Preparation and application method of spinel type iron-copper oxide
By preparing spinel-type iron-copper oxide catalysts, the problems of high energy consumption and prone to secondary pollution in the prior art are solved, and the effect of efficient degradation of organic pollutants is achieved, and the characteristics of easy recycling and low toxicity are achieved.
Patent Information
- Application Number
- CN202311632945.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-11-29
- Publication Date
- 2025-07-08
AI Technical Summary
The prior art is difficult to prepare catalysts under low energy consumption, so that they efficiently degrade organic pollutants in wastewater without secondary pollution, and the catalysts are easy to be recycled.
Spinel-type iron-copper oxide is used as a catalyst, and is prepared by mixing copper salt and iron salt with citric acid, evaporating, drying, grinding and calcining, and a catalyst with good uniformity and stable crystal structure is prepared for sulfite oxidation and degradation of organic pollutants.
It has achieved efficient degradation of organic pollutants, with a degradation efficiency of more than 85%, low toxicity of the catalyst, not easy to produce secondary pollution, and easy to separate and recycle, with broad application prospects.
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Figure CN120268398A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of catalysts, and specifically discloses a preparation and application method of spinel-type iron copper oxide. Background Technique
[0002] In recent years, a large number of artificially synthesized organic and inorganic pollutants have been discharged into water bodies, causing serious water pollution. Among them, the pollution of persistent and difficult-to-degrade organic pollutants is particularly serious and difficult to solve, becoming a major problem in environmental treatment and restoration. These organic pollutants have a long residence time in the environment, are not easily degraded by microorganisms, and have biological enrichment properties. They will accumulate along the food chain and ultimately endanger human health. Therefore, in the current situation, there is an urgent need for more effective technologies to remove refractory organic pollutants in wastewater.
[0003] Based on sulfate radical (SO4 - ·) advanced oxidation technology is a new type of technology developed at home and abroad in recent years and has also become one of the relatively popular wastewater treatment technologies at present. It is found that SO4 - · has strong oxidation ability, can maintain its activity in a wide pH range (4.0 - 9.0), effectively and stably contact with organic pollutants and react, can rapidly degrade most organic pollutants, and mineralize them into CO2 and inorganic acids.
[0004] Sulfite S(IV) is a desulfurization by-product. The atmospheric pollutant SO2 generated by the oxidation and release of sulfur substances, the smelting of sulfide ores, and the combustion of fossil fuels dissolves in water to form SO3 2- and HSO3 - . S(IV) is widely sourced, has a price only half that of persulfate (PS), is low in toxicity, and is easy to prepare. It can be activated to generate sulfate radical (SO4 - ·), peroxymonosulfate radical (SO5 - ·), sulfite radical (SO3 - ·) and hydroxyl radical (·OH) and other active substances with high oxidation potentials, which can rapidly and efficiently oxidize and degrade various organic pollutants. In addition, the reducing S(IV) is easily naturally oxidized to harmless sulfate in water and is not likely to produce toxic and harmful substances that cause secondary pollution. However, sulfite activation to generate sulfate radical (SO4 - ·), peroxymonosulfate radical (SO5 - ·), sulfite radical (SO3 -·) and various active substances with high oxidation potential such as hydroxyl radicals (·OH) to complete the above reactions quickly and efficiently. To oxidize and degrade various organic pollutants, a suitable catalyst is required. How to prepare a catalyst with low energy consumption, so that the prepared catalyst will not react with other substances in the wastewater, has low toxicity itself, will not cause secondary pollution, and is convenient for recycling after recovery is an urgent problem to be solved by those skilled in the art. Summary of the Invention
[0005] To solve the technical problems listed in the background art, the present invention provides a preparation method of spinel-type iron copper oxide, and the specific technical solution is as follows:
[0006] S1. Mix copper salt, iron salt and citric acid evenly according to the molar ratio of the reaction equation, and evaporate the water to a sol-state mixed solution;
[0007] S2. The sol-state mixed solution is dried, ground into solid powder, and then calcined;
[0008] S3. Cool, wash, dry and grind the system obtained in step S2 to obtain spinel-type iron copper oxide.
[0009] Preferably, the copper salt and iron salt are at least one of nitrate, sulfate, and chloride salt, the temperature for evaporating water is 50-80°C, and the time is 1.5-8h.
[0010] Preferably, the calcination temperature is 400-600°C, the calcination atmosphere is air, and the duration is 2-5h; the heating program is to heat from room temperature to 300°C at a rate of 1°C / min, keep the temperature at 300°C for 1-2h, and then quickly raise the temperature to the calcination temperature.
[0011] Preferably, the drying temperature is controlled at 60-80°C, and the drying time is 8-20h.
[0012] The present invention also provides an application method of spinel-type iron copper oxide, including using the spinel-type iron copper oxide prepared by the above preparation method as a catalyst to degrade organic pollutants in wastewater by sulfite.
[0013] Furthermore, the concentration of the organic pollutants in the wastewater is 0.01-0.2 mM, the dosage of the spinel-type iron copper oxide in the wastewater is 0.42-1.68 mM, and the dosage of the sulfite in the wastewater is 1.25-10 mM.
[0014] The above scheme is preferably applicable to degrading any one of organic pollutants including Orange II, Rhodamine B, Reactive Brilliant Blue and Methyl Orange.
[0015] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0016] The preparation method provided by the present invention has low energy consumption in the process, reduces the consumption of solvents, and has low manufacturing and production costs. The raw materials for preparing the catalyst in the present invention are widely sourced, and the prepared spinel-type iron copper oxide has good particle uniformity and a stable crystal structure; its catalytic performance is excellent.
[0017] Since the prepared product has low toxicity and is not a potential carcinogen, it is creatively applied to the field of sewage purification processes for the oxidation and degradation of various organic pollutants by sulfite. It has excellent ability in the direction of efficiently removing refractory organic pollutants, with a degradation efficiency of over 85%. Moreover, this catalyst has strong magnetism, is easy to separate and recycle, and can be recycled multiple times, having broad economic benefits and application prospects in the field of remediation of water bodies polluted by refractory organic pollutants. Description of the Drawings
[0018] Figure 1 X-ray powder diffraction pattern of the spinel-type iron copper oxide prepared in Example 1;
[0019] Figure 2 SEM image of the spinel-type iron copper oxide prepared in Example 1;
[0020] Figure 3 Comparison chart of the degradation effects of individual sulfite, individual spinel-type iron copper oxide, and the present invention on Orange II;
[0021] Figure 4 Comparison chart of the degradation effects of the spinel-type iron copper oxide / sulfite system on different refractory organic pollutants. Detailed Embodiments
[0022] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be described below in conjunction with the accompanying drawings and specific embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. Based on these embodiments, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the scope of protection of the present invention.
[0023] Example 1
[0024] Preparation of spinel-type iron copper oxide:
[0025] According to the stoichiometric ratios of the elements in the chemical formula CuFe2O4, the raw materials were weighed respectively: 1 mmol of iron(III) nitrate nonahydrate, 0.5 mmol of copper(II) nitrate trihydrate, and 1.5 mmol of citric acid.
[0026] Mix ferric nitrate nonahydrate, copper nitrate trihydrate and citric acid evenly, adjust the temperature of the water bath to 50 - 80 °C, evaporate the water, and dry the obtained transparent sol to get a gel; transfer the gel into a muffle furnace, the calcination temperature is 400 - 600 °C, the calcination time is 2 - 5 h, the heating program is from room temperature to 300 °C at a rate of 1 °C / min, hold at 300 °C for 1 - 2 h, then rapidly heat to above 400 °C, the calcination atmosphere is air, and then cool to room temperature; take out the sample, grind it, rinse it with pure water for multiple times until the solution is neutral, then transfer it into an oven, dry it at 60 - 80 °C for 8 - 20 h to obtain a powdery sample.
[0027] As Figure 1 shown, it is the X-ray powder diffraction pattern of the spinel-type iron copper oxide prepared in Example 1, and the results show that the prepared product is a pure substance composed of spinel-type iron copper oxide.
[0028] As Figure 2 shown, it is the SEM (scanning electron microscope) image of the spinel-type iron copper oxide prepared in Example 1; it can be seen that the prepared spinel-type iron copper oxide has good crystallization, uniform particles, and the particle size is 10 - 30 nm.
[0029] Example 2
[0030] Apply the spinel-type iron copper oxide prepared in Example 1 to the catalyst for removing Orange II.
[0031] Experiment 1: Take 100 mL of Orange II solution with a concentration of 0.1 mM, add the prepared spinel-type iron copper oxide in an amount of 0.63 mM, and react at room temperature for 60 min.
[0032] Experiment 2: Take 100 mL of Orange II solution with a concentration of 0.1 mM, add sulfite in an amount of 5 mM, and react at room temperature for 60 min.
[0033] Experiment 3: Take 100 mL of Orange II solution with a concentration of 0.1 mM, add the spinel-type iron copper oxide in an amount of 0.63 mM, add sulfite in an amount of 5 mM, and react at room temperature for 60 min.
[0034] As Figure 3 shown, it is the comparison chart of the degradation effects of removing the organic pollutant Orange II in Experiments 1 - 3. It can be seen that the spinel-type iron copper oxide / sulfite (CuFe2O4 / SO3 2- ) system can greatly improve the efficiency of sulfite in degrading Orange II. After reacting for 60 min, the removal effects of Orange II under the conditions of sulfite alone, spinel-type iron copper oxide alone, and spinel-type iron copper oxide / sulfite are 2.1%, 4.8%, and 98.1% in sequence.
[0035] Example 3
[0036] Research on the application of spinel-type iron copper oxide / sulfite system in treating different organic pollutants.
[0037] Experiment 4: Take 100 mL of orange II solution with a concentration of 0.1 mM, add spinel-type iron copper oxide in an amount of 0.15 g / L, add sulfite in an amount of 0.73 g / L, and react at room temperature for 60 min.
[0038] Experiment 5: Take 100 mL of rhodamine B solution with a concentration of 0.1 mM, add spinel-type iron copper oxide in an amount of 0.15 g / L, add sulfite in an amount of 0.73 g / L, and react at room temperature for 60 min.
[0039] Experiment 6: Take 100 mL of reactive brilliant blue solution with a concentration of 0.1 mM, add spinel-type iron copper oxide in an amount of 0.15 g / L, add sulfite in an amount of 0.73 g / L, and react at room temperature for 60 min.
[0040] Experiment 7: Take 100 mL of methyl orange solution with a concentration of 0.1 mM, add spinel-type iron copper oxide in an amount of 0.15 g / L, add sulfite in an amount of 0.73 g / L, and react at room temperature for 60 min.
[0041] As Figure 4 shown, it is a comparison chart of the removal capabilities of different pollutants in Experiments 4 - 7 under the spinel-type iron copper oxide / sulfite (CuFe2O4 / SO3 2- ) system. It can be seen that this system has good degradation effects on pollutants. After reacting for 60 min, the degradation rates of orange II, rhodamine B, reactive brilliant blue, and methyl orange all reached over 95.0%. Thus, it can be known that the spinel-type iron copper oxide / sulfite system has low selectivity for pollutants and has good application and development prospects.
[0042] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
Claims
1. A preparation method of a spinel-type iron copper oxide, characterized in that, It includes the following steps: S1. Mix copper salt, iron salt and citric acid evenly according to the molar ratio of the reaction equation, and evaporate the water to a sol-state mixed solution; S2. Dry and grind the sol-state mixed solution into a solid powder, and then conduct calcination; S3. Cool, wash, dry and grind the system obtained in step S2 to obtain spinel-type iron copper oxide.
2. The preparation method of a spinel-type iron copper oxide as described in claim 1, characterized in that: The copper salt and iron salt are at least one of nitrate, sulfate and chloride salt. The temperature for evaporating the water is 50-80 °C and the time is 1.5-8 h.
3. The preparation method of a spinel-type iron copper oxide as described in claim 2, characterized in that: The temperature of the calcination is 400-600 °C, the atmosphere of the calcination is air, and the duration is 2-5 h; the heating program is to heat from room temperature to 300 °C at a rate of 1 °C / min, keep the temperature at 300 °C for 1-2 h, and then quickly heat up to the calcination temperature.
4. The preparation method of a spinel-type iron copper oxide as described in claim 3, characterized in that: The temperature of the drying is controlled at 60-80 °C and the drying time is 8-20 h.
5. A method for applying a spinel-type iron copper oxide, characterized in that, It includes using the spinel-type iron copper oxide prepared by the preparation method of a spinel-type iron copper oxide according to any one of claims 1-4 as a catalyst to degrade organic pollutants in sulfite-containing wastewater.
6. The application method of a spinel-type iron copper oxide as described in claim 5, characterized in that, The concentration of the organic pollutants in the wastewater is 0.01-0.2 mM, the dosage of the spinel-type iron copper oxide in the wastewater is 0.42-1.68 mM, and the dosage of the sulfite in the wastewater is 1.25-10 mM.
7. The application method of a spinel-type iron copper oxide as described in claim 6, characterized in that, The organic pollutants include any one of Orange II, Rhodamine B, Reactive Brilliant Blue and Methyl Orange.