Preparation of lanthanum-containing Schwertmannite material and application of lanthanum-containing Schwertmannite material in antibiotic wastewater treatment

Abstract

The invention belongs to the field of materials and water treatment, and provides preparation of a lanthanum-containing Schwertmannite material and application of the lanthanum-containing Schwertmannite material in antibiotic wastewater treatment.The preparation method comprises the steps that Schwertmannite is added into an alkali solution, La salt is added, and the lanthanum-containing Schwertmannite material is obtained through reaction, aging, sediment collection, washing, drying and grinding; the mass ratio of the Schwertmannite to the La salt is (1-2): (0.147-1.47). The lanthanum-containing Schwertmannite material can rapidly remove antibiotic residues in water, the preparation method is simple, the cost is low, the used raw materials are wide in source, and the lanthanum-containing Schwertmannite material has good application prospects. The material does not generate secondary pollution in the process of treating environmental pollutants, and is environment-friendly. Under the condition of no external energy input, the lanthanum-containing Schwertmannite material provided by the invention can remove more than 90% of doxycycline, and is obviously superior to the Schwertmannite synthesized by a common chemical method.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of materials and water treatment, and relates to preparation of a lanthanum-containing schwertmannite material and application of the lanthanum-containing schwertmannite material in antibiotic wastewater treatment. BACKGROUND

[0002] The information disclosed in this BACKGROUND section is only for the purpose of increasing the understanding of the general background of the present application and should not be taken as an acknowledgement or any form of suggestion that this information forms prior art that is already known to a person of ordinary skill in the art.

[0003] In recent years, with the wide application of antibiotics, the residues of antibiotics not only destroy the microbial community structure and affect the balance of the water ecosystem, but also further threaten human health and public health safety. In some intensive breeding areas, the concentration of antibiotics in water bodies has reached the level of μg / L or even mg / L. Long-term exposure to such an environment inhibits the growth and reproduction of aquatic organisms, and the food chain is at risk of being destroyed.

[0004] Among numerous antibiotic removal materials, schwertmannite has a large specific surface area and rich surface active sites, and has high removal potential and environmental friendliness. However, the natural schwertmannite has defects such as limited adsorption capacity, poor selectivity, and insufficient affinity for antibiotics, which limits its large-scale application in antibiotic wastewater treatment.

[0005] At present, there are studies on the use of lanthanum-modified schwertmannite to remove antibiotics in wastewater, but the removal efficiency still needs to be improved. SUMMARY

[0006] In order to solve the above problems, the present application provides a lanthanum-containing schwertmannite material, which can quickly remove antibiotic residues in water bodies, has a simple preparation method, low cost, and widely available raw materials, and has good application prospects. The material does not produce secondary pollution and is environmentally friendly in the process of treating environmental pollutants. Without external energy input, the lanthanum-containing schwertmannite material provided by the present application can remove more than 90% of doxycycline, which is significantly better than ordinary chemically synthesized schwertmannite.

[0007] In order to achieve the above purpose, the present application adopts the following technical solutions: The first aspect of the present application provides a preparation method of a lanthanum-containing schwertmannite material, comprising: adding the schwertmannite into an alkali solution, then adding a La salt, and performing reaction, aging, collecting precipitate, washing, drying, and grinding to obtain the lanthanum-containing schwertmannite material; The mass ratio of the schwertmannite to the La salt is (1-2):(0.147-1.47).

[0008] The present application focuses on the adsorption removal of antibiotics by lanthanum-modified scherrerite, optimizes the material preparation and adsorption process, aims to provide theoretical basis and technical support for solving the problem of antibiotic wastewater pollution, helps the ecological restoration and protection of water environment, and promotes the innovative development of adsorption materials in the field of water pollution control.

[0009] In a second aspect, the present application provides a lanthanum-containing scherrerite material prepared by the above method.

[0010] In a third aspect, the present application provides the use of the above lanthanum-containing scherrerite material in antibiotic wastewater treatment.

[0011] Advantages of the present application (1) The present application discloses a lanthanum-containing scherrerite material, which can quickly remove antibiotic residues in water, has a simple preparation method, low cost, and widely available raw materials, and has good application prospects. The material does not produce secondary pollution in the process of treating environmental pollutants, and is friendly to the environment. Without external energy input, the lanthanum-containing scherrerite material provided by the present application can remove more than 90% of doxycycline (20 mg / L), which is significantly better than ordinary chemical synthesis of scherrerite.

[0012] (2) The preparation method of the present application is simple, practical and easy to popularize. DETAILED DESCRIPTION

[0013] The accompanying drawings, which form a part of this application, are included to provide a further understanding of the application, and are incorporated in and constitute a part of this application. The embodiments of the present application and their description are used to explain the present application, and do not constitute an improper limitation of the present application.

[0014] Figure 1 The scanning electron microscope image of the lanthanum-containing scherrerite material provided for the embodiments of the present application.

[0015] Figure 2 The energy spectrum diagram of the lanthanum-containing scherrerite material provided for the embodiments of the present application.

[0016] Figure 3 The specific surface area graph of the lanthanum-containing scherrerite material provided for the embodiments of the present application.

[0017] Figure 4 The doxycycline removal graph of the comparative example and the example provided for the embodiments of the present application. DETAILED DESCRIPTION

[0018] It should be pointed out that the following detailed description is exemplary, and is intended to provide further explanation of the present application. Unless otherwise specified, all technical and scientific terms used in the present application have the same meaning as generally understood by those skilled in the art to which the present application belongs.

[0019] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The materials used to practice the present application are those that are currently in use, and are available from commercial vendors such as are commonly used and are widely available to those skilled in the art, unless otherwise indicated. Similarly, the methods used to practice the present application are those generally used and practiced in the art, unless otherwise indicated. Also, any method and material similar or equivalent to those described herein can be used in the practice of the present application. The methods and materials described herein are illustrative only and not intended to be limiting.

[0020] The present application provides a preparation method of lanthanum-containing schlegelite material, comprising: adding the schlegelite into an alkali solution, adding a La salt, performing a reaction, aging, collecting a precipitate, washing, drying, and grinding to obtain the lanthanum-containing schlegelite material; The amount of the schlegelite and the La salt will affect the adsorption effect, and therefore, the mass ratio of the schlegelite and the La salt is studied in the present application. In some embodiments, the mass ratio of the schlegelite and the La salt is (1-2):(0.147-1.47), and a more optimal antibiotic removal effect has been obtained. Preferably, the amount of 0.2 mol / L LaCl3 added is 3-30 mL.

[0021] The kind of the La salt is not particularly limited in the present application, as long as it can be uniformly dispersed in the alkali solution. In some embodiments, the La salt is LaCl3, which has high purity and a simple preparation method.

[0022] The reaction temperature will affect the reaction rate and yield of the schlegelite and the La salt, and therefore, the temperature of the reaction is studied in the present application. In some embodiments, the temperature of the reaction is 90-95℃, so as to improve the reaction rate and yield of the schlegelite and the La salt.

[0023] If the reaction time is too short, the reaction of the schlegelite and the La salt is not complete, and if the reaction time is too long, side reactions are prone to occur. Therefore, the reaction time is studied in the present application. In some embodiments, the reaction time is 6-8h, so as to improve the reaction efficiency.

[0024] The type of the alkali solution is not particularly limited in the present application, as long as it can provide an alkaline environment for the reaction. In some embodiments, the alkali solution is a NaOH solution, and the concentration is 6.0-8.0 mol / L, so as to provide an alkaline environment for the reaction of the schlegelite and the La salt.

[0025] The aging time can affect the product of the co-precipitation process, and therefore, the aging time is studied in some embodiments, and the aging time is 12-16 h to prepare the lanthanum-containing schiessite material by co-precipitation.

[0026] The speed and time of centrifugation can affect the separation effect of the precipitate, and therefore, the speed and time of centrifugation are studied in some embodiments, and the centrifugation conditions are 5000-6000 rpm for 8-10 min to improve the separation efficiency of the precipitate.

[0027] The preparation method of the schiessite is optimized to improve the yield and purity of the schiessite. In some embodiments, the preparation method of the schiessite comprises: uniformly mixing FeSO4·7H2O and H2O2 in water, culturing under certain conditions, and collecting the system mineral after the culturing is completed.

[0028] The system mineral is washed with H2SO4 and water, freeze-dried, and sieved to obtain the schiessite. The acid washing can effectively remove the impurities loaded on the mineral and improve the purity of the schiessite.

[0029] More specifically, it comprises: (1) Synthesis of schiessite by chemical method: FeSO4·7H2O is dissolved in deionized water, H2O2 (30%) is added and uniformly mixed, and then placed in a 250 mL triangular flask, and then placed in a constant temperature shaker, and cultured at a temperature of 28°C and a speed of 180 rpm. After culturing for 24 h, the system mineral is collected, and the mineral is washed with H2SO4 and deionized water to remove residual impurity ions on the surface of the mineral. The mineral is freeze-dried in a freeze dryer for 24 h, ground through a 100 mesh sieve, and stored in a dry and cool place for standby. The obtained mineral is the schiessite.

[0030] (2) Synthesis of lanthanum-containing schiessite material by co-precipitation method: Schiessite is weighed and added to a 6.0 mol / L NaOH solution, 0.2 mol / L LaCl3 is added under magnetic stirring at 90°C, and high-temperature magnetic stirring is continued for 6 h, and then room temperature aging is performed for 12 h; the precipitate is washed with pure water by centrifugation until it is neutral, and is dried at 60°C for 12 h; it is ground in a maroon mortar and sieved through a 200 mesh sieve to obtain the lanthanum-containing schiessite.

[0031] Preferably, the pH of the H2SO4 solution is 2.5.

[0032] Alternatively, the washing with H2SO4 and deionized water should be more than 3 times.

[0033] The application will be further described in detail below with specific examples. It should be pointed out that the specific examples are an explanation of the application rather than a limitation.

[0034] Example 1: A preparation method of a lanthanum-containing schiessite material, specifically as follows: (1) Preparation of schiessite by chemical method Dissolve 6.67 g of FeSO4·7H2O in 150 mL of deionized water, add 1.8 mL of H2O2 (30%) and mix uniformly, then place in a 250 mL triangular flask, seal with 8 layers of gauze, and then place in a constant temperature shaker at a temperature of 28°C and a rotation speed of 180 rpm. After 24 h of culture, collect the minerals in the system with a 0.45 μm filter membrane, and wash the minerals with H2SO4 with a pH of about 2.50 for 3 times, and then wash with deionized water for 3 times to remove the impurity ions remaining on the surface of the minerals. After freeze-drying the minerals in a freeze dryer for 24 h, grind through a 100 mesh sieve, and store in a dry and cool place for standby. The obtained minerals are schiessite.

[0035] (2) Preparation of lanthanum-containing schiessite material by coprecipitation method Add 2.0 g of schiessite to 100 mL of 6.0 mol / L NaOH solution, and add 3.6 mL of 0.2 mol / L LaCl3 under magnetic stirring at 90°C, continue high-temperature magnetic stirring for 6 h, and then room temperature aging for 12 h; the precipitate is washed to neutral by centrifugation (6000 r / min, 10 min) with pure water, and dried at 60°C for 12 h; grind with an agate mortar and sieve through a 200 mesh sieve to obtain a lanthanum-containing schiessite.

[0036] Example 2: A preparation method of a lanthanum-containing schiessite material, specifically as follows: (1) Preparation of schiessite by chemical method The preparation method is the same as step (1) in Example 1.

[0037] (2) Preparation of lanthanum-containing schiessite material by coprecipitation method The preparation method is basically the same as step (2) in Example 1, except that the addition amount of 0.2 mol / L LaCl3 is 7.2 mL.

[0038] Example 3: A preparation method of a lanthanum-containing schiessite material, specifically as follows: (1) Preparation of schiessite by chemical method The preparation method is the same as step (1) in Example 1.

[0039] (2) Preparation of lanthanum-containing schiessite material by coprecipitation method 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.

[0040] Example 4: A preparation method of a lanthanum-containing schiessite material, specifically as follows: (1) Preparation of schiessite by chemical method The preparation method is the same as step (1) in Example 1.

[0041] (2) Preparation of lanthanum-containing schiessite material by coprecipitation method 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.

[0042] Comparative Example 1: A preparation method of a schiessite material, specifically as follows: The preparation method is the same as step (1) in Example 1.

[0043] Comparative Example 2: A preparation method of a schiessite material, specifically as follows: (1) Preparation of schiessite by chemical method The preparation method is the same as step (1) in Example 1.

[0044] (2) Preparation of schiessite material by coprecipitation method 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.

[0045] Comparative Example 3 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: Zinc oxide / schiessite: Take zinc acetate dihydrate in a 500 mL conical flask, add 125 mL of ultrapure water, ultrasonically mix uniformly, then add schiessite, and place it on a magnetic stirrer for stirring for 30 min to make the schiessite completely dispersed, which is a suspension A. In a beaker, add 1.05 g of NaHCO3, dissolve with 125 mL of ultrapure water to obtain solution B. Slowly drop solution B into suspension A at a rate of 1 mL / min through a peristaltic pump while continuing to stir. The brownish red precipitate filtered through a Buchner funnel is washed with anhydrous ethanol three times and then with ultrapure water three times. Collect the precipitate, freeze-dry, and calcine at 200°C for 5 h, grind, and sieve to obtain zinc oxide / schiessite powder.

[0046] Comparative Example 4 The difference from Example 1 is that equimolar amount of molybdenum disulfide is used to replace LaCl3. The specific preparation method is as follows: (1) Dissolve molybdenum disulfide powder in ethanol solution, and obtain a molybdenum disulfide solution with good dispersibility by ultrasonic treatment; (2) Dissolve FeSO4·7H2O in 0.5 L of the molybdenum disulfide solution, and then adjust the pH of the solution to 2.5 with 0.5 mol / L sulfuric acid. After adding 6 mL of hydrogen peroxide (30 wt%), the mixed solution is continuously oscillated at a speed of 180 rpm for 24 hours. Then, the precipitate formed is filtered with a 0.45 µm membrane, and washed with dilute sulfuric acid (pH 2.0) and deionized water for 4 times. Finally, the obtained product is collected after vacuum drying at 60°C for 24 hours.

[0047] Experimental Example 1 The lanthanum-scheelite-containing material prepared in Example 1 is characterized, and the scanning electron microscope image is as shown in Figure 1 , the energy spectrum diagram is as shown in Figure 2 , and the specific surface area diagram is as shown in Figure 3 .

[0048] 0.05 g of the samples prepared in Examples 1-4 and Comparative Examples 1 and 2 are respectively placed in 50 mL of doxycycline (20 mg / L) containing water, and treated under stirring conditions for 120 min. The content of doxycycline in the water is tested, and the removal rate is calculated. The results are as shown in Figure 4 .

[0049] From the comparison of Example 1 with Comparative Examples 1 and 2, it can be seen that the addition of lanthanum element effectively improves the doxycycline removal effect of the scheelite-based material.

[0050] From the comparison of Example 1 with Comparative Examples 3 and 4, it can be seen that compared with zinc and molybdenum elements, the doxycycline removal effect of the scheelite-based material prepared by using lanthanum as a modification element is better.

[0051] The above only describes the preferred embodiments of the present application and is not used to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for producing a lanthanum schiessite-containing material, characterized in that, The method comprises the following steps: The lanthanum-containing schulteite material is prepared by adding schulteite into an alkali solution, adding a La salt, reacting, aging, collecting precipitate, washing, drying and grinding. The mass ratio of the schulteite to the La salt is (1-2):(0.147-1.47).

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 reaction temperature is 90-95 DEG C.

4. The method for preparing lanthanum-containing Schieli mineral material as described in claim 1, characterized in that, The reaction time is 6-8 h.

5. The method for preparing lanthanum-containing Schielich mineral material as described in claim 1, characterized in that, The alkali solution is NaOH solution with a concentration of 6.0-8.0 mol / L.

6. The method for preparing lanthanum-containing Schieli mineral material as described in claim 1, characterized in that, The aging time is 12-16 h.

7. The method for preparing lanthanum-containing Schieli mineral material as described in claim 1, characterized in that, The centrifugation condition is 5000-6000 rpm for 8-10 min.

8. The method for preparing lanthanum-containing Schieli mineral material as described in claim 1, characterized in that, The preparation method of the schulteite comprises the following steps: uniformly mixing FeSO4·7H2O and H2O2 in water, culturing under certain conditions, and collecting the system mineral after the culturing is completed. The system mineral is washed with H2SO4 and water, freeze-dried and sieved. 9.The lanthanum-containing schulteite material prepared by the method in any one of claims 1-8. 10.The application of the lanthanum-containing schulteite material in claim 9 in antibiotic wastewater treatment.

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