Preparation method of iron-based catalyst for treating wastewater by advanced oxidation method
By loading iron hydroxyl oxide on the foam nickel foam matrix at room temperature to form a self-supporting catalyst, the problems of complex preparation process and difficulty in recycling and separation of traditional iron-based catalysts are solved, and efficient wastewater degradation effect is achieved.
Patent Information
- Application Number
- CN202311482159.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-11-09
- Publication Date
- 2025-05-13
AI Technical Summary
The preparation method of traditional iron-based catalysts has problems such as high-temperature treatment steps, many types of reagents, high equipment requirements, and difficulty in recycling and separation of powdered catalysts, resulting in complex preparation process and low efficiency.
The iron hydroxyoxide is directly loaded on the foam nickel foam matrix at room temperature to form a self-supporting catalyst, simplifying the preparation steps and improving the requirements of reagents and equipment.
The efficient preparation of self-supported iron hydroxyoxide catalyst is achieved, which reduces the complexity of the preparation process and equipment requirements, and improves the circulating performance of the catalyst and wastewater degradation efficiency.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of environmental protection, and relates to a method for preparing a self-supporting iron oxyhydroxide catalyst, and in particular to a method for preparing a self-supporting iron oxyhydroxide catalyst for treating wastewater by an advanced oxidation process. Background Art
[0002] With the overall improvement of human living standards, a large amount of organic matter is used in the development of human society, such as dyes, antibiotics, organic pesticides, etc. The wastewater generated by these organic substances is highly toxic and highly polluting, which not only causes damage to the ecosystem, but also interferes with the physiological activities of organisms.
[0003] Advanced oxidation process is a highly efficient method for treating organic wastewater, which mainly utilizes hydroxyl radicals (·OH) and superoxide radicals (·O2 - ) and sulfate radicals (SO4 - ·) and other strong oxidizing free radicals to degrade highly toxic and highly polluting organic matter.
[0004] Iron-based catalysts have the advantages of high catalytic efficiency and thorough reaction, and are commonly used catalysts in advanced oxidation reactions. However, the traditional preparation methods of iron-based catalysts face some difficulties and cumbersome processes. For example, the synthesis of iron-based catalysts usually requires high-temperature treatment steps to promote phase change, grain growth or the formation of active sites. High-temperature treatment has high requirements for reaction conditions and equipment, which increases the complexity of the preparation process. Taking powdered iron-based catalysts as an example, the preparation process requires many types of reagents, and often requires a molding step to form the desired particle shape and size. At the same time, powdered catalysts face the problem of difficulty in recycling and separation during wastewater treatment.
[0005] In summary, developing a simple and feasible method for preparing self-supporting iron-based catalysts has important application value. Summary of the invention
[0006] The purpose of the present invention is to provide a method for preparing nickel foam loaded with ferric oxyhydroxide (FeOOH / Ni) which can be applied to the degradation of organic wastewater by an advanced oxidation process, wherein the active component ferric oxyhydroxide is directly loaded on a nickel foam matrix at room temperature to form a continuous structure, synthesize a self-supporting catalyst, simplify the preparation steps of the catalyst, improve the problems of excessive reagents and high equipment requirements in the preparation process, and ensure that the self-supporting catalyst prepared according to the method can efficiently catalyze the degradation experiment of organic wastewater, thereby solving the problems existing in the prior art.
[0007] To achieve the above purpose, the technical solution adopted by the present invention is as follows:
[0008] (1) Using deionized water as solvent, prepare a solution containing iron ions and chloride ions;
[0009] (2) The nickel foam sheet is placed in the solution of (1) and reacted at room temperature for a period of time to synthesize iron oxyhydroxide with uniform size and nanosheet morphology grown on the nickel foam substrate.
[0010] In the configuration of the solution in step (1), the solution containing iron ions and chloride ions is selected from one of ferric chloride, ferric nitrate and sodium chloride, ferric sulfate and potassium chloride, and ferric acetate and sodium chloride. The mass ratio of ferric nitrate to sodium chloride is: (1-3): (4-7). In the configuration of the solution in step (1), the solution containing iron ions and chloride ions is selected from one of ferric chloride, ferric nitrate and sodium chloride, ferric sulfate and potassium chloride, and ferric acetate and sodium chloride. The mass ratio of ferric nitrate to sodium chloride is: (1-3): (4-7).
[0011] In the configuration of the solution in step (1), the concentration of the solution containing iron ions and chloride ions is 0.01-1 mol / L, and the concentration ratio of iron ions to chloride ions is less than or equal to 1:1.
[0012] In the preparation of the solution in step (1), the beaker containing the solution is placed on a magnetic stirrer and stirred for 5 min to 30 min to fully dissolve the drug.
[0013] In the step (2), the nickel-iron foam is preliminarily washed with a hydrochloric acid aqueous solution, anhydrous ethanol, and deionized water, respectively.
[0014] In the step (2), after the nickel foam is placed, the beaker is sealed with a sealing film and then reacted at room temperature for 6 to 8 hours.
[0015] After the reaction in step (2) is completed, the mixture is rinsed alternately with deionized water and anhydrous ethanol for three or more times, placed in a vacuum drying oven, evacuated and dried at 60-100° C. for 8-16 h, and naturally cooled to room temperature to obtain a self-supporting iron oxyhydroxide catalyst (FeOOH / Ni).
[0016] Compared with the prior art, the present invention has the following beneficial effects:
[0017] 1. Room temperature synthesis and mild reaction conditions effectively solve the problems of excessive reagents, complicated steps, and high equipment requirements of commonly used iron-based catalysts.
[0018] 2. The morphology of the product can be effectively regulated by controlling the reaction conditions and preparation parameters.
[0019] 3. Compared with powdered catalysts, self-supporting iron-based catalysts are more conducive to solving the recovery and separation difficulties faced in the process of wastewater treatment and improving the recycling performance of the catalyst. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Figure 1 . Digital photo of the self-supporting iron oxyhydroxide catalyst prepared in Example 1.
[0021] Figure 2 . XRD spectrum of the self-supporting iron oxyhydroxide catalyst prepared in Example 1.
[0022] Figure 3 . SEM image of the self-supporting iron oxyhydroxide catalyst prepared in Example 1.
[0023] Figure 4 . Performance diagram of the self-supporting iron oxyhydroxide catalyst prepared in Example 1 for catalytic degradation of RhB using advanced oxidation method (Fenton oxidation). DETAILED DESCRIPTION
[0024] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0025] Example 1
[0026] preparation:
[0027] Cut a 2×4 cm nickel foam sheet, rinse it with deionized water three times, immerse it in dilute hydrochloric acid (the dilute hydrochloric acid completely covers the nickel foam) and ultrasonically pickle it for 10 min to remove the surface oxide layer and some impurities, rinse it with deionized water three times, and continue to ultrasonicate it in anhydrous ethanol for 10 min to completely remove the residual dilute hydrochloric acid. After ultrasonication, rinse it with deionized water and anhydrous ethanol alternately for 3 times and then dry it for use. 0.2020 g (0.5 mmol) of Fe(NO3)3·9H2O and 0.7890 g of NaCl were weighed and put into a beaker, and 50 mL of deionized water was added to prepare a solution. The solution was placed on a magnetic stirrer and stirred for 10 min to fully dissolve the drug. A dried nickel foam sheet was put in with its concave surface facing down to avoid contact with the magnetic rotor. The beaker was sealed with a sealing film and reacted for 6 h. After the reaction, deionized water and anhydrous ethanol were used to rinse alternately three times, placed in a vacuum drying oven, evacuated and dried at 60°C for 12 h, and naturally cooled to room temperature to obtain a self-supporting iron oxyhydroxide catalyst (FeOOH / Ni). The digital photo is shown in FIG. Figure 1 .
[0028] application:
[0029] The self-supporting iron oxyhydroxide-material was used as a catalyst to degrade the organic dye RhB by the advanced oxidation Fenton reaction. The concentration of RhB was characterized by its visible light absorbance at 554 nm. t is the absorbance of the solution at time t, and C0 is the absorbance at the initial time. Under the reaction conditions of temperature 48°C, pH = 2, 30% hydrogen peroxide dosage 10 mL, RhB concentration 15 mg / L, and RhB solution volume 150 mL, C t The curve of / C0 changing with time is as follows Figure 3 shown.
[0030] Example 2
[0031] Cut a 2×4 cm nickel foam sheet, rinse it with deionized water three times, immerse it in dilute hydrochloric acid (the dilute hydrochloric acid completely covers the nickel foam) and ultrasonically pickle it for 10 min to remove the surface oxide layer and some impurities, rinse it with deionized water three times, and continue to ultrasonicate it in anhydrous ethanol for 10 min to completely remove the residual dilute hydrochloric acid. After ultrasonication, rinse it with deionized water and anhydrous ethanol alternately for 3 times and then dry it for use. 0.2010 g (0.5 mmol) of Fe2(SO4)3·7H2O and 1.987 g of KCl were weighed and put into a beaker, and 80 mL of deionized water was added to prepare a solution. The solution was placed on a magnetic stirrer and stirred for 20 min to fully dissolve the drug. A dried nickel foam sheet was put in with its concave surface facing down to avoid contact with the magnetic rotor. The beaker was sealed with a sealing film and reacted for 7 h. After the reaction, the solution was rinsed alternately with deionized water and anhydrous ethanol three times, placed in a vacuum drying oven, evacuated and dried at 80°C for 10 h, and naturally cooled to room temperature to obtain a self-supporting iron oxyhydroxide catalyst (FeOOH / Ni).
[0032] Example 3
[0033] Cut a 2×4 cm nickel foam sheet, rinse it with deionized water three times, immerse it in dilute hydrochloric acid (the dilute hydrochloric acid completely covers the nickel foam) and ultrasonically pickle it for 10 min to remove the surface oxide layer and some impurities, rinse it with deionized water three times, and continue to ultrasonicate it in anhydrous ethanol for 10 min to completely remove the residual dilute hydrochloric acid. After ultrasonication, rinse it with deionized water and anhydrous ethanol alternately for 3 times and then dry it for use. 0.4011 g (1.0 mmol) of Fe(NO3)3·9H2O and 1.521 g of NaCl were weighed and put into a beaker, and 100 mL of deionized water was added to prepare a solution. The solution was placed on a magnetic stirrer and stirred for 30 min to fully dissolve the drug. A dried nickel foam sheet was put in with its concave surface facing down to avoid contact with the magnetic rotor. The beaker was sealed with a sealing film and reacted for 8 h. After the reaction, deionized water and anhydrous ethanol were used to rinse alternately three times, and the solution was placed in a vacuum drying oven, evacuated and dried at 100°C for 8 h. After naturally cooling to room temperature, a self-supporting iron oxyhydroxide catalyst (FeOOH / Ni) was obtained.
[0034] Example 4
[0035] Cut a 2×4 cm nickel foam sheet, rinse it with deionized water three times, put it into dilute hydrochloric acid (the dilute hydrochloric acid completely covers the nickel foam) and ultrasonic pickling for 10 min to remove the surface oxide layer and some impurities, rinse it with deionized water three times, continue ultrasonication in anhydrous ethanol for 10 min to completely remove the residual dilute hydrochloric acid, rinse it with deionized water and anhydrous ethanol alternately for 3 times after ultrasonication, and then dry it for use. Weigh 0.1909 g (1.0 mmol) C4H7FeO5 and 1.521 g NaCl into a beaker, add 150 mL of deionized water to make a solution, place it on a magnetic stirrer and stir for 25 min to fully dissolve the drugs, put the dried nickel foam sheet into it, so that its concave side faces down to avoid contact with the magnetic rotor, seal the beaker mouth with a sealing film and react for 6.5 h. After the reaction, rinse it with deionized water and anhydrous ethanol alternately three times, place it in a vacuum drying oven, evacuate it and dry it at 90 ° C for 9 h, and cool it naturally to room temperature to obtain a self-supporting iron hydroxide oxide catalyst (FeOOH / Ni).
[0036] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.
Claims
1. A method for preparing a self-supporting iron oxyhydroxide catalyst for treating wastewater by an advanced oxidation process, characterized in that: Includes the following sections: (1) Using deionized water as solvent, prepare a solution containing iron ions and chloride ions; (2) placing the nickel foam sheet into the solution in (1) and reacting at room temperature for a period of time to synthesize iron oxyhydroxide having a uniform size and a nanosheet-like morphology grown on the nickel foam substrate.
2. The preparation method according to claim 1, characterized in that: In the preparation of the solution in step (1), the solution containing iron ions and chloride ions is selected from ferric chloride, ferric nitrate and sodium chloride, ferric sulfate and potassium chloride, and ferric acetate and sodium chloride, the mass ratio of ferric nitrate to sodium chloride is: (1-3): (4-7), and the amount of deionized water used as the solvent is 40-80 ml.
3. The concentration of the solution containing iron ions and chloride ions is 0.01-1 mol / L, and the concentration ratio of iron ions to chloride ions is less than or equal to 1:
1. The preparation method according to claim 1, characterized in that: In the preparation of the solution in step (1), the beaker containing the solution is placed on a magnetic stirrer and stirred for 5 min to 30 min to fully dissolve the drug.
4. The preparation method according to claim 1, characterized in that: The nickel-iron foam is preliminarily washed with a hydrochloric acid solution, anhydrous ethanol and deionized water.
5. The preparation method according to claim 1, characterized in that: In the step (2), the nickel foam is placed in the beaker and the beaker is sealed with a sealing film and then reacted at room temperature for 6 to 8 hours.
6. The preparation method according to claim 1, characterized in that: After the reaction in step (2) is completed, the mixture is rinsed alternately with deionized water and anhydrous ethanol for three or more times, placed in a vacuum drying oven, evacuated and dried at 60-100° C. for 8-16 h, and naturally cooled to room temperature to obtain a self-supporting iron oxyhydroxide catalyst (FeOOH / Ni).
7. Use of a self-supporting iron oxyhydroxide catalyst for treating wastewater by an advanced oxidation process prepared by the preparation method according to any one of claims 1 to 6, characterized in that: The self-supporting iron oxyhydroxide catalyst can be used in combination with Fenton's reagent to efficiently treat some pollutants in wastewater, especially organic pollutants such as dyes and antibiotics; in addition, it can also efficiently adsorb inorganic pollutants such as sulfur, carbon, nitrogen, and phosphorus.