fe 83 Si2B 15 AR The SEM image of shows that the surface of Fe 83 Si2B 15 AR is completely smooth and has no obvious defects ( Figure 1 b). The subsequent SEM-EDS diagram ( Figure 1 b) further reveals the uniform distribution of Fe, Si, and B elements. For Fe 83 Si2B 15 AR The XPS spectrum of also confirms the presence of Fe, Si, and B elements. The Fe2p XPS spectrum ( Figure 1 c) shows 5 sub-bands at binding energies of 706.7, 710.3 / 722.9, and 711.2 / 725.2 eV, corresponding to the binding energies of Fe 0 , Fe(II), and Fe(III) respectively. The appearance of the Fe(II) and Fe(III) characteristic peaks may be due to the formation of iron oxide during the preparation and storage of the material. The Si 2p spectrum ( Figure 1 d) shows two obvious peaks at 100.1 and 102.2 eV, attributed to Si-Si and Si-O bonds respectively. Meanwhile, the binding energies of B 1s at 187.4 and 191.8 eV ( Figure 1 e) are consistent with the B-B and B-O bands respectively.

[0039] Figure 2 Shows Fe 83 Si2B 15AR Removal rates of the single systems of FF or Cu(II) and the binary system of FF and Cu(II). Fe 83 Si2B 15 AR The removal rate of FF was only 9.70% in the single system and increased by 7.5 times to 85.23% in the binary system ( Figure 2 a). Meanwhile, Fe 83 Si2B 15 AR The redox reaction of Cu(II) showed high reactivity in both the single and binary systems, with removal rates of 92.75% and 93.09% respectively ( Figure 2 b). This highlights the role of copper ions in the co-removal of FF.

[0040] The initial pH value (pH0) of the solution affects the reaction process by influencing the surface charge of the catalyst and the state of the pollutants. Figure 3 Shows the co-removal efficiency of FF and Cu(II) by Fe 83 Si2B 15 AR under the condition of pH 2 - 5. As Figure 3 shown in a, the lower the pH, the higher the final removal rate of FF. This may be because a lower pH is conducive to the cyclic transformation between Fe0 / Fe(II) / Fe(III) and the generation of ·OH, thus accelerating the reduction of Cu(II) as well ( Figure 3 b).

[0041] The dosage of the material is another key factor affecting the removal of FF and Cu(II) by Fe 83 Si2B 15 AR As Figure 3 shown in c, with the increase of the catalyst dosage, the removal rates of FF and Cu(II) gradually increased from 0.1 g / L to 0.75 g / L. When the dosage increased from 0.5 g / L to 0.75 g / L, the removal rates of FF and Cu(II) only increased by 2.47% and 1.58% respectively. Considering the cost, the catalyst dosage was determined to be 0.5 g / L in the subsequent experiments.

[0042] As can be seen from Figure 2 a, Cu(II) has an extremely important influence on the removal of FF by Fe 83 Si2B 15 AR Therefore, the influence of the initial Cu(II) concentration ([Cu(II)]) on the co-removal of the reaction was studied. When [Cu(II)] increased from 0 mg / L to 10 mg / L, the degradation rate of FF increased from 9.70% to 76.58%, almost increasing by 7 times (Figure 3 c). When the [Cu(II)] concentration increases from 10 mg / L to 100 mg / L, the removal rate only increases by 8.65%. The results show that Cu(II) actively participates in the removal of FF through the activation of Fe 83 Si2B 15 AR This activation may be due to the redox reaction between Fe0 and Cu(II), generating Fe(II) or Fe(III), which is crucial in the production of ROS and ultimately degrades FF.

[0043] Various anions and dissolved organic matters widely exist in natural waters and wastewaters. The present invention studied the effects of different anions and humic acid (HA, 10 mg / L) on the co-removal performance of Fe 83 Si2B 15 AR As shown in Figure 4 a - b, SO4 2- has little effect on the removal rate of Cu(II) and slightly promotes the degradation of FF. HA inhibits the removal of Cu(II) because HA can form strong complexes with copper ions, thus reducing the free Cu(II) available for reduction. At the same time, HA contains abundant functional group structures such as hydroxyl, carboxyl, and quinone, which can promote the continuous release of iron ions and thus degrade FF. Cl - significantly inhibits the removal of Cu(II), which may be due to the formation of stable complexes such as [CuCl4] 2- , reducing the availability of Cu(II). While Cl - significantly promotes the degradation of FF, which may be due to the formation of reactive chlorine species (Cl2 / HClO) by excessive Cl - . NO3 - has certain oxidation ability to form NO2 - , promoting the removal of Cu(II). This can be explained that the reduction of NO3 - results in the release of Fe(II) in F e83 Si2B 15 AR to reduce Cu(II). It is worth noting that H2PO4 - significantly promotes the removal of FF and Cu(II) ( Figure 4 c - d). When the concentration of H2PO4 - increases from 0 to 10 mM, the removal rate of FF increases from 84.53% to 100%, and the removal rate of Cu(II) increases from 90.67% to 98.59%. Further detection of the pH value change during this reaction process ( Figure 5 ). When H2PO4 -When it is 10 mM or 5 mM, due to its buffering effect, the pH of the solution remains stable below 4 within 120 min, which is beneficial to the degradation of FF, while the final pH of the solution is 5.63 or 5.98, accelerating the precipitation of Cu(II).

[0044] Fe 83 Si2B 15 AR The / FF / Cu(II) system can adapt to complex water environments and has been studied in natural waters. As Figure 6 shown, various complex trace ions in tap water and Liuyang River water slightly promoted the degradation rate of FF, but the removal rate was low. At the same time, these ions competed with Cu(II) for the active sites of the catalyst, inhibiting the removal of Cu(II). In contrast, both FF and Cu(II) could be completely removed from medical wastewater.

[0045] Fe 83 Si2B 15 AR The reusability study of Figure 4 is shown in e-f. The degradation rates of FF in the first 3 cycles were 84.53%, ~93.80%, and 90.3% respectively. The reason for the degradation fluctuation may be due to the increased surface area and structural collapse of the Fe 83 Si2B 15 AR belt. In addition, there was no obvious difference between the XRD patterns of fresh Fe 83 Si2B 15 AR and used Fe 83 Si2B 15 AR ( Figure 7 ), indicating that the catalyst has considerable stability.

[0046] Figure 8 shows the co-removal effects of different iron-based materials on FF and Cu(II). In the removal of Cu(II), the effects of two materials, FePC (77.83%) and FeSiBP (76.55), were poor, and the removal rates of Cu(II) by the other 4 materials were all above 85%. Among them, the removal rate of Fe 83 Si2B 15 AR reached 90.92%. However, in the process of co-removing FF, Fe 83 Si2B 15 AR (86.68%) had a significantly higher removal rate of FF than iron powder (66.42%), Fe 83 Si2B 15 CR (80.19%), Fe78 Si9B 13 AR (58.50%), FePC (56.05%), and FeSiBP (53.30%). Therefore, Fe 83 Si2B 15 AR has higher co-removal performance, and this material was selected for research.

[0047] Apply Fe 83 Si2B 15 AR to different complex water bodies ( Figure 9 ). It was found that Fe 83 Si2B 15 AR not only had significant removal effects in the co-removal of FF (86.68%) and Cu(II) (90.92%), but also had high removal effects on the FF (76.87%) and Sb(V) (87.84%) composite pollution system. It shows that this amorphous alloy material can achieve the co-removal of heavy metal ions (Cu, Sb) and antibiotics in wastewater.

[0048] The above-described embodiments only represent several implementation manners of the present invention. The description is relatively specific and detailed, but it should not be construed as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. Application of an iron-based amorphous alloy material in co-removing heavy metal ions and antibiotics from wastewater, characterized in that, The iron-based amorphous alloy material is an alloy strip, and its chemical formula is Fe 83 Si2B 15 ; the heavy metal is Cu and / or Sb; the antibiotic is a chloramphenicol antibiotic; The preparation method of the alloy strip comprises: placing Fe, Si and FeB alloys in an Al2O3 crucible and melting them in a vacuum induction melting furnace: firstly, washing the gas, and evacuating the induction furnace chamber to a vacuum of 5.0×10 -3 Pa, and then fill with high-purity argon gas to a vacuum of 400-600 Pa for protection. Repeat the gas washing 2-4 times before induction heating to synthesize Fe 83 SiC 15 alloy ingot; placing the master alloy ingot into a quartz tube, and when the vacuum degree of the belt spinning machine drops below 5 Pa, introducing high-purity argon gas until the vacuum degree of the belt spinning machine chamber reaches 800-1000 Pa, then rotating the copper roller and maintaining the rotation speed at 30-40 m / s, and then turning on the induction coil to heat the master alloy ingot in the quartz tube, and after the ingot is melted, introducing argon gas into the quartz tube and using the pressure difference to spray the liquid metal onto the high-speed rotating copper roller, thereby preparing an amorphous alloy strip.

2. The application according to claim 1, wherein The width of the amorphous alloy strip is 0.8 - 1.2 μm, and the thickness is 25 - 30 μm.

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