Basalt modified material as well as preparation method and application thereof

Abstract

The invention relates to a basalt modified material and a preparation method and application thereof, and belongs to the field of basalt modified materials, the basalt modified material provided by the invention is simple in preparation method, the material is easy to obtain, manganese dioxide is loaded on the basalt material in a tetragonal crystal system structure, alpha-MnO2 crystal system structure characteristic peaks exist at the positions of 2theta = 28.7 degrees, 32.06 degrees, 37.5 degrees, 42.18 degrees, 49.86 degrees and 60.27 degrees, and the characteristic peaks of the alpha-MnO2 crystal system structure characteristic peaks exist at the positions of 2theta = 28.7 degrees, 32.06 degrees, 37.5 degrees, 42.18 degrees, 49.86 degrees and 60.27 degrees. Manganese dioxide is loaded on a basalt material in a tetragonal system structure, and the obtained basalt modified material has good physical adsorption and chemical adsorption performance on tetracycline, is low in price, and has good industrial application value as a tetracycline adsorbent.

Description

Technical Field

[0001] This invention belongs to the field of basalt modified materials, specifically, it relates to a basalt modified material, its preparation method and application. Background Technology

[0002] Basalt is highly durable, with numerous joints, many of which are hexagonal, and it is brittle, making it difficult to mine large blocks. The degree of crystallization and grain size of basalt mainly depend on the cooling rate of the magma. Under normal surface conditions, basalt is primarily fine-grained to cryptocrystalline or glassy, ​​with a few examples being medium-grained. It often contains phenocrysts of olivine, pyroxene, and plagioclase, forming a porphyritic texture. The chemical composition of basalt is similar to that of gabbro, mainly consisting of silicon dioxide, aluminum oxide, iron oxide, calcium oxide, and magnesium oxide (with small amounts of potassium oxide and sodium oxide), with SiO2 being the most abundant, generally between 45% and 52%. Its mineral composition is mainly composed of basic feldspar and pyroxene, with minor minerals including olivine, amphibole, and biotite. Basalt is characterized by high compressive strength, low crushing value, wear resistance, low water absorption, weak electrical conductivity, and strong corrosion resistance. Furthermore, porous basalt, also known as pumice, is characterized by its numerous pores and hard texture. Basalt materials possess a rich porous structure, and its chemically inert framework (SiO2 / Al2O3 content > 80%) maintains structural stability during acid washing / alkali etching. Dazhou, Sichuan Province, possesses abundant basalt mineral resources, providing a unique resource advantage for the development of the basalt fiber industry. Dazhou is focusing on cultivating a new materials industry featuring basalt fiber and has formulated clear development goals.

[0003] Tetracycline, as an antibiotic, is widely used in the medical industry. However, tetracycline residues in the environment can cause toxicity to aquatic organisms when they enter water bodies, potentially affecting the growth and reproduction of algae, zooplankton, and fish. When it enters the soil, it can inhibit the activity of soil microorganisms, affecting soil fertility and ecological functions. Furthermore, tetracycline in the soil can be absorbed by plants, leading to antibiotic residues in plants. This not only affects plant growth but may also pose a potential threat to human health through the food chain.

[0004] Currently, the main methods for treating tetracycline include biological treatment, adsorption, and advanced oxidation. Biological treatment degrades tetracycline through anaerobic and aerobic reactions, but tetracycline has an inhibitory effect on microorganisms, so it is necessary to screen for tolerant strains. Adsorption has the problem of high cost of adsorbents. Advanced oxidation has a fast reaction rate and good treatment effect, but it also has problems such as high cost and difficulty in recovering catalysts. Summary of the Invention

[0005] To overcome the problems existing in the background technology, the present invention provides a basalt modified material, its preparation method and application. The provided basalt modified material has manganese dioxide mounted on basalt material in a tetragonal crystal system structure, and has characteristic peaks of α-MnO2 crystal system structure at 2θ = 28.7°, 32.06°, 37.5°, 42.18°, 49.86°, and 60.27°. The basalt modified material obtained by mounting manganese dioxide on basalt material in a tetragonal crystal system structure has good physical and chemical adsorption performance for tetracycline.

[0006] The first objective of this invention is to provide a basalt-modified material in which manganese dioxide is mounted on basalt material in a tetragonal crystal system and has characteristic peaks of α-MnO2 crystal system at 2θ = 28.7°, 32.06°, 37.5°, 42.18°, 49.86°, and 60.27°.

[0007] The second objective of this invention is to provide the application of basalt-modified materials in the treatment of tetracycline wastewater.

[0008] A third objective of this invention is to provide the application of basalt-modified materials in the adsorption of tetracycline.

[0009] The adsorption further includes chemisorption and physisorption.

[0010] The fourth objective of this invention is to provide a method for preparing basalt-modified materials, which involves reacting basalt ore powder, manganese chloride, and potassium permanganate to obtain the material.

[0011] Furthermore, the preparation method includes the following steps:

[0012] (1) Crush the basalt and add it to distilled water, and add manganese chloride to dissolve it completely;

[0013] (2) With Mn 2+ :MnO4 - The molar ratio is 3:2, and potassium permanganate solution is added dropwise continuously under stirring conditions;

[0014] (3) Liquid-solid separation, washing, and obtaining filter cake;

[0015] (4) The basalt modified material is obtained after the filter cake is dried.

[0016] Furthermore, the application of the prepared basalt-modified material in the adsorption of tetracycline.

[0017] This invention also protects basalt-modified materials obtained by the above preparation method.

[0018] The beneficial effects of this invention are:

[0019] The basalt-modified material of the present invention has a good adsorption effect on tetracycline, and the highest adsorption rate of tetracycline can reach more than 88.05%.

[0020] The basalt-modified material prepared by this invention has characteristic peaks at 2θ = 28.7°, 32.06°, 37.5°, 42.18°, 49.86°, and 60.27°. Manganese dioxide is mounted on the basalt material in a tetragonal crystal system and has both physical and chemical adsorption effects on tetracycline.

[0021] The basalt adsorbent material of the present invention uses basalt as a matrix, which is readily available and inexpensive. When used as a tetracycline adsorbent, it can greatly reduce the cost of tetracycline adsorbent materials and has good industrial application value. Attached Figure Description

[0022] Figure 1 This is the infrared spectrum of basalt and basalt-modified materials of Embodiment 1 of the present invention;

[0023] Figure 2 This is the XRD pattern of basalt and basalt-modified materials in Example 1 of the present invention;

[0024] Figure 3 This is a SEM image of the basalt and basalt-modified materials of this invention;

[0025] Figure 4 This is the fitting curve (time versus adsorption amount) of the pseudo-first-order kinetic model in Embodiment 2 of the present invention;

[0026] Figure 5 This is the fitting curve (time versus adsorption amount) of the pseudo-second-order kinetic model in Embodiment 2 of the present invention;

[0027] Figure 6 This is the adsorption of tetracycline by basalt modified materials with different manganese dioxide loadings in Example 2 of the present invention.

[0028] Figure 7 It is the standard curve of tetracycline hydrochloride. Detailed Implementation

[0029] To make the objectives, technical solutions, and beneficial effects of this invention clearer, the technical solutions of this invention will be described in detail below. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are all within the scope of protection of this invention.

[0030] To illustrate the present invention more clearly, the following embodiments will be described in detail.

[0031] Example 1

[0032] Preparation of basalt modified materials

[0033] Different masses of basalt ore powder and manganese chloride were weighed into 100 mL beakers, and distilled water was added to dissolve the manganese chloride; then, the process was carried out according to the Mn standard. 2+ :MnO4 - The stoichiometric molar ratio of the basalt powder and manganese chloride was 3:2. Potassium permanganate solution was added dropwise to the mixed solution of basalt powder and manganese chloride under constant stirring. After the addition was completed, the mixture was allowed to stand for a period of time, the supernatant was poured off, and the mixture was filtered. The filter cake was washed three times with distilled water and anhydrous ethanol. The washed filter cake was dried in an oven at 60°C for 6 hours to obtain basalt modified materials with different manganese dioxide loadings.

[0034] Infrared spectra of the obtained basalt and basalt-modified materials (attached) Figure 1 The main functional groups of basalt and basalt-modified materials are mainly -OH (3443cm). -1 ), C=O / C=C(1630cm) -1 ), CO (1014cm) -1 Mn-O (551cm) -1 ) and Mn-O-Mn(700cm) -1 The adsorption bands of BF (basalt) and Mn-BF (basalt-modified material loaded with manganese dioxide) are similar, with a band at 3433 cm⁻¹. -1 A relatively wide adsorption band was observed at 1630 cm⁻¹. -1 The adsorption bands at 551 cm⁻¹ are related to the tensile and bending vibrations of hydroxyl groups or -OH groups in the adsorbed water, respectively, indicating that both materials contain a large amount of phenols, alcohols, carboxylic acids, and other substances, as well as lattice oxygen or a small amount of water molecules. In the low-frequency region at 551 cm⁻¹... -1 The nearby absorption peaks indicate Mn-O bonds, suggesting that the Mn-BF spectrum is at 551 cm⁻¹. -1 The presence of Mn-O asymmetric stretching nearby indicates that MnO2 was loaded onto the surface of the basalt material.

[0035] XRD patterns of the obtained basalt and basalt-modified materials (attached) Figure 2The XRD pattern shows that the diffraction peaks of the basalt material at 2θ = 28.13°, 42.38°, 43.69°, and 59.17° are (040), (101), (210), and (202) crystal plane diffraction peaks, respectively. The basalt matrix material is mainly composed of plagioclase. The diffraction peaks of the manganese dioxide-loaded basalt modified material at 2θ = 28.7°, 32.06°, 37.5°, 42.18°, 49.86°, and 60.27° are (220), (310), (211), (301), (411), and (521) crystal plane diffraction peaks, respectively. The XRD pattern shows that the preparation method of the present invention, the manganese dioxide-loaded basalt modified material, has manganese dioxide mounted on the basalt material in a tetragonal crystal system.

[0036] SEM (with attachment) Figure 3 The results show that the basalt substrate particles are irregular in shape, have a layered structure, and have an uneven surface (Fig. a and Fig. b); the basalt modified material loaded with manganese dioxide retains the original shape of the basalt substrate particles and has granular MnO2 loaded on its surface (Fig. c and Fig. d, c and d are basalt modified materials with a loading of 100 mg / g).

[0037] Example 2

[0038] Application of basalt modified materials

[0039] Tetracycline was adsorbed using the basalt-modified material with a manganese dioxide loading of 100 mg / g as described in Example 1:

[0040] When the solid-liquid ratio of the basalt-modified material was 0.5 g / L and the initial concentration was 150 mg / L, the manganese dioxide-modified basalt-based material was subjected to tetracycline hydrochloride adsorption experiments at 293 K, 303 K, 313 K, and 323 K. The experimental data were fitted using pseudo-first-order kinetic equations (Equation 1) and pseudo-second-order kinetic equations (Equation 2), and the fitting results are shown in Table 1. The fitting relationship between time and adsorption rate is as follows: Figure 4 , Figure 5 As shown.

[0041] ln(Q 1e -Q t )=lnQ 1e -k1t Equation (1)

[0042]

[0043] In equations (1) and (2): Q e Qt represents the adsorption amount at adsorption equilibrium (mg / g); Qt represents the adsorption amount at time t (mg / g); k1 and k2 are the pseudo-first-order rate constants (min). -1), pseudo-second-order rate constant (g / (mg·min)).

[0044] As shown in Table 1, comparing the fitting results of the pseudo-first-order kinetic model and the pseudo-second-order kinetic model for the adsorption kinetics of TC on modified basalt-based materials at four different ambient temperatures (293K, 303K, 308K, and 313K), it can be clearly observed that the R1 of the pseudo-first-order kinetic model is lower at 293K. 2 The coefficient (0.93166) is lower than the R-value of the pseudo-second-order dynamics model. 2 The coefficient (0.95741) indicates that the adsorption process of the modified basalt-based material on TC at room temperature better conforms to the characteristics of the pseudo-second-order kinetic model, and the adsorption process includes both physical and chemical adsorption. As the temperature increases, the R0 of the pseudo-first-order kinetic model... 2 The coefficients (0.93934, 0.92526, and 0.92578, respectively) are significantly higher than those of the pseudo-second-order dynamic model R. 2 The coefficients (0.89636, 0.86642, and 0.80916, respectively) indicate that physical adsorption is also involved in this process. Therefore, the adsorption of TC in the modified basalt-based material is more consistent with the pseudo-first-order kinetic model, indicating that physical adsorption and chemical adsorption occur simultaneously.

[0045] Table 1. Fitting parameters for the adsorption kinetic model of manganese dioxide modified basalt-based materials. (Pseudo-first-order kinetic model)

[0046] Temperature / K <![CDATA[Q e / (mg / g)]]> <![CDATA[Q 1e / (mg / g)]]> <![CDATA[k1 / (min -1 )]]> <![CDATA[R 2 ]]> 293 172.793 114.435 <![CDATA[5.72×10 -3 ]]> 0.93166 303 219.791 201.714 <![CDATA[6.96×10 -3 ]]> 0.93934 313 229.712 198.02 <![CDATA[4.81×10 -3 ]]> 0.92526 323 233.890 217.07 <![CDATA[6.37×10 -3 ]]> 0.92578

[0047] Table 2. Fitting parameters for the adsorption kinetic model of manganese dioxide modified basalt-based materials (continued) (Pseudo-second-order kinetics)

[0048] Temperature / K <![CDATA[Q e / (mg / g)]]> <![CDATA[Q 2e / (mg / g)]]> <![CDATA[k2 / (g / (mg·min))]]> <![CDATA[R 2 ]]> 293 172.793 171.2328 <![CDATA[1.3×10 -3 ]]> 0.95741 303 219.791 235.2941 <![CDATA[4.9×10 -3 ]]> 0.89636 313 229.712 221.7294 <![CDATA[5.31×10 -3 ]]> 0.86642 323 233.890 257.7319 <![CDATA[3.68×10 -3 ]]> 0.80916

[0049] Comparison of the adsorption capacity of tetracycline for basalt-modified materials with different manganese dioxide loadings:

[0050] In Example 1, Mn-BF with manganese dioxide loadings of 25 mg / g, 50 mg / g, and 100 mg / g were used for tetracycline adsorption, with unloaded basalt substrate serving as a blank control. The initial tetracycline concentration was 150 mg / L, the adsorption time was 180 min, and the adsorption temperature was 313 K. The results showed that compared to the 25% tetracycline adsorption rate of unloaded basalt powder, the adsorption rate of tetracycline hydrochloride by Mn-BF with a loading of 25 mg / g increased to 40.2%; when the manganese dioxide loading increased to 100 mg / g, the adsorption rate of tetracycline hydrochloride by Mn-BF increased to 79.53%. With increasing manganese dioxide loading, the adsorption capacity of Mn-BF for tetracycline hydrochloride also increased (see Appendix). Figure 6 , Figure 6In the text, a, b, c, and d represent basalt powder, basalt modified material with a manganese dioxide loading of 100 mg / g, basalt modified material with a manganese dioxide loading of 50 mg / g, and basalt modified material with a manganese dioxide loading of 25 mg / g, respectively.

[0051] SEM images of basalt-modified material after tetracycline adsorption by Mn-BF with a manganese dioxide loading of 100 mg / g are attached. Figure 3 The SEM images of e and f show that the particle aggregation on the surface of the basalt modified material is intensified after tetracycline adsorption. This may be because tetracycline molecules react effectively with the active sites in the basalt modified material, enriching the tetracycline molecules.

[0052] Example 3

[0053] Adsorption of tetracycline by basalt-modified materials

[0054] Adsorption Experiment 1: 0.01 g of basalt-modified material with a manganese dioxide loading of 100 mg / g was weighed and added to 20 mL of tetracycline hydrochloride solution (concentration 100 mg / L, temperature 313 K). After adsorption for 180 min, the adsorption rate was 75.69%.

[0055] Adsorption Experiment 2: 0.01 g of basalt modified material with a manganese dioxide loading of 100 mg / g was weighed and added to 20 mL of tetracycline hydrochloride solution (concentration 150 mg / L, temperature 313 K). After adsorption for 120 min, the adsorption rate was 71.73%.

[0056] Adsorption Experiment 3: 0.01 g of basalt-modified material with a manganese dioxide loading of 100 mg / g was weighed and added to 20 mL of tetracycline hydrochloride solution (concentration 150 mg / L, temperature 313 K). Adsorption was carried out for 240 min, and the adsorption rate was 84.6%.

[0057] Adsorption Experiment 4: Weigh 0.01 g of basalt-modified material with a manganese dioxide loading of 100 mg / g and add it to 20 mL of tetracycline hydrochloride solution (concentration 150 mg / L, temperature 323 K). Adsorption was carried out for 240 min, and the adsorption rate was 88.05%.

[0058] Description of the analytical detection method for the adsorption experiment of this invention:

[0059] (1) Preparation of tetracycline hydrochloride standard solution

[0060] Tetracycline hydrochloride powder was dissolved in deionized water and transferred to a 1000 mL volumetric flask, then diluted to the mark with deionized water. A 1 g / L tetracycline hydrochloride stock solution was prepared and stored in a light-protected environment for later use. A 100 mL volumetric flask was used to dilute the stock solution to prepare standard tetracycline hydrochloride solutions of 5 mg / L, 10.0 mg / L, 15 mg / L, 20 mg / L, and 25 mg / L. Using a UV-Vis spectrophotometer, with deionized water as a blank for calibration, the absorbance of each tetracycline hydrochloride concentration was measured at the maximum absorption wavelength of 356 nm. A standard curve for tetracycline hydrochloride was plotted with different tetracycline hydrochloride solution concentrations on the x-axis and the corresponding absorbance on the y-axis. Figure 7 ).

[0061] according to Figure 6 The calculated equation for the standard curve is shown in Equation 3:

[0062] y = 0.0383x + 0.0064 (Equation 3)

[0063] In the formula: y is the absorbance of tetracycline hydrochloride; x is the concentration of tetracycline hydrochloride. The linear correlation of this equation is R² = 0.9985.

[0064] (2) Adsorption performance test

[0065] The adsorbent was placed in 20 mL of tetracycline hydrochloride solution of a certain concentration and stirred and adsorbed at a certain temperature. After adsorption was completed, it was centrifuged at 3500 r / min for 5 min, the supernatant was poured off, the solution was filtered, and the volume was adjusted. The absorbance at 356 nm was measured. The concentration of the supernatant was calculated according to the standard curve equation (3) of tetracycline hydrochloride solution, and the adsorption capacity Q of the adsorbent was calculated according to equations (4) and (5). t And adsorption rate R.

[0066]

[0067]

[0068] In the formula: Q t R is the amount of tetracycline hydrochloride adsorbed at adsorption time t (mg / g); R is the adsorption rate of tetracycline hydrochloride at adsorption time t; ρ0 is the initial concentration of tetracycline hydrochloride (mg / L); ρ t V represents the concentration of tetracycline hydrochloride solution at adsorption time t (mg / L); V represents the volume of tetracycline hydrochloride solution (L); and m represents the mass of manganese dioxide modified basalt mineral powder adsorbent (g).

[0069] (3) Adsorbent characterization

[0070] Fourier Transform Infrared Spectrometer (FT-IR):

[0071] The structure of the functional groups on the surface of the adsorbent material was analyzed and characterized in the range of λ = 400 to 4000 cm⁻¹ using a FT-IR-850 Fourier transform infrared spectrometer manufactured by Tianjin Gangdong Technology Co., Ltd. and the potassium bromide pellet method.

[0072] X-ray diffraction (XRD):

[0073] The catalyst was characterized using a SmartLab 9kW (Rigaku, Japan) microscope. The scanning range was 2θ = 10°–80°, the measurement speed was 10, and the step size was 0.02°.

[0074] Field emission scanning electron microscopy (SEM) analysis:

[0075] The microstructure and morphology of the samples were examined using a Thermo Scientific scanning electron microscope. The samples were dried before and after adsorption. Approximately 10 mg of the sample was then fixed onto a dedicated sample stage using conductive adhesive. Due to the poor conductivity of the material, it was sputter-coated with gold to enhance conductivity. After being stabilized at the electron microscope mounting position, the sample morphology was observed, and energy dispersive spectroscopy (EDS) mapping was performed.

[0076] Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that various changes can be made to it in form and detail without departing from the scope defined by the claims of the present invention.

Claims

1. A basalt-modified material, characterized in that, Manganese dioxide, in a tetragonal crystal structure, is mounted on basalt material and exhibits characteristic peaks at 2θ: 28.7°, 32.06°, 37.5°, 42.18°, 49.86°, and 60.27°.

2. The application of the basalt-modified material as described in claim 1 in the treatment of tetracycline-containing wastewater.

3. The application of the basalt-modified material as described in claim 1 in the adsorption of tetracycline.

4. The application as described in claim 3, characterized in that, The adsorption includes both chemical adsorption and physical adsorption.

5. A method for preparing a basalt-modified material, characterized in that, It is obtained by reacting basalt powder, manganese chloride and potassium permanganate.

6. The preparation method according to claim 5, characterized in that, Includes the following steps: (1) Crush the basalt and add it to distilled water, and add manganese chloride to dissolve it completely; (2) With Mn 2+ :MnO4 - The molar ratio is 3:2, and potassium permanganate solution is added dropwise continuously under stirring conditions; (3) Liquid-solid separation, washing, and obtaining filter cake; (4) The basalt modified material is obtained after the filter cake is dried.

7. The application of the basalt-modified material obtained by the preparation method of claim 5 in the adsorption of tetracycline.

8. The basalt-modified material obtained by the preparation method of claim 5.

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