Iron salt loaded tourmaline catalyst, its preparation method and application
By preparing iron salt-supported tourmaline catalysts, the permanent self-polarization effect of tourmaline is used to accelerate the Fe2+/Fe3+ cycle under visible light, which solves the problem of low efficiency of existing photocatalysts and achieves efficient degradation of antibiotics, making it suitable for industrial applications.
Patent Information
- Application Number
- CN202310844885.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-07-11
- Publication Date
- 2025-12-09
- Estimated Expiration
- 2043-07-11
AI Technical Summary
Existing photocatalysts such as graphitic carbon nitride and titanium dioxide have low catalytic efficiency in degrading antibiotics and low solar energy utilization, making it difficult to effectively remove antibiotic pollution from water.
A catalyst with high catalytic activity was prepared by calcining a mixture of tourmaline and iron salts using iron salt supported catalyst. The permanent self-polarization effect of tourmaline was utilized to accelerate the Fe2+/Fe3+ cycle under visible light, thereby improving the activation efficiency of the oxidant.
The degradation rate of sulfadiazine reaches over 90% within 80–240 minutes, significantly improving the photocatalytic degradation efficiency of the catalyst. It is low-cost, environmentally friendly, and suitable for industrial production.
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of catalysts, in particular to an iron salt loaded tourmaline catalyst and a preparation method and application thereof. BACKGROUND
[0002] Antibiotics are a kind of organic pollutants with persistence and difficulty in biodegradation, and have potential risks to natural ecology and human health, and therefore are particularly concerned. Therefore, it is particularly important to seek a high-efficiency, inexpensive and easily available catalyst to activate an oxidizing agent to degrade antibiotic drugs in water. As a kind of natural energy, solar energy has the characteristics of low cost, cleanliness, safety, greenness and renewability, and is gradually valued by mankind. In China, although great breakthroughs have been made in solar energy technology, the utilization of solar energy cannot solve some current environmental pollution problems due to the low energy conversion rate. Meanwhile, the existing photocatalytic technology, such as the photocatalyst based on graphite phase carbon nitride, titanium dioxide and boron nitride, still has the problem of low catalytic efficiency in degrading antibiotics. SUMMARY
[0003] Therefore, the purpose of the present application is to provide an iron salt loaded tourmaline catalyst and a preparation method and application thereof, and the iron salt loaded tourmaline catalyst prepared by the present application has high catalytic activity for organic pollutants such as antibiotics.
[0004] In order to achieve the above-mentioned purpose, the present application provides the following technical scheme:
[0005] The present application provides a preparation method of an iron salt loaded tourmaline catalyst, comprising the following steps: mixing tourmaline and iron salt, calcining to obtain an iron salt loaded tourmaline catalyst.
[0006] Preferably, the mass ratio of the tourmaline to the iron salt is 1:0.1-1.
[0007] Preferably, the particle size of the tourmaline is 5000-20000 mesh.
[0008] Preferably, the iron salt comprises one or more of ferric nitrate, ferric chloride, ferric sulfate and ferric citrate.
[0009] Preferably, the calcining comprises a temperature rising stage and a temperature holding stage, the temperature rising rate of the temperature rising stage is 2.5-5.5℃ / min; the temperature of the temperature holding stage is 500-800℃, and the holding time is 1-3h; and the atmosphere of the calcining is air.
[0010] Preferably, after the calcining, the obtained calcined product is cooled to room temperature, then dispersed in a washing agent for washing, solid-liquid separation is performed, and the obtained solid product is dried.
[0011] Preferably, the washing agent comprises one or more of water, ethanol, tetrahydrofuran and hydrochloric acid.
[0012] Preferably, the drying temperature is 100-150℃.
[0013] The application provides the iron salt loaded tourmaline catalyst prepared by the preparation method.
[0014] The application also provides application of the iron salt loaded tourmaline catalyst in photocatalytic degradation of organic pollutants.
[0015] The application uses tourmaline and iron salt as raw materials to prepare the iron salt loaded tourmaline catalyst by calcination. Tourmaline is a kind of natural silicate mineral with abundant reserves, and has permanent self-polarization effect. Under visible light irradiation, tourmaline can provide electrons for iron ions in the iron salt, accelerate Fe 2+ / Fe 3+ cycle and improve the efficiency of activated oxidants, thereby significantly improving the photocatalytic degradation efficiency of the catalyst on organic pollutants. Moreover, the preparation method provided by the application is simple in process and easy to operate, the raw materials used are widely available and low in price, the production cost is low, the method is green and environmentally friendly, and is suitable for industrial production. As shown in the test results of the examples, the degradation rate of the iron salt loaded tourmaline catalyst prepared by the application on sulfadiazine is more than 90% within 80-240 min, which indicates that the iron salt loaded tourmaline catalyst prepared by the application has high catalytic efficiency and high catalytic activity on organic pollutants. DETAILED DESCRIPTION
[0016] The application provides a preparation method of an iron salt loaded tourmaline catalyst, which comprises the following steps: mixing tourmaline and iron salt, and calcining to obtain the iron salt loaded tourmaline catalyst.
[0017] Unless otherwise specified, the raw materials used in the application are all commercially available.
[0018] In the application, the mass ratio of the tourmaline to the iron salt is preferably 1:0.1-1, more preferably 1:0.2-0.9, and further preferably 1:0.4-0.8. In the application, the particle size of the tourmaline is preferably 5000-20000 mesh, more preferably 5000-15000 mesh, and further preferably 5000-10000 mesh. In the application, the iron salt preferably comprises one or more of ferric nitrate, ferric chloride, ferric sulfate and ferric citrate.
[0019] In the application, the mixing is preferably grinding mixing, and the application does not have special limitations on the grinding mixing, and the raw materials can be mixed uniformly.
[0020] In the present application, the calcination preferably comprises a temperature rising stage and a temperature keeping stage, the temperature rising rate of the temperature rising stage is preferably 2.5-5.5℃ / min, more preferably 2.5-4.5℃ / min, further preferably 2.5-3.5℃ / min, and the initial temperature of the temperature rising stage is preferably room temperature; the temperature of the temperature keeping stage is preferably 500-800℃, more preferably 500-700℃, further preferably 500-600℃, and the temperature keeping time of the temperature keeping stage is preferably 1-3h, more preferably 1-2h; the atmosphere of the calcination is preferably air; and the calcination is preferably carried out in a muffle furnace.
[0021] After the calcination, the present application preferably further comprises cooling the obtained calcination product to room temperature, then dispersing it in a washing agent, separating the solid and the liquid, drying the obtained solid product, and obtaining the iron salt loaded tourmaline catalyst. The present application is not particularly limited to the cooling, and the cooling to room temperature can be carried out by using a cooling method well known to those skilled in the art, such as natural cooling. In the present application, the washing agent preferably comprises one or more of water, ethanol, tetrahydrofuran and hydrochloric acid aqueous solution; the water preferably comprises deionized water; the concentration of the hydrochloric acid aqueous solution is preferably 1-5%, more preferably 2-3%; and the number of times of the washing is preferably 3-5, more preferably 3-4. In the present application, the solid-liquid separation is preferably centrifugal separation, the rotation speed of the centrifugal separation is preferably 5000-8000r / min, more preferably 7000-8000r / min; and the time of the centrifugal separation is preferably 5-20min, more preferably 10-15min. In the present application, the temperature of the drying is preferably 100-150℃, more preferably 100-120℃, and the present application is not particularly limited to the time of the drying, and the drying to constant weight is enough.
[0022] The present application provides the iron salt loaded tourmaline catalyst prepared by the preparation method of the above technical solution.
[0023] The application further provides application of the ferric salt loaded tourmaline catalyst in photocatalytic degradation of organic pollutants. In the application, the organic pollutants preferably include antibiotics, the antibiotics preferably include one or more of sulfonamide antibiotics, tetracycline antibiotics and quinolone antibiotics; the sulfonamide antibiotics preferably include sulfadiazine (SD) and / or sulfonamide quinolyl; the tetracycline antibiotics preferably include tetracycline hydrochloride; and the quinolone antibiotics preferably include ofloxacin and / or ciprofloxacin. In the application, the photocatalytic degradation is preferably carried out in the presence of hydrogen peroxide. In the application, the molar ratio of the ferric salt loaded tourmaline catalyst to the organic pollutants is preferably 1:500-4000, and more preferably 1:2000-2500. In the application, the mass ratio of the ferric salt loaded tourmaline catalyst to the substance amount of the organic pollutants is preferably 1g:0.01-1mol, and more preferably 1g:0.05mol.
[0024] The technical solutions in the application will be described clearly and completely below in combination with the embodiments in the application. Obviously, the described embodiments are only some of the embodiments of the application, but not all the embodiments. Based on the embodiments in the application, all the other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.
[0025] Embodiment 1
[0026] 5.0g of 10000-mesh tourmaline and 3.6g of ferric nitrate were uniformly mixed, uniformly ground in a mortar, the obtained mixture was placed in a crucible, the crucible cover was covered, then the mixture was placed in a muffle furnace, heated to 500℃ at a heating rate of 2.5℃, and then heat-treated for 1h, naturally cooled, taken out, washed with methanol for 3 times, and a ferric salt loaded tourmaline catalyst was obtained.
[0027] Embodiment 2
[0028] 5.0g of 20000-mesh tourmaline and 2.4g of ferric chloride were uniformly mixed, uniformly ground in a mortar, the obtained mixture was placed in a crucible, the crucible cover was covered, then the mixture was placed in a muffle furnace, heated to 700℃ at a heating rate of 4.5℃, and then heat-treated for 2h, naturally cooled, taken out, washed with deionized water for 3 times, and a ferric salt loaded tourmaline catalyst was obtained.
[0029] Embodiment 3
[0030] 5.0 g of tourmaline with a particle size of 20000 and 3.58 g of iron sulfate were uniformly mixed, and the obtained mixture was ground in a mortar, and then was placed in a crucible, and after the crucible was covered with a crucible cover, was placed in a muffle furnace, and was calcined at a temperature rising rate of 3.5 ℃ to 600 ℃ and then was kept at 600 ℃ for 1 h, and was taken out after natural cooling, and was washed with 3% hydrochloric acid aqueous solution for 3 times to obtain the iron salt loaded tourmaline catalyst.
[0031] Example 4
[0032] 5.0 g of tourmaline with a particle size of 5000 and 2.46 g of iron citrate were uniformly mixed, and the obtained mixture was ground in a mortar, and then was placed in a crucible, and after the crucible was covered with a crucible cover, was placed in a muffle furnace, and was calcined at a temperature rising rate of 2.5 ℃ to 500 ℃ and then was kept at 500 ℃ for 1 h, and was taken out after natural cooling, and was washed with 5% hydrochloric acid aqueous solution for 3 times to obtain the iron salt loaded tourmaline catalyst.
[0033] Test Example 1
[0034] The performance of the iron salt loaded tourmaline catalysts prepared in Examples 1-3 in degrading sulfadiazine (SD) was evaluated by using a Q-Sun III type photocatalytic reaction system of Q-Lab Company of the United States.
[0035] 20 mL of a mixed aqueous solution of sulfadiazine-hydrogen peroxide (sulfadiazine concentration: 0.02 mmol / L, hydrogen peroxide concentration: 5 mmol / L) was used as a target pollutant, and 4 mg of the iron salt loaded tourmaline catalyst prepared in each of Examples 1-3 was added, and a degradation reaction was carried out under simulated sunlight irradiation.
[0036] The degradation rate of SD of the iron salt loaded tourmaline catalyst prepared in Example 1 was 90% or more at 180 min of the reaction. The degradation rate of SD of the iron salt loaded tourmaline catalyst prepared in Example 2 was 90% or more at 240 min of the reaction. The degradation rate of SD of the iron salt loaded tourmaline catalyst prepared in Example 3 was 90% or more at 100 min of the reaction. The degradation rate of SD of the iron salt loaded tourmaline catalyst prepared in Example 4 was 90% or more at 80 min of the reaction. It is shown that the iron salt loaded tourmaline catalyst prepared in the present application has high catalytic efficiency and high catalytic activity.
[0037] The above only describes the preferred embodiments of the present application, and it should be noted that those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.
Claims
1. A method for preparing an iron salt-supported tourmaline catalyst for photocatalytic degradation of organic pollutants, comprising the following steps: Tourmaline was mixed with iron salts and calcined to obtain an iron salt-supported tourmaline catalyst. The mass ratio of tourmaline to iron salt is 1:0.1~1; The tourmaline has a particle size of 5000~20000 mesh; The iron salts include one or more of ferric nitrate, ferric chloride, ferric sulfate, and ferric citrate; The mixing is a grinding mixture; The calcination includes a heating stage and a holding stage. The heating rate in the heating stage is 2.5~5.5℃ / min. The temperature in the holding stage is 500~800℃, and the holding time is 1~3h. The atmosphere for calcination is air. The calcination process further includes: cooling the obtained calcined product to room temperature, then dispersing it in a detergent for washing, separating the solid from the liquid, and drying the obtained solid product.
2. The preparation method according to claim 1, characterized in that, The detergent includes one or more of water, ethanol, tetrahydrofuran, and aqueous hydrochloric acid.
3. The preparation method according to claim 1, characterized in that, The drying temperature is 100~150℃.
4. The iron salt supported tourmaline catalyst prepared by the preparation method according to any one of claims 1 to 3.
5. The application of the iron salt supported tourmaline catalyst according to claim 4 in the photocatalytic degradation of organic pollutants.