A micro-energy driven multiphase Fenton water purifier and its preparation method and application

Abstract

The present invention relates to the field of water treatment technology, and more particularly to a micro-energy-driven multiphase Fenton water purifier and its preparation method and application, wherein the preparation method comprises the following steps: in a mixed solution of ferric chloride hexahydrate and zinc sulfate heptahydrate, a selenium dioxide solution, a hydrated hydrazine solution and a 3-mercaptopropyltriethoxysilane solution are sequentially added, and after sufficient stirring, a solid product is centrifuged and filtered out, and then the solid product is alternately washed with deionized water and ethanol, and dried to obtain the water purifier. The preparation method of the present invention has simple process, high efficiency and low consumption, and a short cycle, which greatly reduces the cost of water treatment and is conducive to large-scale production; in addition, the obtained water purifier has good stability and catalytic activity, realizes the activation of trace hydrogen peroxide, and significantly improves the effect of degrading organic pollutants in water.

Description

Technical Field

[0001] The present invention relates to the technical field of water treatment, and in particular to a micro-energy driven multiphase Fenton water purifier and a preparation method and application thereof. Background Art

[0002] Currently, wastewater treatment is plagued by excessive resource and energy consumption, a bottleneck in the development of wastewater treatment technology. Advanced oxidation processes (ADPs) are considered promising water purification technologies, but the classic Fenton reaction, due to its rate-limiting step, not only suffers from poor reactivity under neutral conditions but also suffers from severe energy waste. For example, H₂O₂ is ultimately inefficiently oxidized and decomposed into oxygen, resulting in low utilization. Iron ions are continuously consumed, ultimately forming large amounts of iron sludge, which wastes resources and increases treatment energy consumption. Therefore, developing water purification agents that can trigger the reaction with trace amounts of hydrogen peroxide would help address the issue of excessive H₂O₂ consumption and reduce wastewater treatment costs. Furthermore, emerging pollutants have a wide range of sources, pose serious hazards, and pose hidden environmental risks, making their treatment difficult. The development of such water purification agents would not only address the technical bottlenecks of high energy consumption and low efficiency associated with the traditional Fenton reaction, but also enable the efficient and cost-effective treatment of a variety of trace emerging pollutants in water. Summary of the Invention

[0003] The purpose of the present invention is to overcome the shortcomings of the prior art mentioned in the above background technology and propose a method for preparing a simple and low-cost micro-energy-driven multiphase Fenton water purifier and a water purifier prepared by this method with good stability and catalytic activity.

[0004] A first aspect of the present invention provides a method for preparing a micro-energy-driven multiphase Fenton water purifier, comprising the following steps: sequentially adding a selenium dioxide solution, a hydrazine hydrate solution, and a 3-mercaptopropyltriethoxysilane solution to a mixed solution of ferric chloride hexahydrate and zinc sulfate heptahydrate; stirring thoroughly; centrifuging to remove a solid product; then washing the solid product alternately with deionized water and ethanol; and drying to obtain the water purifier.

[0005] Preferably, the method comprises the following steps:

[0006] (1) dissolving ferric chloride hexahydrate and zinc sulfate heptahydrate in deionized water and stirring to obtain a mixed solution A;

[0007] (2) dissolving selenium dioxide in deionized water, stirring and mixing, and then adding the mixture to the mixed solution A in step (1) to obtain a mixed solution B;

[0008] (3) dissolving hydrazine hydrate in deionized water, stirring and mixing, and then adding the mixture to the mixed solution B in step (2) to obtain a mixed solution C;

[0009] (4) dissolving 3-mercaptopropyltriethoxysilane in ethanol, stirring and mixing uniformly, and then adding the mixture to the mixed solution C in step (3) to obtain a mixed solution D;

[0010] (5) Centrifuge the mixed solution D to remove the solid product, then wash the solid product alternately with deionized water and ethanol, and dry it;

[0011] (6) Grinding the dried solid product into powder to obtain the water purifier.

[0012] Preferably, the molar ratio of ferric chloride hexahydrate, zinc sulfate heptahydrate, and selenium dioxide is (0.5-2.5):(2-3):(20-25); more preferably, the molar ratio of ferric chloride hexahydrate, zinc sulfate heptahydrate, and selenium dioxide is 2:2.5:25, 0.5:2:20, or 2.5:2:25.

[0013] Preferably, the concentration of the hydrazine hydrate solution is 0.4-1.8 mol / L; more preferably, the concentration of the hydrazine hydrate solution is 0.6-0.9 mol / L; further, the concentration of the hydrazine hydrate solution is 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, or 0.9 mol / L.

[0014] Preferably, the concentration of the 3-mercaptopropyltriethoxysilane solution is 0.05-0.25 mol / L; more preferably, the concentration of the 3-mercaptopropyltriethoxysilane solution is 0.05-0.1 mol / L; further, the concentration of the 3-mercaptopropyltriethoxysilane solution is 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L, or 0.1 mol / L.

[0015] Preferably, in step (4), the stirring time is 8-12 h and the temperature is 20-30°C; more preferably, the stirring time is 10 h and the temperature is 25°C.

[0016] Preferably, in step (4), after the 3-mercaptopropyltriethoxysilanol solution is added, foam emerges during the stirring of the mixed solution and the solution gradually turns red.

[0017] Preferably, in step (5), the centrifugal speed is 8000-12000 r / min, and the centrifugal time is 3-10 minutes; more preferably, the centrifugal speed is 10000 r / min, and the centrifugal time is 5 minutes.

[0018] Preferably, in step (5), the drying temperature is 50-70°C and the drying time is 8-24h; more preferably, the drying temperature is 60°C and the drying time is 12h.

[0019] Preferably, in step (5), the alternating washing is performed at least 3 times; more preferably, the alternating washing is performed 4 times.

[0020] The second aspect of the present invention provides a method for preparing a micro-energy-driven multi-phase Fenton water purifier, and a micro-energy-driven multi-phase Fenton water purifier prepared therefrom.

[0021] Preferably, the finished product of the micro-energy driven multiphase Fenton water purifier is soft, uniform and dark red.

[0022] The third aspect of the present invention provides the use of the above-mentioned micro-energy-driven multiphase Fenton water purifier in treating organic pollutants in water.

[0023] Preferably, the organic pollutants include: one or more of Acid Orange 7, bisphenol A, ciprofloxacin, and diphenhydramine.

[0024] Preferably, the water purifier and H2O2 are added to wastewater containing organic pollutants such as acid orange 7, bisphenol A, ciprofloxacin, diphenhydramine, etc. for degradation.

[0025] The present invention has the following beneficial effects compared to the prior art:

[0026] (1) The preparation method of the water purifier of the present invention has simple process, low cost, short cycle, and is conducive to large-scale production.

[0027] (2) The water purifier of the present invention is a solid catalyst, which is easy to separate from water and can be easily recycled and reused.

[0028] (3) The water purifier of the present invention has a wide pH response range, and the reaction process does not require the system pH to be adjusted to such harsh conditions as 2-3. Under neutral conditions, it has excellent catalytic degradation activity for organic pollutants.

[0029] (4) The water purifier of the present invention has good stability in the process of removing organic pollutants.

[0030] (5) The water purifier of the present invention only requires a small amount of H2O2 to trigger the degradation reaction, has a good removal effect on organic pollutants in water, greatly improves the utilization rate of H2O2, and reduces the cost of water treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0032] Figure 1 This is a scanning electron microscope image of the water purifier prepared in Example 1 of the present invention.

[0033] Figure 2 This is a graph showing the stability test results of the water purifier in Test Example 1 of the present invention.

[0034] Figure 3 This is a graph evaluating the degradation activity of the water purifier on various pollutants in Test Example 2 of the present invention. DETAILED DESCRIPTION

[0035] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of the present application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present application belongs.

[0036] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present application. As used herein, unless the context clearly indicates otherwise, the singular also includes the plural. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, they indicate the presence of features, steps, operations, devices, components and / or combinations thereof.

[0037] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0038] Example 1

[0039] This embodiment provides a micro-energy driven multiphase Fenton water purifier, the preparation method of which includes the following steps:

[0040] (1) Dissolve 2 mmol of ferric chloride hexahydrate and 2.5 mmol of zinc sulfate heptahydrate in a certain amount of deionized water and stir to obtain a mixed solution A;

[0041] (2) dissolving 25 mmol of selenium dioxide in 30 mL of deionized water, stirring evenly, and adding the mixture to the mixed solution A in step (1) to obtain a mixed solution B;

[0042] (3) dissolving 25 mmol of hydrated hydrazine in 30 mL of deionized water, mixing well, and adding the mixture to the mixed solution B in step (2) to obtain a mixed solution C;

[0043] (4) Dissolve 1 mmol of 3-mercaptopropyltriethoxysilane (MTPS) solution in 10 mL of ethanol, mix well, and then add the mixture to the mixed solution C in step (3) to obtain a red mixed solution D;

[0044] (5) The solid product obtained from the mixed solution D was centrifuged and filtered, then washed alternately with deionized water and ethanol four times, and dried;

[0045] (6) Grinding the dried solid material into powder to obtain the water purifier.

[0046] The scanning electron microscope image of the micro-energy driven multiphase Fenton water purifier prepared in this embodiment is as follows: Figure 1 As can be seen from the figure: a lot of nano-microsphere particles grow on the staggered rod-like structure.

[0047] Example 2

[0048] This embodiment provides a micro-energy driven multiphase Fenton water purifier, the preparation method of which includes the following steps:

[0049] (1) Dissolve 0.5 mmol of ferric chloride hexahydrate and 2 mmol of zinc sulfate heptahydrate in a certain amount of deionized water and stir to obtain a mixed solution A;

[0050] (2) dissolving 20 mmol of selenium dioxide in 30 mL of deionized water, stirring evenly, and adding the mixture to the mixed solution A in step (1) to obtain a mixed solution B;

[0051] (3) dissolving 20 mmol of hydrazine hydrate in 30 mL of deionized water, mixing well, and adding the mixture to the mixed solution B in step (2) to obtain a mixed solution C;

[0052] (4) Dissolve 0.5 mmol of 3-mercaptopropyltriethoxysilane (MTPS) solution in 10 mL of ethanol, mix well, and then add the mixture to the mixed solution C in step (3) to obtain a red mixed solution D;

[0053] (5) The solid product obtained from the mixed solution D was centrifuged and filtered, then washed alternately with deionized water and ethanol four times, and dried;

[0054] (6) Grinding the dried solid material into powder to obtain the water purifier.

[0055] Scanning electron microscopy results show that the structure of the micro-energy-driven multiphase Fenton water purifier prepared in this example is consistent with the structure of the micro-energy-driven multiphase Fenton water purifier prepared in Example 1.

[0056] Example 3

[0057] This embodiment provides a micro-energy driven multiphase Fenton water purifier, the preparation method of which includes the following steps:

[0058] (1) Dissolve 2.5 mmol of ferric chloride hexahydrate and 2 mmol of zinc sulfate heptahydrate in a certain amount of deionized water and stir to obtain a mixed solution A;

[0059] (2) dissolving 25 mmol of selenium dioxide in 30 mL of deionized water, stirring evenly, and adding the mixture to the mixed solution A in step (1) to obtain a mixed solution B;

[0060] (3) dissolving 25 mmol of hydrated hydrazine in 30 mL of deionized water, mixing well, and adding the mixture to the mixed solution B in step (2) to obtain a mixed solution C;

[0061] (4) Dissolve 1 mmol of 3-mercaptopropyltriethoxysilane (MTPS) solution in 10 mL of ethanol, mix well, and then add the mixture to the mixed solution C in step (3) to obtain a red mixed solution D;

[0062] (5) The solid product obtained from the mixed solution D was centrifuged and filtered, then washed alternately with deionized water and ethanol four times, and dried;

[0063] (6) Grinding the dried solid material into powder to obtain the water purifier.

[0064] Scanning electron microscopy results show that the structure of the micro-energy-driven multiphase Fenton water purifier prepared in this example is consistent with the structure of the micro-energy-driven multiphase Fenton water purifier prepared in Example 1.

[0065] Test Example 1

[0066] In order to investigate the stability of the water purifier in long-term use, this test example prepared a 10 mg / L solution of ciprofloxacin (CIP). 0.3 g / L of the water purifier prepared in Example 1 and H2O2 were put into a 100 mL pollutant system for degradation. After 10 consecutive runs, the test results were as follows: Figure 2 shown.

[0067] Figure 2 The results showed that after 10 consecutive runs, the removal rate of ciprofloxacin by the water purifier remained above 95%, indicating that the water purifier had good stability and high practical application value in water treatment.

[0068] Test Example 2

[0069] 0.03 g of the micro-energy driven multiphase Fenton water purifier prepared in Example 1 and 10 μL of H2O2 were added into 100 mL of a 10 mg·L -1The pollutant solution was kept at a constant temperature of 35°C and magnetic stirring was continued to start the degradation reaction. Samples were taken at 0, 10, 20, 30, 40, 50, and 60 minutes and the concentration of the pollutants was tested. The test results are as follows: Figure 3 shown.

[0070] Figure 3 The results showed that within 60 minutes, the water purifier could almost completely degrade bisphenol A and ciprofloxacin, and its removal rates for acid orange 7 and diphenhydramine were between 80-90%, indicating that the water purifier prepared by the present invention has a significant degradation effect on different pollutants.

[0071] Comparative Example 1

[0072] In this comparative example, except that step (2) is not performed, the remaining steps are the same as those in Example 1.

[0073] The results show that this control example cannot prepare a multi-phase water purifier.

[0074] Comparative Example 2

[0075] In this comparative example, except that step (3) is not performed, the remaining steps are the same as those in Example 1.

[0076] After testing, the catalytic activity of the water purifier prepared in this control example was greatly weakened.

[0077] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a micro-energy driven multiphase Fenton water purifier, characterized in that: The method comprises the following steps: sequentially adding a selenium dioxide solution, a hydrazine hydrate solution and a 3-mercaptopropyltriethoxysilane solution into a mixed solution of ferric chloride hexahydrate and zinc sulfate heptahydrate, fully stirring, centrifuging and filtering out a solid product, then washing the solid product alternately with deionized water and ethanol, and drying to obtain the water purifier.

2. The method for preparing the micro-energy driven multiphase Fenton water purifier according to claim 1, characterized in that: The steps include: (1) dissolving ferric chloride hexahydrate and zinc sulfate heptahydrate in deionized water and stirring to obtain a mixed solution A; (2) dissolving selenium dioxide in deionized water, stirring and mixing, and then adding the mixture to the mixed solution A in step (1) to obtain a mixed solution B; (3) dissolving hydrazine hydrate in deionized water, stirring and mixing, and then adding the mixture to the mixed solution B in step (2) to obtain a mixed solution C; (4) dissolving 3-mercaptopropyltriethoxysilane in ethanol, stirring and mixing uniformly, and then adding the mixture to the mixed solution C in step (3) to obtain a mixed solution D; (5) Centrifuge the mixed solution D to remove the solid product, then wash the solid product alternately with deionized water and ethanol, and dry it; (6) Grinding the dried solid product into powder to obtain the water purifier.

3. The method for preparing the micro-energy driven multiphase Fenton water purifier according to claim 1, characterized in that: The molar ratio of the ferric chloride hexahydrate, the zinc sulfate heptahydrate and the selenium dioxide is (0.5-2.5):(2-3):(20-25).

4. The method for preparing the micro-energy driven multiphase Fenton water purifier according to claim 1, characterized in that: The concentration of the hydrazine hydrate solution is 0.4-1.8 mol / L.

5. The method for preparing the micro-energy driven multiphase Fenton water purifier according to claim 1, characterized in that: The concentration of the 3-mercaptopropyltriethoxysilane solution is 0.05-0.25 mol / L.

6. The method for preparing the micro-energy driven multiphase Fenton water purifier according to claim 2, characterized in that: In step (5), the centrifugal speed is 8000-12000 r / min, and the centrifugal time is 3-10 minutes.

7. The method for preparing a micro-energy driven multiphase Fenton water purifier according to claim 2, characterized in that: In step (5), the drying temperature is 50-70° C. and the drying time is 8-24 h.

8. A micro-energy driven multi-phase Fenton water purifier prepared according to the method for preparing a micro-energy driven multi-phase Fenton water purifier according to any one of claims 1 to 7.

9. Use of the micro-energy driven multiphase Fenton water purifier according to claim 8 in treating organic pollutants in water.

10. The use according to claim 9, characterized in that The organic pollutants include: one or more of Acid Orange 7, bisphenol A, ciprofloxacin, and diphenhydramine.

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