A new method for degrading bisphenol a in water

Abstract

The application provides a new method for degrading bisphenol A in water. A copper-loaded CHA type molecular sieve (Cu x SSZ-13, and x is the content of Cu) is used to activate hydrogen peroxide process to realize efficient oxidative degradation of bisphenol A in water. Compared with the traditional H2O2 / Fe(II) system for oxidatively degrading bisphenol A, the utilization rate of the oxidant is greatly improved, the required amounts of the oxidant and the catalyst are greatly reduced, the catalyst can be reused, and the method has great advantages in improving the degradation efficiency of bisphenol A and widening the pH range.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of environmental pollution treatment, and particularly relates to a new type of copper-loaded catalyst (Cu x -SSZ-13) for catalyzing hydrogen peroxide to degrade bisphenol A in water. BACKGROUND

[0002] Bisphenol A (BPA) is widely present in various household and consumer products, including various reusable water bottles, microwaveable lunch boxes, electronic devices, automobiles, sports helmets and pads, lenses, children's toys, dental fillings, printed circuit boards, protective coatings, and food and beverage can coatings. However, bisphenol A is an alkyl phenolic environmental estrogen, and long-term exposure to bisphenol A can interfere with endocrine and metabolic activities in the human body, leading to metabolic disorders, harm to the reproductive system, and a great impact on the behavior development and immunity of infants. Therefore, bisphenol A entering water, air, and soil during use and consumption has caused serious environmental pollution problems.

[0003] To address the problem of bisphenol A pollution, various process technologies have been developed to remove bisphenol A, such as adsorption, biological treatment, membrane separation, and advanced oxidation processes. Among them, advanced oxidation technology has been widely concerned because it can generate a large number of highly active and strong oxidizing free radicals and completely mineralize bisphenol A into CO2 and H2O. Metal ions as activators of oxidizing agents have been widely concerned.

[0004] In recent years, domestic and foreign scholars have actively researched copper-based activators. Jeremy A. et al. compared the inactivation effects of Fe 2+ / H2O2 and Cu 2+ / H2O2 on MS2 coliphage inactivation experiments and found that the inactivation effect of Cu 2+ / H2O2 was better than that of Fe 2 + / H2O2, indicating that Cu 2+ has higher catalytic activation ability than Fe 2+ . He Ru et al. studied the comparative experiments of Fe 2+ and Cu 2+ catalytic H2O2 oxidation degradation of phenol, and the results showed that the catalytic activity of Cu 2+ was much higher than that of Fe 2+ , in which the degradation rate of Fe 2+ to phenol was less than 80%, while the degradation rate of Cu 2+ to phenol was maintained at more than 90%. He Ru et al. analyzed that the electron transfer efficiency of Cu 2+ was higher than that of Fe 2+Faster, and the removal rate is also faster, and then the author uses zeolite and activated carbon as a carrier to make a heterogeneous catalyst of Fe and Cu for the oxidative degradation of phenol, and the results are consistent with the homogeneous, indicating that Cu 2+ has high catalytic activity and development prospects.

[0005] The application uses HSSZ-13 material as a carrier, and different amounts of copper nitrate are loaded on the carrier by an impregnation method to obtain a copper-loaded CHA type molecular sieve catalytic activator, activate hydrogen peroxide, and realize efficient oxidative degradation of bisphenol A in water. Compared with the traditional Fenton technology, the oxidative degradation efficiency of the target pollutant is improved, the amount of oxidant is reduced, the pH adaptation range is widened, and compared with zeolite and activated carbon, the catalyst has high reusability, clean sanitation, and great advantages in pore size and adsorption capacity. SUMMARY

[0006] The purpose of the present application is to make a copper-loaded CHA type molecular sieve (Cu x -SSZ-13, x is the Cu content) as a catalytic activator, activate hydrogen peroxide, and realize efficient degradation of bisphenol A in water.

[0007] To achieve the above-mentioned purpose, the following technical solutions are adopted in the present application:

[0008] A certain amount of Cu x -SSZ-13 is added to a bisphenol A aqueous solution with a certain concentration, stirred thoroughly, adjusted to a specific pH, a certain amount of hydrogen peroxide is added, the reaction starts, samples are taken at intervals, 0.2 mL of methanol is added, the reaction is stopped, the sample solution is filtered through a 0.22 μm membrane, and then stored at 4°C, and the residual bisphenol A content in the solution is analyzed by high performance liquid chromatography within 24 hours.

[0009] The oxidizing agent, characterized in that the oxidizing agent is preferably hydrogen peroxide.

[0010] The hydrogen peroxide, characterized in that the optimal concentration is 10 mM.

[0011] A new type of copper-loaded catalyst (Cu x -SSZ-13), the catalyst Cu x -SSZ-13, the content x of Cu is 1.34% to 4.03%, and the preferred value is 2.58%.

[0012] The Cu 2.58 -SSZ-13, characterized in that the optimal concentration of the catalyst is 0.3 g / L.

[0013] A new type of copper-loaded catalyst (Cu2.58 -SSZ-13) and its degradation of bisphenol A in water, characterized in that the optimal pH is 7.

[0014] The new method for degrading bisphenol A in water is characterized in that the selected bisphenol A concentration is 10 mg / L, 15 mg / L, 20 mg / L.

[0015] Compared with the prior art, the beneficial effects of the present application include but are not limited to:

[0016] The present application provides a copper-loaded CHA type molecular sieve (Cu x -SSZ-13, x is the Cu content) has significant positive advantages in improving the targeted utilization rate of oxidants, improving the oxidation and degradation efficiency of target pollutants, reducing the amount of catalyst and oxidant, and the pH adaptation range compared with traditional Fenton technology. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 The curve for the influence of different oxidants (hydrogen peroxide, sodium persulfate) and the optimal copper-loaded CHA molecular sieve catalyst on the degradation of bisphenol A in Example 1.

[0018] Figure 2 The curve for the influence of different dosages of hydrogen peroxide (1 mM, 5 mM, 10 mM, 20 mM, 50 mM) on the degradation of bisphenol A in Example 2.

[0019] Figure 3 The curve for the influence of different copper loadings of the catalytic activator Cu x -SSZ-13 (Cu 1.34 -SSZ-13, Cu 1.92 -SSZ-13, Cu 2.58 -SSZ-13, Cu 3.26 -SSZ-13, Cu 4.03 -SSZ-13) on the degradation of bisphenol A.

[0020] Figure 4 The curve for the influence of different Cu 2.58 -SSZ-13 dosages (0.1 g / L, 0.3 g / L, 0.5 g / L, 0.7 g / L) on the degradation of bisphenol A in Example 4.

[0021] Figure 5 The curve for the influence of different pH values on the degradation of bisphenol A in the hydrogen peroxide and new copper-loaded catalytic activator Cu 2.58 -SSZ-13 combined system in Example 5.

[0022] Figure 6 The curve for the influence of different pH values on the degradation of bisphenol A in the hydrogen peroxide and new copper-loaded catalytic activator Cu 2.58- Degradation curve of different concentrations of bisphenol A in SSZ-13 combined system. DETAILED DESCRIPTION

[0023] The following examples facilitate a better understanding of the present application, but do not limit the present application.

[0024] In the following examples, the experimental methods are conventional methods, unless otherwise specified.

[0025] In the following examples, the BPA concentration test method is as follows: high performance liquid chromatography is used to analyze the sample, and the specific conditions are: the mobile phase is methanol and water (70:30); the column temperature is 35°C; the DAD ultraviolet detector (278mm); the flow rate is 1.0mL / min; and the injection volume is 40μl.

[0026] In the following examples, the test materials used are purchased from conventional biochemical reagent stores, unless otherwise specified: HSSZ-13, hydrogen peroxide (30%), copper nitrate, sodium hydroxide, and concentrated hydrochloric acid are all AR grade.

[0027] Example 1

[0028] This example is to achieve efficient degradation of bisphenol A in water using a new copper-loaded catalytic activator, using hydrogen peroxide as an oxidizing agent, Cu 2.58 -SSZ-13 is a catalyst to achieve efficient oxidative degradation of bisphenol A in water, and the specific process is:

[0029] Cu 2.58 -SSZ-13 (0.5g / L) is added to a water solution containing a certain concentration of bisphenol A, and after stirring thoroughly, it is adjusted to a specific pH, hydrogen peroxide or sodium persulfate (1mM, 5mM, 10mM, 20mM, 50mM) is added, and the reaction starts, samples are taken at intervals, and 0.2mL of methanol is added to stop the reaction, the sample solution is passed through a 0.22μm membrane and stored at 4°C, and the residual bisphenol A content in the solution is analyzed by high performance liquid chromatography within 24 hours.

[0030] This example has good degradation effect on bisphenol A in water, and the degradation of bisphenol A is significantly improved when the oxidizing agent is hydrogen peroxide, so hydrogen peroxide is the preferred oxidizing agent.

[0031] Example 2

[0032] This example is to achieve efficient degradation of bisphenol A in water using a new copper-loaded catalyst prepared, using hydrogen peroxide as an oxidizing agent, Cu 2.58 -SSZ-13 is a catalyst to achieve efficient oxidative degradation of bisphenol A in water, and the specific process is:

[0033] Cu 2.58-SSZ-13 (0.5 g / L), after stirring sufficiently, adjusting to a specific pH, adding hydrogen peroxide (1 mM, 5 mM, 10 mM, 20 mM, 50 mM), starting the reaction, sampling at intervals, adding 0.2 mL of methanol to the sample, stopping the reaction, passing the sample solution through a 0.22 μm membrane, and storing at 4°C, and analyzing the remaining bisphenol A content in the solution by high performance liquid chromatography within 24 hours.

[0034] The bisphenol A degradation effect in water in this example is good, and when the oxidant is 10 mM, the bisphenol A degradation rate can reach 88.16%, so the preferred oxidant concentration is 10 mM.

[0035] Example 3

[0036] This example is the efficient degradation of bisphenol A in water using the prepared new copper-supported catalyst, with hydrogen peroxide as the oxidant, Cu x -SSZ-13 as the catalyst, achieving efficient oxidative degradation of bisphenol A in water, and the specific process is as follows:

[0037] A certain amount of Cu x -SSZ-13 (Cu 1.34 -SSZ-13, Cu 1.92 -SSZ-13, Cu 2.58 -SSZ-13, Cu 3.26 -SSZ-13, Cu 4.03 -SSZ-13), stirring sufficiently, adjusting to a specific pH, adding a certain amount of hydrogen peroxide, starting the reaction, sampling at intervals, adding 0.2 mL of methanol to the sample, stopping the reaction, passing the sample solution through a 0.22 μm membrane, and storing at 4°C, and analyzing the remaining bisphenol A content in the solution by high performance liquid chromatography within 24 hours.

[0038] The bisphenol A degradation effect in water in this example is good, and when the catalyst is Cu 2.58 -SSZ-13, the bisphenol A degradation rate can reach 88.16%, so the preferred catalyst is Cu 2.58 -SSZ-13.

[0039] Example 4

[0040] This example is the efficient degradation of bisphenol A in water using the prepared new copper-supported catalyst, with hydrogen peroxide as the oxidant, Cu 2.58 -SSZ-13 as the catalyst, achieving efficient oxidative degradation of bisphenol A in water, and the specific process is as follows:

[0041] A certain amount of Cu8-SSZ-13 (0.1 g / L, 0.3 g / L, 0.5 g / L, 0.7 g / L) was added to an aqueous solution containing a certain concentration of bisphenol A. After stirring thoroughly, the pH was adjusted to a specific value. A certain amount of hydrogen peroxide was added, and the reaction began. Samples were taken at intervals, and 0.2 mL of methanol was added to stop the reaction. The sample solution was passed through a 0.22 μm membrane and stored at 4 °C. The remaining bisphenol A content in the solution was analyzed by high performance liquid chromatography within 24 hours.

[0042] The example demonstrates good degradation effect on bisphenol A in water. When the catalyst concentration is 0.3 g / L, the degradation rate of bisphenol A is 97.17%.

[0043] Example 5

[0044] This embodiment demonstrates the efficient degradation of bisphenol A in water using a novel copper-supported catalyst, with hydrogen peroxide as the oxidant and Cu... 2.58 -SSZ-13 is used as a catalyst to achieve efficient oxidative degradation of bisphenol A in water. The specific process is as follows:

[0045] A certain amount of Cu8-SSZ-13 was added to an aqueous solution containing a certain concentration of bisphenol A. After stirring thoroughly, the pH was adjusted to (3, 5, 7, 9, 11). After adding a certain amount of hydrogen peroxide, the reaction started. Samples were taken at intervals, and 0.2 mL of methanol was added to stop the reaction. The sample solution was passed through a 0.22 μm membrane and stored at 4 °C. The remaining bisphenol A content in the solution was analyzed by high performance liquid chromatography within 24 hours.

[0046] The example showed good degradation effect on bisphenol A in water. When pH=7, the degradation rate of bisphenol A was 97.17%, so pH 7 is the preferred pH.

[0047] Example 6

[0048] This embodiment demonstrates the efficient degradation of bisphenol A in water using a novel copper-supported catalyst, with hydrogen peroxide as the oxidant and Cu... 2.58 -SSZ-13 is used as a catalyst to achieve efficient oxidative degradation of bisphenol A in water. The specific process is as follows:

[0049] A certain amount of Cu was added to bisphenol A aqueous solutions with concentrations of 10 mg / L, 15 mg / L, and 20 mg / L, respectively. 2.58 -SSZ-13 (0.3 g / L), after stirring thoroughly, adjust to a specific pH, add a certain amount of hydrogen peroxide, the reaction begins, take samples at intervals, add 0.2 mL of methanol to stop the reaction, pass the sample solution through a 0.22 μm membrane and store at 4 °C, and analyze the remaining bisphenol A content in the solution by high performance liquid chromatography within 24 hours.

[0050] The embodiment has good degradation effect on bisphenol A in water, and the degradation effect on 10 mg / L, 15 mg / L and 20 mg / L bisphenol A aqueous solution can reach 97.17%, 90.13% and 75.27%.

[0051] Finally, it should be noted that in this application, the relationship terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply that there is any such actual relationship or order between the entities or operations. Moreover, the terms "include", "contain" or any other variants thereof are intended to cover non-exclusive inclusion, so that the process, method, article or equipment including a series of elements not only includes those elements, but also includes other elements not explicitly listed or inherent to such process, method, article or equipment. Without more limitations, the element defined by the statement "including a" does not exclude the presence of other identical elements in the process, method, article or equipment including the element.

[0052] Although the present application has been disclosed by the description of the specific embodiments of the present application above, it should be understood that those skilled in the art can design various modifications, improvements or equivalents of the present application within the spirit and scope of the appended claims. These modifications, improvements or equivalents should also be considered to be included in the scope of the present application.

Claims

1. A novel method for degrading bisphenol A in water, characterized by, The copper-loaded CHA type molecular sieve is used as a catalyst, and the copper-loaded CHA type molecular sieve is Cu x -SSZ-13, x is the Cu content, and in the presence of an oxidant, efficient oxidative degradation of bisphenol A in water is achieved, and the specific process is: To a solution of bisphenol A in water at a certain concentration, Cu x -SSZ-13, adjust to a certain pH, add hydrogen peroxide, start the reaction, take samples at intervals, add 0.2 mL of methanol to the sample at the same time, stop the reaction, store the sample solution after passing through a 0.22 μm membrane at 4°C, and analyze the bisphenol A content in the sample within 24 hours by high performance liquid chromatography.

2. A novel method of degrading bisphenol A in water as claimed in claim 1 wherein, The oxidizing agent is selected from hydrogen peroxide or sodium persulfate.

3. A novel method of degrading bisphenol A in water according to claim 2, characterized by, The concentration of hydrogen peroxide ranges from 1 mM to 50 mM.

4. A novel method of degrading bisphenol A in water as claimed in claim 1, wherein: Catalyst Cu x - Cu in SSZ-13 is present as copper ions, the content x of which is 1.34% to 4.03%.

5. A novel method of degrading bisphenol A in water as claimed in claim 1, wherein: The concentration of the catalyst ranges from 0.1 g / L to 0.7 g / L.

6. A novel method of degrading bisphenol A in water as claimed in claim 1, wherein: The pH ranges from 3 to 11.

7. A novel method of degrading bisphenol A in water as claimed in claim 1, wherein: The concentration of bisphenol A is selected from 10 mg / L, 15 mg / L and 20 mg / L.

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