A method for preparing a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride

Abstract

The application discloses a preparation method of a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride, and relates to the technical field of functional materials and the field of environment; the method comprises the following steps: step 1, a sodium molybdate aqueous solution is prepared by using sodium molybdate dihydrate, thiourea and metal chlorides are added into the sodium molybdate aqueous solution, the mixed solution is completely reacted at 100-180 DEG C, the product is cooled to room temperature, black precipitates are collected by centrifugation, and the black precipitates are washed and dried to obtain fine powder of sulfided metal-doped molybdenum disulfide, step 2, a carboxymethyl cellulose solution with a mass concentration of 0.4-3% is prepared, 10-50% of tannic acid by mass of the carboxymethyl cellulose is added into the carboxymethyl cellulose solution and stirred at 50-90 DEG C to obtain a tannic acid-modified carboxymethyl cellulose mixed solution, and step 3, the sulfided metal-doped molybdenum disulfide powder is added into the tannic acid-modified carboxymethyl cellulose mixed solution and stirred at 50-90 DEG C to obtain a composite slurry, and the composite slurry is extruded into an ionic bath containing metal chlorides by using an ionic crosslinking method to prepare the molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent.

Description

Technical Field

[0001] This invention discloses a method for preparing molybdenum disulfide / modified carboxymethyl cellulose hydrogel beads adsorbent for tetracycline hydrochloride, relating to the fields of functional materials technology and environmental technology. Background Technology

[0002] Tetracycline hydrochloride is a broad-spectrum antibiotic used in human medicine, veterinary medicine, and aquaculture. Because it is not metabolized after ingestion and has extremely poor biodegradability, it is often found in surface water, groundwater, and drinking water sources.

[0003] Currently, adsorption, membrane filtration, and advanced oxidation are commonly used and effective strategies for removing tetracycline hydrochloride. Compared to membrane filtration and advanced oxidation, adsorption is a simple and effective method for concentrating pollutants on a solid phase, enabling rapid and easy concentration of pollutants. Activated carbon is commonly used as an adsorbent among traditional adsorbent materials; however, its moderate affinity for certain antibiotics, relatively slow adsorption kinetics, complex regeneration process, and high chemical strength limit its widespread application in water treatment. Two-dimensional transition metal molybdenum disulfide (MoS2) has also emerged as a potential adsorbent, but its application in antibiotic removal is limited by the tendency of MoS2 to aggregate and the difficulty in separating it from treated wastewater in powder form. Summary of the Invention

[0004] This invention addresses the problems of existing technologies by providing a method for preparing molybdenum disulfide / modified carboxymethyl cellulose hydrogel beads adsorbents for tetracycline hydrochloride. The method involves modifying carboxymethyl cellulose with natural plant polyphenol tannic acid, doping it with metal elements, and composite nano-MoS2 to obtain hydrogel beads, which significantly improves the adsorption efficiency of the composite beads for tetracycline hydrochloride.

[0005] The specific solution proposed in this invention is as follows: This invention provides a method for preparing a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride, comprising: Step 1: Prepare an aqueous solution of sodium molybdate using sodium molybdate dihydrate. Add thiourea and a metal chloride to the sodium molybdate dihydrate. The mass ratio of sodium molybdate dihydrate to thiourea is 1:1–1:4, and the amount of metal chloride added is 1 / 5–1 of the mass of sodium molybdate dihydrate. The mixed solution was allowed to react completely at 100–180°C. The product was cooled to room temperature, and the black precipitate was collected by centrifugation. After washing, the metal-doped molybdenum disulfide was obtained, dried, and ground into a fine powder. Step 2: Prepare a carboxymethyl cellulose solution with a mass concentration of 0.4–3%, and add 10–50% (by mass) tannic acid of carboxymethyl cellulose at 50–90°C with stirring to obtain a tannic acid-modified carboxymethyl cellulose mixture. Step 3: Add metal-doped molybdenum disulfide powder to the tannic acid-modified carboxymethyl cellulose mixture at 50–90°C and stir to obtain a composite slurry. The mass ratio of tannic acid to metal-doped molybdenum disulfide is 1:2–1:10. Molybdenum disulfide / modified carboxymethyl cellulose hydrogel beads adsorbent were prepared by extruding the composite slurry into an ion bath containing metal chlorides using an ion crosslinking method.

[0006] Furthermore, step 1 of the method for preparing a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride includes: adding sodium molybdate dihydrate to distilled water and mixing thoroughly, stirring on a magnetic stirrer until a transparent solution is formed, adding thiourea in proportion, continuing to stir until it becomes a blue transparent solution, and adding metal chloride in proportion.

[0007] Furthermore, step 1 of the method for preparing a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride includes: adding chlorides of zinc, nickel, cobalt, manganese or copper in proportion.

[0008] Furthermore, step 3 of the method for preparing a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride specifically includes: dissolving the composite slurry at 5–100 mL·h⁻ 1 The flow rate is squeezed into an ion bath containing metal chloride. Upon contact, the droplets atomize into spherical hydrogel beads. The suspension is allowed to stand to ensure complete cross-linking. The spherical hydrogel beads are repeatedly washed and freeze-dried to obtain molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent.

[0009] The present invention also provides a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride, wherein the molybdenum disulfide doped with metal sulfide is embedded in a tannic acid modified carboxymethyl cellulose matrix as nanorod-shaped particles to form a composite material, wherein the metal includes zinc, nickel, cobalt, manganese or copper.

[0010] The present invention also provides a method for applying a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride, wherein the hydrogel bead adsorbent is applied to water to adsorb tetracycline hydrochloride.

[0011] The main mechanism of action in this invention is as follows: (1) Electrostatic interaction: Under neutral pH conditions, the negatively charged COO⁻ on the surface of carboxymethyl cellulose and the protonated amino group of tetracycline hydrochloride produce a charge complementary effect. These oppositely charged functional groups lead to a strong electrostatic attraction between the adsorbent surface and the antibiotic molecules.

[0012] (2) π−π interaction: There is a π−π stacking / interaction between the aromatic ring of tannic acid, the electron-rich MoS2 nanosheets, and the biconjugated colored molecule of tetracycline hydrochloride. Among them, MoS2 can generate strong interfacial interaction with the entire π-electron system of the tetracycline hydrochloride molecule, further enhancing the adsorption performance.

[0013] (3) Coordination / complexation: Metals such as Zn on the surface of the composite gel 2 ⁺、Mn 2 ⁺、Ni 2 ⁺、Co 2 ⁺、Cu 2 ⁺、Mo 4 As Lewis acid centers, ⁺ and other compounds coordinate / complex with the highly electronegative oxygen and nitrogen atoms on the carbonyl and amine functional groups of tetracycline hydrochloride to form stable coordination polymers, thereby achieving strong and effective adsorption.

[0014] The advantages of this invention are: (1) High material utilization rate, controllable raw material cost, easy to scale up production, and easy to transfer from laboratory scale to industrial production.

[0015] (2) Both carboxymethyl cellulose and tannic acid are biodegradable, and the burden of waste adsorbent treatment is small.

[0016] (3) The preparation process is simple, mainly using aqueous preparation, avoiding the use of large amounts of organic solvents.

[0017] (4) The synergistic effect of metal sulfide, molybdenum disulfide, tannic acid, and carboxymethyl cellulose (CMFC) is significant, enabling rapid and easy adsorption. Among them, metal sulfide-doped molybdenum disulfide has an excellent high specific surface area, providing abundant adsorption active sites; tannic acid-modified CMFC constructs a polymer network, giving the material the spherical particle morphology necessary for practical applications; at the same time, metal ions are introduced as ionic crosslinking agents, making the preparation process green and environmentally friendly, without secondary pollution. The three components synergistically construct an adsorption hydrogel bead with high mechanical stability, large specific surface area, and uniform distribution of active sites, which can achieve rapid and efficient adsorption and removal of tetracycline hydrochloride from wastewater.

[0018] (5) The composite material is a hydrogel bead, which is not easy to block the pipe and can be easily separated from the treated water. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, some simple figures will be drawn below to describe the sample data characterization process in the implementation of the present invention.

[0020] Figure 1 This is a schematic diagram illustrating the synthesis process of the method of the present invention.

[0021] Figure 2 The images are scanning electron microscope (SEM) images. Among them, (a) is an SEM image of the composite material after polymerization of tannic acid and carboxymethyl cellulose in Example 2, (b) is an SEM image of the composite material with zinc doped on molybdenum disulfide in Example 2, and (c) is an SEM image of the composite material of tannic acid modified carboxymethyl cellulose supported on zinc sulfide and molybdenum disulfide in Example 2.

[0022] Figure 3 The images show the UV spectra of the initial solution and the adsorption after adsorption in Example 2.

[0023] Figure 4 Bar graph showing the removal rate and adsorption capacity of tetracycline hydrochloride in Case 2. Detailed Implementation

[0024] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments described are not intended to limit the present invention. Example

[0025] A method for preparing a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride, comprising: Step 1: Add 10g of sodium molybdate dihydrate to 100mL of distilled water and mix thoroughly until a clear solution is formed. Add 20g of thiourea and continue stirring until the solution turns blue and clear. Add 4g of anhydrous zinc chloride, transfer the solution to a high-pressure reactor, and react at 140°C for 12 hours.

[0026] The product was naturally cooled to room temperature, and the black precipitate was collected by centrifugation. It was washed several times with distilled water and anhydrous ethanol to remove residual ions and byproducts, yielding zinc sulfide-doped molybdenum disulfide (MoS2-ZnS). The precipitate was dried in a vacuum oven and ground into a fine powder for further use.

[0027] Step 2: Dissolve 2.0g of carboxymethyl cellulose in 200mL of distilled water. Under continuous magnetic stirring, after the carboxymethyl cellulose is completely dissolved, add 1g of tannic acid and stir at 60°C for 8 hours to obtain a TA-CMC mixture.

[0028] Step 3: Add 3g of the prepared MoS2-ZnS fine powder to the TA-CMC solution and stir at 60°C for 6 hours to obtain the MoS2-ZnS / TA-CMC composite slurry. Ion crosslinking was used at a flow rate of 30mL·h⁻¹. 1Droplets were squeezed into an ion bath of zinc chloride solution to obtain a suspension. The suspension was left to stand for 16 hours to ensure complete cross-linking, and then repeatedly washed with deionized water and anhydrous ethanol. After freeze-drying for 24 hours, MoS2-ZnS / TA-CMC composite bead adsorbent was obtained. Example

[0029] A method for preparing a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride, comprising: Step 1: Add 10g of sodium molybdate dihydrate to 100mL of distilled water and mix thoroughly until a clear solution is formed. Add 30g of thiourea and continue stirring until a blue transparent solution is formed. Add 6g of anhydrous zinc chloride, transfer the solution to a high-pressure reactor, and react at 160°C for 20 hours. After naturally cooling to room temperature, collect the black precipitate by centrifugation, and wash it several times with distilled water and anhydrous ethanol to remove residual ions and byproducts, obtaining zinc sulfide-doped molybdenum disulfide (MoS2-ZnS). The final product is dried in a vacuum oven and ground into a fine powder for further use.

[0030] Step 2: Dissolve 4g of carboxymethyl cellulose in 200mL of distilled water. Under continuous magnetic stirring, after the carboxymethyl cellulose is completely dissolved, add 2g of tannic acid and stir at 90°C for 8 hours to obtain a TA-CMC mixture.

[0031] Step 3: Add 6g of the prepared MoS2-ZnS fine powder to the TA-CMC solution and stir at 80°C for 10 hours to obtain the MoS2-ZnS / TA-CMC composite slurry. Ion crosslinking was used at a flow rate of 50mL·h⁻¹. 1 Droplets were squeezed into an ion bath of zinc chloride solution to obtain a suspension. The suspension was left to stand for 16 hours to ensure complete cross-linking, and then repeatedly washed with deionized water and anhydrous ethanol. After freeze-drying for 48 hours, MoS2-ZnS / TA-CMC composite bead adsorbent was obtained.

[0032] refer to Figure 2 (a) Scanning electron microscopy image of the composite material after polymerization of tannic acid and carboxymethyl cellulose, showing that the material surface is smooth and flat, without obvious large pores, and has a compact structure; Figure 2 (b) is a scanning electron microscope image of a composite material doped with zinc on molybdenum disulfide, showing that the material surface has a layered stacked nanoflower-like structure with a uniform size distribution and a clear and orderly hierarchical structure. Figure 2 (c) is a scanning electron microscope image of a tannic acid-modified carboxymethyl cellulose-supported zinc sulfide-doped molybdenum disulfide composite material, showing that the material is transformed from an independent nanoflower-like structure into irregular rod-shaped particles, which are uniformly embedded in the tannic acid-modified carboxymethyl cellulose matrix. Example

[0033] A method for preparing a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride, comprising: Step 1: Add 20g of sodium molybdate dihydrate to 100mL of distilled water and mix thoroughly until a clear solution is formed. Add 40g of thiourea and continue stirring until a blue transparent solution is formed. Add 16g of anhydrous zinc chloride, transfer the solution to a high-pressure reactor, and react at 180°C for 20 hours. After naturally cooling to room temperature, collect the black precipitate by centrifugation, and wash it several times with distilled water and anhydrous ethanol to remove residual ions and byproducts, obtaining zinc sulfide-doped molybdenum disulfide (MoS2-ZnS). The final product is dried in a vacuum oven and ground into a fine powder for further use.

[0034] Step 2: Dissolve 6g of carboxymethyl cellulose in 200mL of distilled water. Under continuous magnetic stirring, after the carboxymethyl cellulose is completely dissolved, add 3g of tannic acid and stir at 80°C for 10 hours to obtain a TA-CMC mixture.

[0035] Step 3: Add 6g of the prepared MoS2-ZnS fine powder to the TA-CMC solution and stir at 70°C for 10 hours to obtain the MoS2-ZnS / TA-CMC composite slurry. Ion crosslinking was used at a flow rate of 70mL·h⁻¹. 1 Droplets were squeezed into an ion bath of zinc chloride solution to obtain a suspension. The suspension was left to stand for 16 hours to ensure complete cross-linking, and then repeatedly washed with deionized water and anhydrous ethanol. After freeze-drying for 48 hours, MoS2-ZnS / TA-CMC composite bead adsorbent was obtained. Example

[0036] A method for preparing a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride, comprising: Step 1: Add 20g of sodium molybdate dihydrate to 100mL of distilled water and mix thoroughly until a clear solution is formed. Add 40g of thiourea and continue stirring until a blue transparent solution is formed. Add 28g of nickel chloride hexahydrate, transfer the solution to a high-pressure reactor, and react at 180°C for 20 hours. After naturally cooling to room temperature, collect the black precipitate by centrifugation, and wash it several times with distilled water and anhydrous ethanol to remove residual ions and byproducts, obtaining nickel sulfide-doped molybdenum disulfide (MoS2-NiS). The final product is dried in a vacuum oven and ground into a fine powder for further use.

[0037] Step 2: Dissolve 4g of carboxymethyl cellulose in 200mL of distilled water. Under continuous magnetic stirring, after the carboxymethyl cellulose is completely dissolved, add 2g of tannic acid and stir at 90°C for 8 hours to obtain a TA-CMC mixture.

[0038] Step 3: Add 6g of the prepared MoS2-NiS fine powder to the TA-CMC solution and stir at 90°C for 8 hours to obtain the MoS2-NiS / TA-CMC composite slurry. Ion crosslinking was used at a flow rate of 40mL·h⁻¹. 1 Droplets were squeezed into an ion bath of nickel chloride solution to obtain a suspension. The suspension was left to stand for 16 hours to ensure complete cross-linking, and then repeatedly washed with deionized water and anhydrous ethanol. After freeze-drying for 48 hours, MoS2-NiS / TA-CMC composite bead adsorbent was obtained. Example

[0039] A method for preparing a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride, comprising: Step 1: Add 20g of sodium molybdate dihydrate to 100mL of distilled water and mix thoroughly until a clear solution is formed. Add 40g of thiourea and continue stirring until a blue transparent solution is formed. Add 20g of anhydrous cobalt chloride, transfer the solution to a high-pressure reactor, and react at 180°C for 20 hours. After naturally cooling to room temperature, collect the black precipitate by centrifugation, and wash it several times with distilled water and anhydrous ethanol to remove residual ions and byproducts, obtaining cobalt sulfide-doped molybdenum disulfide (MoS2-CoS). The final product is dried in a vacuum oven and ground into a fine powder for further use.

[0040] Step 2: Dissolve 4g of carboxymethyl cellulose in 300mL of distilled water. Under continuous magnetic stirring, after the carboxymethyl cellulose is completely dissolved, add 2g of tannic acid and stir at 90°C for 8 hours to obtain a TA-CMC mixture.

[0041] Step 3: Add 6g of the prepared MoS2-CoS to the TA-CMC solution and stir at 80°C for 6 hours to obtain the MoS2-CoS / TA-CMC composite slurry. Ion crosslinking was used at a flow rate of 80mL·h⁻¹. 1 Droplets were squeezed into an ion bath of cobalt chloride solution to obtain a suspension. The suspension was left to stand for 16 hours to ensure complete cross-linking, and then repeatedly washed with deionized water and anhydrous ethanol. After freeze-drying for 48 hours, MoS2-CoS / TA-CMC composite bead adsorbent was obtained. Example

[0042] A method for preparing a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride, comprising: Step 1: Add 20g of sodium molybdate dihydrate to 100mL of distilled water and mix thoroughly until a clear solution is formed. Add 40g of thiourea and continue stirring until a blue transparent solution is formed. Add 14g of manganese chloride, transfer the solution to a high-pressure reactor, and react at 180°C for 20 hours. After naturally cooling to room temperature, collect the black precipitate by centrifugation, and wash it several times with distilled water and anhydrous ethanol to remove residual ions and byproducts, obtaining manganese sulfide-doped molybdenum disulfide (MoS2-MnS). The final product is dried in a vacuum oven and ground into a fine powder for further use.

[0043] Step 2: Dissolve 4g of carboxymethyl cellulose in 300mL of distilled water. Under continuous magnetic stirring, after the carboxymethyl cellulose is completely dissolved, add 2g of tannic acid and stir at 90°C for 8 hours to obtain a TA-CMC mixture.

[0044] Step 3: Add 6g of the prepared MoS2-MnS fine powder to the TA-CMC solution and stir at 80°C for 6 hours to obtain the MoS2-MnS / TA-CMC composite slurry. Ion crosslinking was used at a flow rate of 50mL·h⁻¹. 1 Droplets were squeezed into an ion bath of manganese chloride solution to obtain a suspension. The suspension was left to stand for 16 hours to ensure complete cross-linking, and then repeatedly washed with deionized water and anhydrous ethanol. After freeze-drying for 48 hours, MoS2-MnS / TA-CMC composite bead adsorbent was obtained. Example

[0045] A method for preparing a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride, comprising: Step 1: Add 20g of sodium molybdate dihydrate to 100mL of distilled water and mix thoroughly until a clear solution is formed. Add 40g of thiourea and continue stirring until a blue transparent solution is formed. Add 16g of copper chloride and transfer the solution to a high-pressure reactor. React at 180°C for 20 hours. After naturally cooling to room temperature, collect the black precipitate by centrifugation and wash it several times with distilled water and anhydrous ethanol to remove residual ions and byproducts, obtaining copper sulfide-doped molybdenum disulfide (MoS2-CuS). The final product is dried in a vacuum oven and ground into a fine powder for further use.

[0046] Step 2: Dissolve 4g of carboxymethyl cellulose in 300mL of distilled water. Under continuous magnetic stirring, after the carboxymethyl cellulose is completely dissolved, add 2g of tannic acid and stir at 90°C for 8 hours to obtain a TA-CMC mixture.

[0047] Step 3: Add 6g of the prepared MoS2-CuS fine powder to the TA-CMC solution and stir at 80°C for 6 hours to obtain the MoS2-CuS / TA-CMC composite slurry. Ion crosslinking was used at a flow rate of 50mL·h⁻¹. 1 Droplets were squeezed into an ion bath of copper chloride solution to obtain a suspension. The suspension was left to stand for 16 hours to ensure complete cross-linking, and then repeatedly washed with deionized water and anhydrous ethanol. After freeze-drying for 48 hours, MoS2-CuS / TA-CMC composite bead adsorbent was obtained.

[0048] Other embodiments of the present invention can be referred to. Figure 2 The morphological images of the composite material after polymerization of tannic acid and carboxymethyl cellulose, the composite material doped with zinc on molybdenum disulfide, and the composite material of tannic acid-modified carboxymethyl cellulose loaded with zinc sulfide and doped molybdenum disulfide, as shown in the electron microscope images, also have similar adsorption technology effects as in Example 2.

[0049] The molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent obtained in this invention comprises molybdenum disulfide nanorod-shaped particles doped with metal sulfide embedded in a tannic acid-modified carboxymethyl cellulose matrix to form a composite material. The metals include zinc, nickel, cobalt, manganese, or copper. It is particularly suitable for adsorbing tetracycline hydrochloride in water.

[0050] The above are preferred embodiments of the present invention. Within the scope of the technical solution of the present invention, the degradation of polybenzoxazine resin can be obtained by adjusting the type and amount of reagents according to the actual situation.

[0051] Unless otherwise specified, all reagents used in the method of this invention were purchased or obtained through legitimate channels.

[0052] The above-described embodiments are merely preferred embodiments provided to fully illustrate the present invention, and the scope of protection of the present invention is not limited thereto. Equivalent substitutions or modifications made by those skilled in the art based on the present invention are all within the scope of protection of the present invention. The scope of protection of the present invention is defined by the claims.

Claims

1. A method for preparing a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride, characterized in that... include: Step 1: Prepare an aqueous solution of sodium molybdate using sodium molybdate dihydrate. Add thiourea and a metal chloride to the sodium molybdate dihydrate. The mass ratio of sodium molybdate dihydrate to thiourea is 1:1–1:4, and the amount of metal chloride added is 1 / 5–1 of the mass of sodium molybdate dihydrate. The mixed solution was allowed to react completely at 100–180°C. The product was cooled to room temperature, and the black precipitate was collected by centrifugation. After washing, the metal-doped molybdenum disulfide was obtained, dried, and ground into a fine powder. Step 2: Prepare a carboxymethyl cellulose solution with a mass concentration of 0.4–3%, and add 10–50% (by mass) tannic acid of carboxymethyl cellulose at 50–90°C with stirring to obtain a tannic acid-modified carboxymethyl cellulose mixture. Step 3: Add metal-doped molybdenum disulfide powder to the tannic acid-modified carboxymethyl cellulose mixture at 50–90°C and stir to obtain a composite slurry. The mass ratio of tannic acid to metal-doped molybdenum disulfide is 1:2–1:

10. Molybdenum disulfide / modified carboxymethyl cellulose hydrogel beads adsorbent were prepared by extruding the composite slurry into an ion bath containing metal chlorides using an ion crosslinking method.

2. The method for preparing a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride according to claim 1, characterized in that... Step 1 includes: adding sodium molybdate dihydrate to distilled water and mixing thoroughly, stirring on a magnetic stirrer until a transparent solution is formed, adding thiourea in proportion, continuing to stir until it becomes a blue transparent solution, and adding metal chloride in proportion.

3. The method for preparing a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride according to claim 1, characterized in that... Step 1 includes adding chlorides of zinc, nickel, cobalt, manganese, or copper in a specific ratio.

4. The method for preparing a molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride according to claim 1, characterized in that... Step 3 specifically includes: dispensing the composite slurry at a rate of 5–100 mL / h⁻ 1 The flow rate is squeezed into an ion bath containing metal chloride. Upon contact, the droplets atomize into spherical hydrogel beads. The suspension is allowed to stand to ensure complete cross-linking. The spherical hydrogel beads are repeatedly washed and freeze-dried to obtain molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent.

5. A molybdenum disulfide / modified carboxymethyl cellulose hydrogel bead adsorbent for tetracycline hydrochloride, characterized in that... The hydrogel bead adsorbent contains molybdenum disulfide doped with metal sulfide in nanorod form, which is embedded in a tannic acid-modified carboxymethyl cellulose matrix to form a composite material. The metal includes zinc, nickel, cobalt, manganese, or copper.

6. A method for applying molybdenum disulfide / modified carboxymethyl cellulose hydrogel beads as an adsorbent for tetracycline hydrochloride, characterized in that... The hydrogel bead adsorbent was applied to water to adsorb tetracycline hydrochloride.

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