Preparation of a lanthanum-containing schermanite material and its use in the treatment of antibiotic wastewater

Abstract

The application belongs to the field of materials and water treatment, and provides a preparation of lanthanum-containing schroeckingerite material and application of the material in antibiotic wastewater treatment, comprising: adding schroeckingerite to an alkali solution, then adding a La salt, performing a reaction, aging, collecting a precipitate, washing, drying, grinding, and obtaining the lanthanum-containing schroeckingerite material; the mass ratio of the schroeckingerite to the La salt is (1-2):(0.147-1.47). The lanthanum-containing schroeckingerite material can quickly remove antibiotic residues in water, has a simple preparation method, low cost, and a wide source of raw materials, and has a good application prospect. The material does not produce secondary pollution in the process of treating environmental pollutants, and is friendly to the environment. In the absence of external energy input, the lanthanum-containing schroeckingerite material can remove more than 90% of doxycycline, and is obviously superior to ordinary chemical synthesis of schroeckingerite.

Description

Technical Field

[0001] This invention belongs to the field of materials and water treatment, and relates to the preparation of a lanthanum-containing Schiele mineral material and its application in antibiotic wastewater treatment. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] In recent years, with the widespread use of antibiotics, antibiotic residues have not only disrupted the structure of microbial communities and affected the balance of aquatic ecosystems, but have also further threatened human health and public health security. In some intensive aquaculture areas, antibiotic concentrations in water bodies have reached μg / L or even mg / L levels. Long-term exposure to such environments inhibits the growth and reproduction of aquatic organisms, and the food chain is at risk of being disrupted.

[0004] Among numerous antibiotic removal materials, Schwertmannite possesses a large specific surface area and abundant surface active sites, exhibiting high removal potential and environmental friendliness. However, natural Schwertmannite suffers from limitations such as limited adsorption capacity, poor selectivity, and insufficient affinity for antibiotics, restricting its large-scale application in antibiotic wastewater treatment.

[0005] Currently, some studies have used lanthanum-modified Schiele minerals to adsorb and remove antibiotics from wastewater, but the removal efficiency still needs to be improved. Summary of the Invention

[0006] To address the aforementioned problems, this invention provides a lanthanum-containing Schöndorfite mineral material. This material can rapidly remove antibiotic residues from water, has a simple preparation method, low cost, and uses widely available raw materials, showing promising application prospects. This material does not generate secondary pollution during the treatment of environmental pollutants, making it environmentally friendly. Without external energy input, the lanthanum-containing Schöndorfite mineral material provided by this invention can remove over 90% of doxycycline, significantly outperforming conventional chemical methods for synthesizing Schöndorfite.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a method for preparing a lanthanum-containing Schiele mineral material, comprising:

[0009] The Schiele mineral was added to an alkaline solution, followed by the addition of La salt. The mixture was then reacted, aged, and the precipitate was collected, washed, dried, and ground to obtain lanthanum-containing Schiele mineral material.

[0010] The mass ratio of the Schiele mineral to the La salt is (1-2):(0.147-1.47).

[0011] This invention focuses on the adsorption and removal of antibiotics by lanthanum-modified Schiele minerals, optimizes material preparation and adsorption processes, and aims to provide theoretical basis and technical support for solving the problem of antibiotic wastewater pollution, contribute to the ecological restoration and protection of the water environment, and promote the innovative development of adsorption materials in the field of water pollution control.

[0012] In a second aspect, the present invention provides a lanthanum-containing Schiele mineral material prepared by the above-described method.

[0013] A third aspect of the present invention provides the application of the above-mentioned lanthanum-containing Schiele mineral material in the treatment of antibiotic wastewater.

[0014] Beneficial effects of the present invention

[0015] (1) This invention discloses a lanthanum-containing Schönbach mineral material that can rapidly remove antibiotic residues from water. The preparation method is simple, low-cost, and uses widely available raw materials, showing promising application prospects. This material does not generate secondary pollution during the treatment of environmental pollutants, making it environmentally friendly. Without external energy input, the lanthanum-containing Schönbach mineral material provided by this invention can remove more than 90% of doxycycline (20 mg / L), significantly superior to conventional chemical methods for synthesizing Schönbach minerals.

[0016] (2) The preparation method of the present invention is simple, practical and easy to promote. Attached Figure Description

[0017] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. Exemplary embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0018] Figure 1 Scanning electron microscope image of lanthanum-containing Schiele mineral material provided in an embodiment of the present invention.

[0019] Figure 2 The energy spectrum of the lanthanum-containing Schiele mineral material provided in the embodiments of the present invention.

[0020] Figure 3 This is a specific surface area diagram of the lanthanum-containing Schiele mineral material provided in an embodiment of the present invention.

[0021] Figure 4 The diagram shows the removal of doxycycline in the comparative and exemplary embodiments of the present invention. Detailed Implementation

[0022] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of skill in the art. The reagents and raw materials used in this invention are readily available through conventional means, and unless otherwise specified, they are used in accordance with conventional methods in the art or product instructions. Similarly, unless otherwise specified, the test methods of this invention are performed in accordance with conventional methods in the art or industry-standard methods or practices. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to the methods of this invention. The preferred embodiments and materials described herein are for illustrative purposes only.

[0024] This invention provides a method for preparing lanthanum-containing Schiele mineral materials, comprising:

[0025] The Schiele mineral was added to an alkaline solution, followed by the addition of La salt. The mixture was then reacted, aged, and the precipitate was collected, washed, dried, and ground to obtain lanthanum-containing Schiele mineral material.

[0026] The amount of Schiele mineral and La salt used affects the adsorption effect. Therefore, this invention studied the mass ratio of Schiele mineral to La salt. In some embodiments, the mass ratio of Schiele mineral to La salt is (1-2):(0.147-1.47), which has resulted in better antibiotic removal effect. Preferably, the amount of 0.2 mol / L LaCl3 added is 3~30 mL.

[0027] This invention does not impose any special limitation on the type of lanthanum salt, as long as it can be uniformly dispersed in an alkaline solution. In some embodiments, the La salt is LaCl3, which has high purity and a simple preparation method.

[0028] The reaction temperature affects the reaction rate and yield of Schiele minerals with La salt. Therefore, the present invention has studied the reaction temperature. In some embodiments, the reaction temperature is 90°C-95°C to improve the reaction rate and yield of Schiele minerals with La salt.

[0029] If the reaction time is too short, the reaction between Schiele mineral and La salt will be incomplete; if the reaction time is too long, side reactions are likely to occur. Therefore, the present invention has studied the reaction time. In some embodiments, the reaction time is 6-8 hours to improve the reaction efficiency.

[0030] The present invention does not impose any special limitation on the type of alkaline solution, as long as it can provide an alkaline environment for the reaction. In some embodiments, the alkaline solution is a NaOH solution with a concentration of 6.0-8.0 mol / L to provide an alkaline environment for the reaction between Schiele mineral and La salt.

[0031] The aging time affects the formation of products in the coprecipitation process. Therefore, this invention studies the aging time. In some embodiments, the aging time is 12-16 h to prepare lanthanum-containing Schiele mineral materials by coprecipitation.

[0032] The speed and time of centrifugation affect the separation effect of precipitates. Therefore, this invention has studied the speed and time of centrifugation. In some embodiments, the centrifugation conditions are 5000-6000 rpm for 8-10 min to improve the separation efficiency of precipitates.

[0033] This invention optimizes the preparation method of Schiele minerals to improve their yield and purity. In some embodiments, the preparation method of Schiele minerals includes: mixing FeSO4·7H2O and H2O2 evenly in water, culturing under certain conditions, and collecting the minerals after culturing.

[0034] The minerals in the system were washed with H2SO4 and water, freeze-dried, and sieved to obtain the final product. Acid washing can effectively remove impurities loaded on the minerals and improve the purity of Schiele minerals.

[0035] More specifically, including:

[0036] (1) Chemical synthesis of Schiele minerals:

[0037] FeSO4·7H2O was dissolved in deionized water, and 30% H2O2 was added. The mixture was then placed in a 250 mL Erlenmeyer flask and incubated in a constant-temperature shaker at 28°C and 180 rpm. After 24 h of incubation, the minerals were collected and washed with H2SO4 and deionized water to remove residual impurities from the mineral surface. The minerals were then freeze-dried for 24 h, ground through a 100-mesh sieve, and stored in a cool, dry place for later use. The resulting mineral is Schöndorfite.

[0038] (2) Synthesis of lanthanum-containing Schiele mineral materials by coprecipitation method:

[0039] Weigh out the Schiele mineral and add it to a 6.0 mol / L NaOH solution. Add 0.2 mol / L NaCl3 while stirring magnetically at 90℃, and continue stirring magnetically at high temperature for 6 h. Then age at room temperature for 12 h. Wash the precipitate with pure water by centrifugation until neutral, and dry it at 60℃ for 12 h. Grind it in an agate mortar and pass it through a 200-mesh sieve to obtain the lanthanum-containing Schiele mineral.

[0040] Preferably, the pH of the H2SO4 solution is 2.5.

[0041] Optionally, the washing with H2SO4 and deionized water should be performed more than three times.

[0042] The present invention will be further described in detail below with reference to specific embodiments. It should be noted that the specific embodiments are explanations of the present invention and not limitations thereof.

[0043] Example 1: A method for preparing a lanthanum-containing Schiele mineral material, as detailed below:

[0044] (1) Chemical preparation of Schiele mineral

[0045] Dissolve 6.67 g of FeSO4·7H2O in 150 mL of deionized water, add 1.8 mL of H2O2 (30%), mix well, and place in a 250 mL Erlenmeyer flask. Seal the flask with 8 layers of gauze and place it in a constant temperature shaker at 28℃ and 180 rpm for incubation. After 24 h of incubation, collect the minerals through a 0.45 μm filter membrane. Wash the minerals three times with H2SO4 (pH approximately 2.50) and three times with deionized water to remove residual impurities on the mineral surface. Freeze-dry the minerals in a freeze dryer for 24 h, grind them through a 100-mesh sieve, and store them in a dry, cool place for later use. The obtained minerals are Schöndorfite.

[0046] (2) Preparation of Lanthanum-Containing Schiele Minerals by Coprecipitation Method

[0047] 2.0 g of Schiele mineral was weighed and added to 100 mL of 6.0 mol / L NaOH solution. 3.6 mL of 0.2 mol / L LaCl3 was added under magnetic stirring at 90 °C. The mixture was then stirred under magnetic stirring at high temperature for 6 h and aged at room temperature for 12 h. The precipitate was washed with pure water by centrifugation (6000 r / min, 10 min) until neutral and dried at 60 °C for 12 h. The precipitate was then ground in an agate mortar and passed through a 200-mesh sieve to obtain lanthanum-containing Schiele mineral.

[0048] Example 2: A method for preparing a lanthanum-containing Schiele mineral material, as detailed below:

[0049] (1) Chemical preparation of Schiele mineral

[0050] The preparation method is the same as step (1) in Example 1.

[0051] (2) Preparation of Lanthanum-Containing Schiele Minerals by Coprecipitation Method

[0052] The preparation method is basically the same as step (2) in Example 1, except that the amount of 0.2 mol / L LaCl3 added is 7.2 mL.

[0053] Example 3: A method for preparing a lanthanum-containing Schiele mineral material, as detailed below:

[0054] (1) Chemical preparation of Schiele mineral

[0055] The preparation method is the same as step (1) in Example 1.

[0056] (2) Preparation of Lanthanum-Containing Schiele Minerals by Coprecipitation Method

[0057] The preparation method is basically the same as step (2) in Example 1, except that the amount of 0.2 mol / L LaCl3 added is 14.4 mL.

[0058] Example 4: A method for preparing a lanthanum-containing Schiele mineral material, as detailed below:

[0059] (1) Chemical preparation of Schiele mineral

[0060] The preparation method is the same as step (1) in Example 1.

[0061] (2) Preparation of Lanthanum-Containing Schiele Minerals by Coprecipitation Method

[0062] The preparation method is basically the same as step (2) in Example 1, except that the amount of 0.2 mol / L LaCl3 added is 28.8 mL.

[0063] Comparative Example 1: A method for preparing a Schiele mineral material, as detailed below:

[0064] The preparation method is the same as step (1) in Example 1.

[0065] Comparative Example 2: A method for preparing a Schiele mineral material, as detailed below:

[0066] (1) Chemical preparation of Schiele mineral

[0067] The preparation method is the same as step (1) in Example 1.

[0068] (2) Preparation of Schiele mineral materials by coprecipitation method

[0069] The preparation method is basically the same as step (2) in Example 1, except that the amount of 0.2 mol / L LaCl3 added is 0 mL.

[0070] Comparative Example 3

[0071] The difference from Example 1 is that an equimolar amount of zinc oxide is used instead of LaCl3. The specific preparation method is as follows:

[0072] Zinc oxide / Schätländer mineral: Weigh zinc acetate dihydrate into a 500 mL Erlenmeyer flask, add 125 mL of ultrapure water, and sonicate to mix thoroughly. Then add Schätländer mineral and stir on a magnetic stirrer for 30 min to ensure complete dispersion of the Schätländer mineral; this is suspension A. Add 1.05 g of NaHCO3 to a beaker and dissolve it in 125 mL of ultrapure water to obtain solution B. Slowly add solution B dropwise to suspension A at a rate of 1 mL / min using a peristaltic pump while continuing to stir. The brown precipitate obtained by filtration through a Buchner funnel is washed three times with anhydrous ethanol, and then three times with ultrapure water. Collect the precipitate, freeze-dry it, calcine it at 200℃ for 5 h, grind it, and sieve it to obtain zinc oxide / Schätländer mineral powder.

[0073] Comparative Example 4

[0074] The difference from Example 1 is that an equimolar amount of molybdenum disulfide is used instead of LaCl3. The specific preparation method is as follows:

[0075] (1) Dissolve molybdenum disulfide powder in an ethanol solution and then sonicate to obtain a well-dispersed molybdenum disulfide solution;

[0076] (2) FeSO4·7H2O was dissolved in 0.5 L of molybdenum disulfide solution, and then the pH of the solution was adjusted to 2.5 with 0.5 mol / L sulfuric acid. After adding 6 mL of hydrogen peroxide (30 wt%), the mixture was shaken at 180 rpm for 24 hours. The precipitate was then filtered through a 0.45 µm membrane and washed four times with dilute sulfuric acid (pH 2.0) and deionized water. Finally, the product was collected after vacuum drying at 60°C for 24 hours.

[0077] Experimental Example 1

[0078] The lanthanum-containing Schiele mineral material prepared in Example 1 was characterized, and the scanning electron microscope image is shown below. Figure 1 As shown, the energy spectrum is as follows Figure 2 As shown in the specific surface area diagram Figure 3 As shown.

[0079] 0.05 g of samples prepared in Examples 1-4 and Comparative Examples 1 and 2 were placed in water containing 50 mL of doxycycline (20 mg / L) and treated for 120 min under stirring. The doxycycline content in the water was tested, and the removal rate was calculated. The results are as follows: Figure 4 As shown.

[0080] As can be seen from the comparison between Example 1 and Comparative Examples 1 and 2, the addition of lanthanum effectively improved the removal effect of Schiele mineral-based materials on doxycycline.

[0081] As can be seen from the comparison between Example 1 and Comparative Examples 3 and 4, compared with elements such as zinc and molybdenum, the doxycycline removal effect of the Scheres mineral-based material prepared by using lanthanum as the modifying element is better.

[0082] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a lanthanum-containing Schielich mineral material, characterized in that, include: The Schiele mineral was added to an alkaline solution, followed by the addition of La salt. The mixture was then reacted, aged, and the precipitate was collected, washed, dried, and ground to obtain lanthanum-containing Schiele mineral material. The mass ratio of the Schiele mineral to the La salt is (1-2):(0.147-1.47). The reaction temperature is 90℃-95℃; The reaction time is 6-8 hours; The alkaline solution is a NaOH solution with a concentration of 6.0-8.0 mol / L; The preparation method of the Schiele mineral includes: mixing FeSO4·7H2O and H2O2 evenly in water, culturing under certain conditions, and collecting the minerals in the system after culturing is completed; The minerals in the system are washed with H2SO4 and water, freeze-dried, and sieved to obtain the final product.

2. The method for preparing lanthanum-containing Schieli mineral material as described in claim 1, characterized in that, The La salt is LaCl3.

3. The method for preparing lanthanum-containing Schieli mineral materials as described in claim 1, characterized in that, The aging time is 12-16 hours.

4. Lanthanum-containing Schiele mineral materials prepared by the method according to any one of claims 1-3.

5. The application of the lanthanum-containing Schiele mineral material according to claim 4 in the treatment of antibiotic wastewater.

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