Method for degrading dye wastewater containing rhodamine B
By preparing Fe-Si-B amorphous nanoparticles and combining them with ultrasonic treatment, the problem of large consumption of traditional iron-based amorphous strips was solved, and the efficient degradation of Rhodamine B dye wastewater was achieved with high degradation rate and low cost.
Patent Information
- Application Number
- CN202511097006.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-06
- Publication Date
- 2025-11-11
AI Technical Summary
In existing technologies, iron-based amorphous strip catalysts are used in large quantities, and traditional methods are difficult to efficiently degrade organic dye wastewater, especially Rhodamine B dye, and are also costly.
Fe-Si-B amorphous nanoparticles were prepared by chemical reduction. By adjusting the pH value to 2.5–3.5, adding Fe-Si-B amorphous nanoparticles and hydrogen peroxide, and then ultrasonically treating Rhodamine B dye wastewater, the degradation efficiency was significantly improved.
It significantly shortens the degradation time of Rhodamine B dye, achieves a degradation rate of over 99%, has a low degradation cost, and solves the problem of large amounts of traditional catalysts.
Smart Images
Figure CN120923006A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of organic dye catalytic degradation technology, and in particular to a method for degrading wastewater containing Rhodamine B dye. Background Technology
[0002] Organic synthetic dyes are widely used in industries such as textiles due to their vibrant colors and low cost. However, the use of organic synthetic dyes generates large amounts of wastewater, ultimately causing water pollution. Because dye wastewater has high color intensity, strong stability, and certain toxicity and carcinogenicity, its treatment is significantly more difficult.
[0003] Amorphous alloys exist in a non-equilibrium state, and the activation energy required for chemical reactions is lower than that of traditional crystalline alloys, making them ideal catalysts. Iron-based amorphous alloys are widely used to degrade organic dyes via Fenton-like reactions, but traditional iron-based amorphous ribbons have the problem of large quantities required. Therefore, it is crucial to explore an amorphous alloy with high degradation efficiency.
[0004] Iron-based amorphous nanoparticles have a much larger specific surface area than traditional iron-based amorphous strips, thus exhibiting higher catalytic degradation efficiency. Furthermore, due to their excellent magnetic properties, the particles can be recovered by applying a magnetic field after the degradation reaction is complete. Therefore, providing iron-based amorphous particles for the catalytic degradation of organic dye wastewater is of great significance. Summary of the Invention
[0005] The purpose of this invention is to provide a method for degrading wastewater containing Rhodamine B dye. By preparing Fe-Si-B amorphous nanoparticles using a specific method and applying them to degrade Rhodamine B dye in wastewater, the degradation time of Rhodamine B dye is significantly shortened and the degradation rate of Rhodamine B dye is improved.
[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:
[0007] This invention provides a method for degrading wastewater containing Rhodamine B dye, comprising the following steps:
[0008] The pH of the Rhodamine B dye wastewater was adjusted to 2.5–3.5, Fe-Si-B amorphous nanoparticles were added, the mixture was sonicated, and hydrogen peroxide was added to obtain the degraded wastewater.
[0009] Preferably, hydrochloric acid or sulfuric acid is used to adjust the pH of the Rhodamine B dye wastewater.
[0010] Preferably, the preparation method of the Fe-Si-B amorphous nanoparticles is as follows: ferrous chloride or ferrous sulfate is mixed with sodium fluorosilicate, sodium borohydride is added under inert gas protection, the mixture is reacted, washed with water and / or anhydrous ethanol, and vacuum dried to obtain the Fe-Si-B amorphous nanoparticles.
[0011] Preferably, the molar ratio of ferrous ions to silicon ions during mixing is 1:0.1 to 0.2; and the particle size of the Fe-Si-B amorphous nanoparticles is 50 to 90 nm.
[0012] Preferably, the inert gas is nitrogen or argon; the molar concentration of sodium borohydride is 1-3 mol / L, and the molar ratio of sodium borohydride to ferrous chloride or ferrous sulfate is 1:0.1-0.3.
[0013] Preferably, the vacuum drying temperature is 50–60°C, and the vacuum drying time is 6–10 hours.
[0014] Preferably, the mass-volume concentration of Rhodamine B dye in the Rhodamine B dye wastewater is 10–50 mg / L.
[0015] Preferably, the mass-to-volume ratio of the Fe-Si-B amorphous nanoparticles to the Rhodamine B dye wastewater is 5–20 mg: 1 L.
[0016] Preferably, the temperature of the ultrasound is 20-30°C, and the duration of the ultrasound is 2-10 minutes.
[0017] Preferably, the molar concentration of the hydrogen peroxide is 4 to 6 mmol / L.
[0018] The beneficial effects of this invention compared to the prior art are as follows:
[0019] This invention prepares Fe-Si-B amorphous nanoparticles via a chemical reduction method. This preparation method is simple to operate and has relatively low preparation cost. Compared with traditional Fe-Si-B amorphous strips, less Fe-Si-B is required for the degradation of organic dyes, thus solving the problem of large amounts of iron-based amorphous alloy catalysts in existing technologies. Furthermore, the prepared Fe-Si-B amorphous nanoparticles can achieve a Rhodamine B degradation rate of over 99% in a short time, and the cost is low, showing potential application prospects in the field of organic dye wastewater degradation. Attached Figure Description
[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0021] Figure 1 The degradation rates of Rhodamine B are shown in Examples 1 and 4 to 6.
[0022] Figure 2 The degradation rate results of Rhodamine B in Examples 1 and 7 to 9 are shown.
[0023] Figure 3 The degradation rates of Rhodamine B are shown in Examples 1 and 10 to 12.
[0024] Figure 4 The degradation rates of Rhodamine B are shown in Example 1 and Comparative Example 1. Detailed Implementation
[0025] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.
[0026] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.
[0027] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.
[0028] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.
[0029] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.
[0030] This invention provides a method for degrading wastewater containing Rhodamine B dye, comprising the following steps:
[0031] The pH of the Rhodamine B dye wastewater was adjusted to 2.5–3.5, Fe-Si-B amorphous nanoparticles were added, the mixture was sonicated, and hydrogen peroxide was added to obtain the degraded wastewater.
[0032] In this invention, hydrochloric acid or sulfuric acid is preferably used to adjust the pH of the Rhodamine B dye wastewater; the molar concentration of the hydrochloric acid or sulfuric acid is preferably 0.5–1.5 mol / L, more preferably 0.8–1.2 mol / L, and even more preferably 1 mol / L; the adjustment temperature is preferably 25–70°C, more preferably 30–60°C, even more preferably 40–50°C, and even more preferably 45°C; the preferred method for preparing the Fe-Si-B amorphous nanoparticles is as follows: ferrous chloride or ferrous sulfate is mixed with sodium fluorosilicate, sodium borohydride is added under inert gas protection, the mixture is reacted, washed with water and / or anhydrous ethanol, and vacuum dried to obtain the Fe-Si-B amorphous nanoparticles. The mixture comprises crystalline nanoparticles; the molar ratio of ferrous chloride or ferrous sulfate to sodium fluorosilicate during mixing is preferably 1:0.1–0.2, more preferably 1:0.14–0.18, and even more preferably 1:0.15; the particle size of the Fe-Si-B amorphous nanoparticles is preferably 50–90 nm, more preferably 60–80 nm, and even more preferably 70 nm; the inert gas is preferably nitrogen or argon; the molar concentration of sodium borohydride is preferably 1–3 mol / L, more preferably 1.5–2.5 mol / L, and even more preferably 2 mol / L; the molar ratio of sodium borohydride to ferrous chloride or ferrous sulfate is preferably 1:0.1–0.3, more preferably 1:0.2; The preferred method for adding sodium borohydride is dropwise addition; the dropwise addition is preferably accompanied by stirring; the preferred reaction temperature is 20–30°C, more preferably 24–28°C, and even more preferably 25°C; the preferred reaction time is 15–30 min, more preferably 20–25 min, and even more preferably 23 min; the preferred reaction is accompanied by stirring; the preferred stirring speed is 200–500 r / min, more preferably 300–400 r / min, and even more preferably 350 r / min. / min; the number of washing cycles is preferably 3 to 5, more preferably 4; the vacuum drying temperature is preferably 50 to 60°C, more preferably 54 to 58°C, and even more preferably 55°C; the vacuum drying time is preferably 6 to 10 hours, more preferably 7 to 9 hours, and even more preferably 8 hours; the mass-volume concentration of Rhodamine B dye in the Rhodamine B dye wastewater is preferably 10 to 50 mg / L, more preferably 20 to 40 mg / L, and even more preferably 30 mg / L; the Fe-Si-B amorphous nanoparticles The preferred mass-to-volume ratio of the granules to the Rhodamine B dye wastewater is 5–20 mg:1 L, more preferably 10–15 mg:1 L, and even more preferably 12 mg:1 L; the preferred ultrasonic temperature is 20–30 °C, more preferably 24–28 °C, and even more preferably 25 °C; the preferred ultrasonic time is 2–10 min, more preferably 5–8 min, and even more preferably 6 min; the preferred molar concentration of hydrogen peroxide is 4–6 mmol / L, more preferably 4.5–5.5 mmol / L, and even more preferably... The preferred concentration of hydrogen peroxide is 5 mmol / L; after adding hydrogen peroxide, stirring is preferably performed, with a stirring speed preferably 200–500 r / min, more preferably 300–400 r / min, and even more preferably 350 r / min; the stirring temperature is preferably 25–70°C, more preferably 30–60°C, even more preferably 40–50°C, and still more preferably 45°C; the stirring time is preferably 15–30 min, more preferably 20–25 min, and even more preferably 23 min.
[0033] Example 1
[0034] A method for degrading wastewater containing Rhodamine B dye, comprising the following steps:
[0035] At 25℃, the pH of 1L of wastewater containing 20mg / L Rhodamine B dye was adjusted to 3.0 using 1.0mol / L hydrochloric acid. 10mg Fe-Si-B amorphous nanoparticles were added, and the mixture was sonicated at 25℃ for 5min. Then, 5mmol / L hydrogen peroxide was added, and the mixture was stirred at 25℃ and 500r / min for 30min to obtain the degraded wastewater.
[0036] The preparation method of the Fe-Si-B amorphous nanoparticles is as follows: 6.255g of ferrous chloride and 0.564g of sodium fluorosilicate are dissolved in 200ml of deionized water to obtain ferrous chloride solution and sodium fluorosilicate solution respectively. Ferrous chloride and sodium fluorosilicate are mixed at a molar ratio of 1:0.1. Under nitrogen protection, 50mL of 2mol / L sodium borohydride solution is added dropwise while stirring at 300r / min. The mixture is stirred at 300r / min for 30min at 25℃. The nanoparticles are washed 5 times with water and / or anhydrous ethanol and dried under vacuum at 60℃ for 10h to obtain 70nm Fe-Si-B amorphous nanoparticles. The particle size of the nanoparticles is observed and determined by transmission electron microscopy.
[0037] Example 2
[0038] A method for degrading wastewater containing Rhodamine B dye, comprising the following steps:
[0039] At 70℃, the pH of 1L of wastewater containing 50mg / L Rhodamine B dye was adjusted to 3.5 using 0.5mol / L sulfuric acid. 20mg of Fe-Si-B amorphous nanoparticles were added, and the mixture was sonicated at 20℃ for 10min. Then, 6mmol / L hydrogen peroxide was added, and the mixture was stirred at 70℃ and 300r / min for 15min to obtain the degraded wastewater.
[0040] The preparation method of the Fe-Si-B amorphous nanoparticles is as follows: 6.255g of ferrous sulfate and 0.564g of sodium fluorosilicate are dissolved in 200ml of deionized water to obtain ferrous sulfate solution and sodium fluorosilicate solution. Ferrous sulfate and sodium fluorosilicate are mixed at a molar ratio of 1:0.2. At 20°C, under argon protection, 50mL of 3mol / L sodium borohydride solution is added dropwise while stirring at 500r / min for 15min. The mixture is washed 4 times with water and / or anhydrous ethanol and dried under vacuum at 50°C for 8h to obtain 50nm Fe-Si-B amorphous nanoparticles.
[0041] Example 3
[0042] A method for degrading wastewater containing Rhodamine B dye, comprising the following steps:
[0043] At 50℃, the pH of 1L of wastewater containing 10mg / L Rhodamine B dye was adjusted to 2.5 using 1.5mol / L hydrochloric acid. 5mg Fe-Si-B amorphous nanoparticles were added, and the mixture was sonicated at 30℃ for 2min. Then, 4mmol / L hydrogen peroxide was added, and the mixture was stirred at 50℃ and 200r / min for 20min to obtain the degraded wastewater.
[0044] The preparation method of the Fe-Si-B amorphous nanoparticles is as follows: 6.255g of ferrous chloride and 0.564g of sodium fluorosilicate are dissolved in 200ml of deionized water to obtain ferrous chloride solution and sodium fluorosilicate solution. Ferrous chloride and sodium fluorosilicate are mixed at a molar ratio of 1:0.15. At 30°C, under nitrogen protection, 100mL of 1mol / L sodium borohydride solution is added dropwise while stirring at 200r / min for 20min. The mixture is washed three times with water and / or anhydrous ethanol and dried under vacuum at 55°C for 6h to obtain 90nm Fe-Si-B amorphous nanoparticles.
[0045] Example 4
[0046] The method described in Example 1 was used to degrade Rhodamine B dye in wastewater, except that "5 mmol / L hydrogen peroxide" was replaced with "2.5 mmol / L hydrogen peroxide".
[0047] Example 5
[0048] The method described in Example 1 was used to degrade Rhodamine B dye in wastewater, except that "5 mmol / L hydrogen peroxide" was replaced with "10 mmol / L hydrogen peroxide".
[0049] Example 6
[0050] The method described in Example 1 was used to degrade Rhodamine B dye in wastewater, except that "5 mmol / L hydrogen peroxide" was replaced with "20 mmol / L hydrogen peroxide".
[0051] Example 7
[0052] The method described in Example 1 was used to degrade Rhodamine B dye in wastewater, except that "adding 10 mg of Fe-Si-B amorphous nanoparticles" was replaced with "adding 5 mg of Fe-Si-B amorphous nanoparticles".
[0053] Example 8
[0054] The method described in Example 1 was used to degrade Rhodamine B dye in wastewater, except that "adding 10 mg of Fe-Si-B amorphous nanoparticles" was replaced with "adding 15 mg of Fe-Si-B amorphous nanoparticles".
[0055] Example 9
[0056] The method described in Example 1 was used to degrade Rhodamine B dye in wastewater, except that "adding 10 mg of Fe-Si-B amorphous nanoparticles" was replaced with "adding 20 mg of Fe-Si-B amorphous nanoparticles".
[0057] Example 10
[0058] The method described in Example 1 was used to degrade Rhodamine B dye in wastewater, except that "stirring at 25°C and 500 rpm for 30 min" was replaced with "stirring at 40°C and 500 rpm for 30 min".
[0059] Example 11
[0060] The method described in Example 1 was used to degrade Rhodamine B dye in wastewater, except that "stirring at 25°C and 500 rpm for 30 min" was replaced with "stirring at 55°C and 500 rpm for 30 min".
[0061] Example 12
[0062] The method described in Example 1 was used to degrade Rhodamine B dye in wastewater, except that "stirring at 25°C and 500 rpm for 30 min" was replaced with "stirring at 70°C and 500 rpm for 30 min".
[0063] Comparative Example 1
[0064] The method described in Example 1 was used to degrade Rhodamine B dye in wastewater, except that "Fe-Si-B amorphous nanoparticles" were replaced with "crystalline reduced iron powder (purchased from Shanghai Maclean Biochemical Technology Co., Ltd.)".
[0065] Experimental Example 1
[0066] Rhodamine B dye in wastewater was degraded according to the methods described in Examples 1, 4 to 12, and Comparative Example 1. 2 mL of the degraded wastewater was collected at 0, 2, 4, 6, 8, 10, 15, 20, 25, and 30 minutes after the addition of hydrogen peroxide and stirring. The absorbance at 554 nm was measured using a visible light spectrophotometer. The concentration of the Rhodamine B solution was directly proportional to its absorbance at 554 nm, thus calculating the degradation rate of Rhodamine B at different time points. The formula for calculating the Rhodamine B degradation rate is: η = (C0 - C...) t ) / C0×100%, where η is the degradation rate, C0 is the initial concentration of Rhodamine B solution, and C t Let be the concentration of Rhodamine B solution at time t. The results are as follows: Figures 1 to 4 As shown.
[0067] The results showed that when the H2O2 concentration increased from 2.5 mmol / L to 5 mmol / L, the time required for the degradation of Rhodamine B decreased from 30 min to 15 min. However, when the initial H2O2 concentration increased to 10 mmol / L and 20 mmol / L, the degradation efficiency actually decreased; after 30 min of degradation, the degradation rates of Rhodamine B were 95.0% and 93.8%, respectively.
[0068] With increasing addition of Fe-Si-B amorphous nanoparticles, the degradation efficiency of Rhodamine B significantly increased. At an addition concentration of 5 mg / L, Rhodamine B was degraded after 30 minutes; when the concentration increased to 20 mg / L, it was degraded in just 2 minutes.
[0069] When the stirring temperature was 25℃, Rhodamine B was degraded after 15 minutes, while when the stirring temperature was 70℃, Rhodamine B was degraded in only 2 minutes.
[0070] After 30 minutes of degradation of Rhodamine B using crystalline reduced iron powder, the degradation rate was 60.8%. However, when Fe-Si-B amorphous nanoparticles were used, the degradation time was significantly shortened and the degradation rate was significantly improved. Therefore, the degradation efficiency of Fe-Si-B amorphous nanoparticles was significantly better than that of crystalline reduced iron powder.
[0071] As can be seen from the above embodiments, the present invention provides a method for degrading wastewater containing Rhodamine B dye. The method can achieve a degradation rate of over 99% for Rhodamine B dye in the wastewater, and the total degradation time is significantly shortened to about 20 minutes.
[0072] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A method for degrading wastewater containing Rhodamine B dye, characterized in that, Includes the following steps: The pH of the Rhodamine B dye wastewater was adjusted to 2.5–3.5, Fe-Si-B amorphous nanoparticles were added, the mixture was sonicated, and hydrogen peroxide was added to obtain the degraded wastewater.
2. The method according to claim 1, characterized in that, Hydrochloric acid or sulfuric acid is used to adjust the pH of the Rhodamine B dye wastewater.
3. The method according to claim 1, characterized in that, The preparation method of the Fe-Si-B amorphous nanoparticles is as follows: ferrous chloride or ferrous sulfate is mixed with sodium fluorosilicate, sodium borohydride is added under inert gas protection, the mixture is reacted, washed with water and / or anhydrous ethanol, and dried under vacuum to obtain the Fe-Si-B amorphous nanoparticles.
4. The method according to claim 3, characterized in that, The molar ratio of ferrous ions to silicon ions during mixing is 1:0.1 to 0.2; the particle size of the Fe-Si-B amorphous nanoparticles is 50 to 90 nm.
5. The method according to claim 3, characterized in that, The inert gas is nitrogen or argon; the molar concentration of sodium borohydride is 1-3 mol / L, and the molar ratio of sodium borohydride to ferrous chloride or ferrous sulfate is 1:0.1-0.
3.
6. The method according to claim 3, characterized in that, The vacuum drying temperature is 50–60°C, and the vacuum drying time is 6–10 hours.
7. The method according to claim 1, characterized in that, The mass-volume concentration of Rhodamine B dye in the Rhodamine B dye wastewater is 10–50 mg / L.
8. The method according to claim 1, characterized in that, The mass-to-volume ratio of the Fe-Si-B amorphous nanoparticles to the Rhodamine B dye wastewater is 5–20 mg: 1 L.
9. The method according to claim 1, characterized in that, The temperature of the ultrasound is 20-30°C, and the duration of the ultrasound is 2-10 minutes.
10. The method according to claim 1, characterized in that, The molar concentration of the hydrogen peroxide is 4–6 mmol / L.