Method for rapidly degrading bisphenol A and bisphenol B in water body

Abstract

The invention relates to a method for rapidly degrading bisphenol A and bisphenol B in a water body, which comprises the following steps: 1) dissolving copper nitrate and palladium nitrate in purified water to obtain a precursor, and then adding sodium hydroxide to obtain a suspension; 2) stirring the suspension, transferring the suspension into a high-pressure sterilizer for sterilization, cooling, centrifugally collecting Cu2PdO3, washing, drying in vacuum, and grinding to obtain Cu2PdO3 nanoparticles; (3) adding the Cu2PdO3 nano-particles into water, so as to obtain a Cu2PdO3 nano-particle dispersion liquid; according to the method, bimetallic oxide nanoparticles Cu2PdO3 are synthesized, and the purpose of completely degrading BPA in a water body is achieved by activating persulfate. The Cu-Pd bimetallic oxide prepared through the method has good catalytic activity when being used for activating the BPA and BPB in the persulfate treatment water, the activity of the persulfate can be stimulated, and efficient degradation of the BPA and BPB is achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of organic pollutant degradation, and in particular relates to a method for rapidly degrading bisphenol A and bisphenol B in water. Background Art

[0002] Bisphenol A (BPA) is an important industrial raw material, commonly used in the synthesis of materials such as epoxy resin and polycarbonate plastics. It can be used as an additive to produce plasticizers, flame retardants, thermal stabilizers and other products. Its consumption in my country has been increasing year by year. However, it is also a typical environmental endocrine disruptor. Long-term exposure to BPA, even at low concentrations, can cause neurotoxicity, hepatotoxicity, reproductive toxicity, immunotoxicity and other toxic damages to the body, causing diabetes, inflammation, obesity, anxiety, depression and even cancer. Bisphenol B (BPB) is a BPA analogue (BPAs), which is a class of chemical substances with similar structures or functions to BPA. Common BPA analogues currently used in various daily products (such as water bottles, food and paper products, thermal receipts and storage containers) include bisphenol B (BPB), bisphenol S (BPS), bisphenol F (BPF) and bisphenol AF (BPAF). These substances can be detected in food, indoor dust, environmental samples, human specimens and consumer products. In laboratory studies, many BPA analogs have exhibited endocrine disrupting effects, genotoxicity, cytotoxicity, reproductive toxicity, dioxin-like effects, and neurotoxicity; BPB, BPS, BPF, and BPAF have been shown to have similar or even greater estrogenic and / or anti-androgenic activities than BPA.

[0003] With the development of the industrial industry, the use of bisphenol A and its analogues is still increasing year by year. The global bisphenol A market size is expected to grow from 7.49 million tons in 2023 to 10.13 million tons in 2028, with a compound annual growth rate of 6.23% during the forecast period (2023-2028). Once BP enters the water, it can participate in the natural water cycle, while polluting groundwater and surface water and entering the atmosphere through the water cycle, expanding the overall distribution range, and easily entering the food chain to affect wildlife and humans. Therefore, before bisphenol A and its analogues are discharged into surface water, it is necessary to remove bisphenol A and its analogues from wastewater.

[0004] At present, the removal processes of bisphenol A in water treatment processes mainly include physical adsorption, biological and chemical methods. Adsorption is one of the most widely used methods for removing bisphenol A-like substances, which mainly uses the adsorption effect of activated carbon or kaolin. In addition, anaerobic sludge also has an adsorption effect on bisphenol A. Biological degradation of bisphenol A mainly uses microorganisms that can metabolize bisphenol A selected from nature or cultivated artificially to degrade it. At present, there are also extensive studies on the degradation of bisphenol A by photocatalytic oxidation, electrochemical oxidation and ozone oxidation. However, the above methods have problems such as high treatment cost and low load resistance during application. At present, the mainstream BPA degradation method is an advanced oxidation method based on persulfate activation. This method mainly degrades organic matter by activating a large amount of reactive oxygen species (ROS) produced by persulfate (PMS) or peroxydisulfate (PDS). Although persulfate anions can react with a variety of organic compounds without activation, their oxidation ability is weaker than that of activated persulfate. Therefore, specific reaction conditions or the addition of catalysts are required to activate PMS. Therefore, seeking an efficient catalytic or activated PMS to achieve efficient degradation of BPA and its analogs in a convenient, safe and pollution-free manner is a hot topic in current research. Summary of the invention

[0005] In view of the problems existing in the prior art, the purpose of the present invention is to provide a method for rapidly degrading bisphenol A and bisphenol B in water, which is specifically achieved through the following technical solutions:

[0006] A method for rapidly degrading bisphenol A and bisphenol B in water, the method comprising the following steps:

[0007] 1) dissolving copper nitrate and palladium nitrate in pure water to prepare a precursor, and stirring by magnetic force until a uniform solution is formed; slowly adding sodium hydroxide to the uniform solution, adjusting the pH to 12, ensuring that the coprecipitation is completely produced, and obtaining a suspension;

[0008] 2) stirring the suspension in step 1) at 70° C. for 1 h to obtain a dark brown solution, then transferring the dark brown solution to a 100 mL teflon-lined stainless steel autoclave for high temperature sterilization, cooling and centrifuging to collect Cu2PdO3, washing with pure water and ethanol at least 3 times in sequence, and then vacuum drying and grinding to obtain Cu2PdO3 nanoparticles;

[0009] 3) adding the Cu2PdO3 nanoparticles prepared in step 2) into water and ultrasonicating for 30 minutes to obtain a Cu2PdO3 nanoparticle dispersion;

[0010] 4) adding persulfate into a solution containing target pollutants bisphenol A and bisphenol B, and finally adding a Cu2PdO3 nanoparticle dispersion to catalyze the degradation of the target pollutants bisphenol A and bisphenol B.

[0011] Furthermore, in step 1), the molar ratio of copper nitrate to palladium nitrate is 2:1.

[0012] Furthermore, in step 2), the temperature of high temperature sterilization is 160°C, the sterilization time is 12h, and the temperature of vacuum drying is 60°C.

[0013] Furthermore, in step 4), the concentrations of BPA and BPB in the bisphenol A and bisphenol B solutions are both 1-20 mg / L, and the pH value of the bisphenol A and bisphenol B solutions is 2-10.

[0014] Furthermore, in step 4), the total mass ratio of Cu2PdO3 nanoparticles to BPA / BPB is 5:1-1:1.

[0015] Furthermore, in step 4), the mass ratio of Cu2PdO3 nanoparticles to persulfate is 1:2-10.

[0016] Furthermore, in step 4), the temperature of catalytic degradation is 15-40° C., and the time of catalytic degradation is 10-15 min.

[0017] The present invention synthesizes bimetallic oxide nanoparticles Cu2PdO3 by using a chemical coprecipitation method, and the nanoparticles achieve the purpose of completely degrading BPA in water by activating persulfate. The Cu-Pd bimetallic oxide prepared by the present invention has good catalytic activity when used to activate BPA and BPB in persulfate-treated water, can stimulate the activity of persulfate, and achieve efficient degradation of BPA and BPB. In addition to BPA and BPB, the present invention can also be applied to the degradation of other difficult-to-degrade organic pollutants in water. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 The degradation effect of pH on BPA and BPB in Example 1;

[0019] Figure 2 The degradation effect of the amount of persulfate (PMS) used in Example 2 on BPA and BPB;

[0020] Figure 3 The degradation effect of the amount of catalyst Cu2PdO3 nanoparticles on BPA and BPB;

[0021] Figure 4 The degradation effects of NaCl, NaHCO3, NaNO3, and NaH2PO4 on BPA and BPB were simulated under high-salt wastewater conditions;

[0022] Figure 5 The degradation effects of single metal nano-oxides CuO and PdO in Comparative Example 1 and double metal nano-oxides Cu2PdO3 in this example on BPA and BPB are compared;

[0023] Figure 6 The degradation effects of BPA and BPB on Comparative Examples 2 and 3 without persulfate, other bimetallic nanooxides, bimetallic nanosulfides and the bimetallic nanooxide Cu2PdO3 of the present application are compared. DETAILED DESCRIPTION

[0024] The present invention is further described below in conjunction with specific embodiments to facilitate a better understanding of the present technical solution.

[0025] The following formula is used for the degradation rate of BPA and BPB:

[0026]

[0027] The following bimetallic oxide nanoparticles Cu2PdO3 can be prepared by the following method:

[0028] (1) Dissolve 0.005 mol copper nitrate and 0.0025 mol palladium nitrate in 30 mL of pure water and stir magnetically for 60 min until a uniform solution is formed;

[0029] (2) slowly adding NaOH to the homogeneous solution to adjust the pH of the solution to 12 to ensure that the coprecipitation is completely produced;

[0030] (3) The suspension produced in step (2) was stirred at 70°C for 1 h to form a uniform dispersion. The dark brown solution was then transferred to a 100 mL teflon-lined stainless steel autoclave and maintained at 160°C for 12 h.

[0031] (4) After cooling, the Cu2PdO3 was collected by centrifugation, washed with pure water and ethanol at least three times in sequence, and finally dried under vacuum at 60° C. The collected precipitate was ground to obtain Cu2PdO3 nanoparticles.

[0032] (5) Accurately weigh 20 mg of Cu2PdO3 nanoparticles and put them into 40 mL of water. Ultrasonicate for 30 min to prepare a Cu2PdO3 nanodispersion liquid with a concentration of 500 mg / L for later use.

[0033] Example 1

[0034] Persulfate was added to the water body containing the target pollutant BPA or BPB. The concentration of BPA and BPB was 10 mg / L, and the amount of persulfate added was 300 mg / L. In order to explore the suitable pH conditions for the experiment, HCl and NaOH were used to adjust the solution pH to 3.5, 5.5, 7.5 and 9.5, respectively. Finally, Cu2PdO3 nanodispersion was added in an amount of 50 mg / L. At the same time, a stirring bar was added to evenly disperse the pollutants, oxidants and Cu2PdO3. The stirring speed was 200 r / min. Samples were taken at certain time intervals, and the quencher methanol was added. After filtering, the concentrations of BPA and BPB remaining in the solution were detected by high performance liquid chromatography.

[0035] The different pH treatment effects obtained in this example are as follows Figure 1 As shown, from Figure 1 It can be seen that Cu2PdO3 nanoparticles are completely degraded within 10 minutes under different pH conditions. Therefore, Cu2PdO3 nanoparticles are suitable for degrading BPA and BPB in a wide range of acidic and alkaline environments.

[0036] Example 2

[0037] Persulfate was added to the water body containing the target pollutant BPA or BPB, the concentration of BPA and BPB was 10 mg / L, the amount of persulfate added was 400, 300, 200, 100, 50 mg / L, and finally Cu2PdO3 nano-dispersion was added, the amount added was 50 mg / L. A stirring bar was added at the same time to make the pollutant, oxidant and Cu2PdO3 dispersed evenly, the stirring speed was 200 r / min, samples were taken at a certain time interval, quencher methanol was added, and the concentration of BPA and BPB remaining in the solution was detected by high performance liquid chromatography after filtration.

[0038] The treatment effects of adding different doses of persulfate on BPA and BPB obtained in this example are as follows: Figure 2 As shown. Figure 2 It can be seen that after a certain amount of persulfate is added, its effect is saturated, and excessive persulfate will not have a significant promoting effect on the degradation of BPA and BPB. Taking all factors into consideration, the optimal amount of persulfate is 200 mg / L.

[0039] Example 3

[0040] Persulfate was added to the water body containing the target pollutant BPA or BPB, the concentration of BPA and BPB was 10 mg / L, the amount of persulfate added was 200 mg / L, and finally Cu2PdO3 nano-dispersion was added, the amount added was 50, 40, 30, 25, 20 mg / L. A stirring bar was added at the same time to make the pollutant, oxidant and Cu2PdO3 dispersed evenly, the stirring speed was 200 r / min, samples were taken at certain time intervals, quencher methanol was added, and the concentration of BPA and BPB remaining in the solution was detected by high performance liquid chromatography after filtration.

[0041] The treatment effects of Cu2PdO3 activated persulfate on BPA of different concentrations are shown in the following table. Figure 3 As shown. Figure 3 It can be seen that with the increase of Cu2PdO3 dosage, BPA is degraded more, but excessive Cu2PdO3 dosage will no longer increase the degradation rate and lead to waste of Cu2PdO3. Considering all factors, the optimal dosage of Cu2PdO3 is 40 mg / L.

[0042] Example 4

[0043] Sodium perchloride, sodium nitrate, sodium bicarbonate, sodium sulfate and sodium dihydrogen phosphate were added to the water containing the target pollutant BPA or BPB. The concentration of BPA and BPB was 10 mg / L, and the amount of persulfate added was 200 mg / L. Finally, Cu2PdO3 nano-dispersion was added in an amount of 40 mg / L. A stirring bar was added at the same time to make the pollutants, oxidants and Cu2PdO3 dispersed evenly. The stirring speed was 200 r / min. Samples were taken at certain time intervals, and quencher methanol was added. After filtering, the concentration of BPA and BPB remaining in the solution was detected by high performance liquid chromatography.

[0044] The treatment effects of the experimental conditions under different salt ion concentrations obtained in this embodiment are as follows: Figure 4 As shown. Figure 4 It can be seen that various salts have limited inhibitory effects on the degradation of BPA and BPB, and BPA and BPB can be basically completely degraded within 10 minutes.

[0045] Comparative Example 1

[0046] Preparation of CuO and PdO nanoparticles, the method is the same as the preparation of nanoparticles Cu2PdO3, but without adding Pd(NO3)2 or Cu(NO3)2. Add persulfate to BPA and BPB containing target pollutants at a concentration of 10 mg / L, and the amount of persulfate added is 200 mg / L. Add CuO, PdO and Cu2PdO3 nanoparticles respectively. In order to make the substances disperse evenly, add a rotor to stir at a speed of 200 r / min. Sampling and filtering at certain intervals, adding quencher methanol, and using high performance liquid chromatography to detect the concentration of BPA or BPB remaining in the solution.

[0047] The results of the degradation of BPA and BPB in water by three types of nanoparticles are shown in Figure 2. Figure 5 As shown in the figure, it can be seen that among the three nanoparticles, bimetallic Cu2PdO3 nanoparticles have the best degradation effect.

[0048] Comparative Example 2

[0049] Cu2PdO3 nanodispersion was added into water containing target pollutants BPA and BPB without adding persulfate. Samples were taken and filtered at a certain time, and quencher methanol was added. The concentration of remaining BPA and BPB in the sample was measured by HPLC to study whether Cu2PdO3 has a degradation effect on the pollutants BPA and BPB.

[0050] The degradation effect of this embodiment is as follows Figure 6 As shown, from Figure 6 It can be seen that without the addition of persulfate (PMS), pure Cu2PdO3 nanoparticles have no degradation effect on the pollutants BPA and BPB.

[0051] Comparative Example 3

[0052] Co2PdO4, Fe2PdO4, Fe2PdS4, Co2PdS4, and Cu2PdS4 were prepared by the same method, among which the preparation method of Fe2PdS4 was as follows: 1mmolFe(NO3)2·9H2O, 2mmol Pd(NO3)2·xH2O, and 8mmolL-cysteine ​​were dissolved in 25mL water and 25mL ethylene glycol, stirred for 30min, transferred to a 100mL Teflon-lined stainless steel autoclave, kept at 160°C for 12h, cooled, washed three times with ethanol and pure water in sequence, and then vacuum dried at 60°C.

[0053] The preparation method of Co2PdS4 is as follows: 1mmolCo(NO3)2·6H2O, 2mmolPd(NO3)2·xH2O, and 8mmolL-cysteine ​​are dissolved in 25mL water and 25mL ethylene glycol, stirred for 30min, transferred to a 100mL teflon-lined stainless steel autoclave, kept at 160℃ for 12h, cooled, washed three times with ethanol and purified water in sequence, and then dried in vacuum at 60℃.

[0054] The preparation method of Cu2PdS4 is as follows: 1mmolCu(NO3)2, 2mmolPd(NO3)2·xH2O, and 8mmolL-cysteine ​​are dissolved in 25mL water and 25mL ethylene glycol, stirred for 30min, transferred to a 100mL teflon-lined stainless steel autoclave, kept at 160℃ for 12h, cooled, washed three times with ethanol and purified water in sequence, and then vacuum dried at 60℃.

[0055] The preparation method of Co2PdO4 is as follows: 0.005molCo(NO3)2·6H2O and 0.0025molPd(NO3)2·xH2O are dissolved in 30mL of pure water, and magnetically stirred for 60min until a uniform solution is formed; NaOH is slowly added to the uniform solution to adjust the pH of the solution to 12 to ensure that the coprecipitation is completely produced; the suspension is then stirred at 70°C for 1h to form a uniform dispersion. The dark brown solution is transferred to a 100mL teflon-lined stainless steel autoclave, maintained at 160°C for 12h, cooled, and the Co2PdO4 is collected by centrifugation, washed with pure water and ethanol at least 3 times in sequence, and finally vacuum dried at 60°C. The collected precipitate is ground to obtain Co2PdO4 nanoparticles.

[0056] The preparation method of Fe2PdO4 is as follows: 0.005 mol Fe(NO3)3·6H2O and 0.0025 mol Pd(NO3)2·xH2O are dissolved in 30 mL of pure water, and magnetically stirred for 60 min until a uniform solution is formed; NaOH is slowly added to the uniform solution to adjust the pH of the solution to 12 to ensure that the coprecipitation is completely produced; the suspension is then stirred at 70°C for 1 h to form a uniform dispersion. The dark brown solution is transferred to a 100 mL teflon-lined stainless steel autoclave and maintained at 160°C for 12 h. After cooling, Fe2PdO4 is collected by centrifugation, washed with pure water and ethanol at least 3 times in sequence, and finally dried in vacuo at 60°C. Grind the collected precipitate to obtain Fe2PdO4 nanoparticles. The effects of Co2PdO4, Fe2PdO4, Fe2PdS4, Co2PdS4, Cu2PdS4, and Cu2PdO3 in degrading BPA and BPB in water are as follows Figure 6As shown, among the nanoparticles prepared with different metals and non-metals, copper-palladium bimetallic oxide has the best degradation effect.

Claims

1. A method for rapidly degrading bisphenol A and bisphenol B in water, characterized in that: The method comprises the following steps: 1) Dissolving copper nitrate and palladium nitrate in pure water to prepare a precursor, and stirring by magnetic force until a uniform solution is formed; slowly adding sodium hydroxide to the uniform solution, adjusting the pH to 12, ensuring that the coprecipitation is completely produced, and obtaining a suspension; 2) Stirring the suspension in step 1) at 70° C. for 1 h to obtain a dark brown solution, then transferring the dark brown solution to a 100 mL teflon-lined stainless steel autoclave for high temperature sterilization, cooling and centrifuging to collect Cu2PdO3, washing with pure water and ethanol at least 3 times in sequence, and then vacuum drying and grinding to obtain Cu2PdO3 nanoparticles; 3) adding the Cu2PdO3 nanoparticles prepared in step 2) into water and ultrasonicating for 30 minutes to obtain a Cu2PdO3 nanoparticle dispersion; 4) Adding persulfate into a solution containing target pollutants bisphenol A and bisphenol B, and finally adding a Cu2PdO3 nanoparticle dispersion to catalyze the degradation of the target pollutants bisphenol A and bisphenol B.

2. A method for rapidly degrading bisphenol A and bisphenol B in water as claimed in claim 1, characterized in that In step 1), the molar ratio of copper nitrate to palladium nitrate is 2:

1.

3. A method for rapidly degrading bisphenol A and bisphenol B in water as claimed in claim 1, characterized in that In step 2), the temperature of high temperature sterilization is 160°C, the sterilization time is 12h, and the temperature of vacuum drying is 60°C.

4. A method for rapidly degrading bisphenol A and bisphenol B in water as claimed in claim 1, characterized in that In step 4), the concentrations of BPA and BPB in the bisphenol A and bisphenol B solutions are both 1-20 mg / L, and the pH value of the bisphenol A and bisphenol B solutions is 2-10.

5. A method for rapidly degrading bisphenol A and bisphenol B in water as claimed in claim 1, characterized in that In step 4), the total mass ratio of Cu2PdO3 nanoparticles to BPA / BPB is 5:1-1:

1.

6. A method for rapidly degrading bisphenol A and bisphenol B in water as claimed in claim 1, characterized in that In step 4), the mass ratio of Cu2PdO3 nanoparticles to persulfate is 1:2-10.

7. A method for rapidly degrading bisphenol A and bisphenol B in water as claimed in claim 1, characterized in that In step 4), the temperature of catalytic degradation is 15-40° C., and the time of catalytic degradation is 10-15 min.

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