Super-adsorption material and application thereof in adsorption of Congo red

Abstract

The invention provides a super adsorption material and application thereof in adsorption of Congo red, a preparation method comprises the following steps: uniformly mixing hydrolyzed peach gum, bi-crosslinked tyrosine-bacterial cellulose microspheres and activated sludge to obtain a mixture, adding deionized water, and stirring; performing drying; putting into deionized water to absorb water, and then freeze-drying to obtain aerogel; placing the aerogel in deionized water, adding sodium bromide and 2, 2, 6, 6-tetramethylpiperidine oxide, and stirring; adding sodium hypochlorite, adding a sodium hydroxide aqueous solution to keep the pH value between 10.0 and 10.5, and stirring; after ending the reaction, washing to be neutral; and freeze-drying to obtain the product. Aerogel is adopted to fix the bi-crosslinked tyrosine-bacterial cellulose microspheres, and the problems that the bi-crosslinked tyrosine-bacterial cellulose microspheres are rich in hydrophilic functional groups such as hydroxyl groups on the surfaces and can be well dispersed in water, so that the bi-crosslinked tyrosine-bacterial cellulose microspheres are difficult to be independently applied to adsorption separation of organic pollutants (Congo red), the recovery effect is poor, and the cost is low are solved. And secondary pollution is easily caused.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment materials technology, specifically to a superadsorption material and its application in adsorbing Congo red. Background Technology

[0002] The dye industry is an important sector of the national economy, with its products primarily used in textiles, leather, food, coatings, inks, and rubber. Dyes are substances that impart color to fibers, and their types can be categorized by characteristics, including direct dyes, sulfur dyes, vat dyes, acid dyes, acid complex dyes, reactive dyes, sodium fuchsin dyes (or insoluble azo dyes or ice dyes), oxidative dyes, disperse dyes, and cationic dyes. Dye wastewater refers to wastewater discharged during the production of dyes and pigments. Statistics show that 12% of synthetic dyes are discharged as wastewater during production and treatment. Congo red is an anionic azo dye wastewater, highly toxic and with a deep color. Unused wastewater from industrial production is discharged into aquatic environments, reducing water transmittance, affecting plant photosynthesis, and eventually leading to black water pollution. This not only damages the living environment of aquatic organisms but also ultimately threatens human health. Currently, there are many methods for treating wastewater pollution, mainly physical, chemical, and biological methods. Adsorption methods are widely used due to their convenience, high efficiency, and simple process. For the adsorption of Congo red, the CuMgAl hydrotalcite prepared by Bharali et al. currently has an adsorption capacity of only 44.5 mg / g; Liao Qinyao et al. obtained MgAl-LDO by calcining magnesium aluminum hydrotalcite, achieving an adsorption capacity of 315.48 mg / g for Congo red. However, the adsorption effect is still not ideal, and there is an urgent need to develop adsorbent materials with better performance for this purpose. Summary of the Invention

[0003] The technical problem to be solved: The purpose of this invention is to provide a super-adsorption material and its application in the adsorption of Congo red. It employs aerogel to immobilize double-crosslinked tyrosine-bacterial cellulose microspheres, solving the problem that the surface of double-crosslinked tyrosine-bacterial cellulose microspheres is rich in hydrophilic functional groups such as hydroxyl groups, which can disperse well in water, making them difficult to use alone for the adsorption and separation of organic pollutants (Congo red). Furthermore, the recovery effect is poor, easily causing secondary pollution. By introducing tyrosine into the bacterial cellulose microspheres, blue light excitation of curcumin and L-arginine initiates the coupling of tyrosine free radicals on adjacent chains to form a double-tyrosine structure, forming covalent crosslinks, thus achieving a double-crosslinked network structure with the bacterial cellulose microspheres, enhancing mechanical and adsorption properties.

[0004] Technical solution: A super-adsorption material, wherein the super-adsorption material is an aerogel with double cross-linked tyrosine-bacterial cellulose microspheres immobilized inside; The particle size of the double-crosslinked tyrosine-bacterial cellulose microspheres is 0.1-1 mm. Furthermore, the preparation method of the double-crosslinked tyrosine-bacterial cellulose microspheres includes the following steps: S1: Transfer the P1 strain of *Acetobacter xylose* to seed culture medium, place it in a 30℃ incubator, adjust the rotation speed to 160r / min and culture for 24h, then dilute and spread it on solid plates, and continue to culture at 30℃ for 3d; S2: Use an inoculation loop to scrape two loops of colonies from a solid plate and transfer them to 30 mL of seed culture medium. After incubating in a 30°C incubator for 24 h, filter with sterile defatted cotton to obtain the seed liquid. S3: Sterilize 2-5g of tyrosine and 250mL of AE fermentation medium separately, mix them, inoculate the seed liquid at an inoculation rate of 8%, and culture continuously at 30℃ and 120r / min for 48-96h in a constant temperature shaking incubator to obtain bacterial cellulose microspheres rich in tyrosine. S4: Take tyrosine-rich bacterial cellulose microspheres, add water, then add curcumin and L-arginine, and stir for 5-10 minutes; S5: Place in a nitrogen atmosphere and react under 467nm blue LED light for 8-10 minutes; S6: Remove, soak and wash with running water, then wash with deionized water, dry, and screen to obtain double cross-linked tyrosine-bacterial cellulose microspheres. Furthermore, the amount of curcumin added is 0.5-1.0% of the tyrosine-rich bacterial cellulose microspheres. Furthermore, the mass ratio of curcumin to L-arginine is 3:(0.5-2). The preparation method of the above-mentioned superadsorption material includes the following steps: Step 1: Mix hydrolyzed peach gum, double cross-linked tyrosine-bacterial cellulose microspheres and activated sludge evenly to obtain a mixture, add 20 times the mass of the mixture of deionized water, and stir for 30 minutes; Step 2: Dry in a 60℃ forced-air dryer for 24 hours; Step 3: After absorbing water in deionized water for 12 hours, freeze-dry to obtain an aerogel; Step 4: Place the aerogel in deionized water, add sodium bromide and 2,2,6,6-tetramethylpiperidine oxide and stir for 5-10 min; Step 5: Add sodium hypochlorite and sodium hydroxide aqueous solution to maintain the pH between 10.0 and 10.5, and stir for 6 h; Step 6: Pour in ethanol to terminate the reaction, and wash with 0.1 mol / L hydrochloric acid aqueous solution and deionized water successively until neutral; Step 7: Freeze-dry to obtain the superadsorbent material. Furthermore, the mass ratio of the hydrolyzed peach gum, the double-crosslinked tyrosine-bacterial cellulose microspheres, and the activated sludge is 6:(3-5):2. Furthermore, the preparation method of the hydrolyzed peach gum is as follows: (1) After cleaning the peach gum, freeze-dry it, grind it in a mortar and pestle, and pass it through a 300-mesh sieve to obtain peach gum powder; (2) Mix 3g of peach gum powder, 0.02g of NaOH and 80mL of deionized water, and stir at 85℃ for 45min; (3) Add dilute hydrochloric acid until the solution is neutral, cool to room temperature, seal, and freeze dry to obtain hydrolyzed peach gum. Furthermore, in step 4, the amount of sodium bromide added is 0.2 mmol / g aerogel, and the amount of 2,2,6,6-tetramethylpiperidine oxide added is 0.2-0.5 mmol / g aerogel. Furthermore, in step 5, the amount of sodium hypochlorite added is 10-20 mmol / g aerogel. Application of the above-mentioned superadsorption materials in the adsorption of Congo red. Beneficial effects: 1. This invention uses aerogel to immobilize double cross-linked tyrosine-bacterial cellulose microspheres, which solves the problem that the surface of double cross-linked tyrosine-bacterial cellulose microspheres is rich in hydrophilic functional groups such as hydroxyl groups. They can be well dispersed in water, so they are difficult to use alone for the adsorption and separation of organic pollutants (Congo red). At the same time, the recovery effect is poor and they are prone to secondary pollution. 2. This invention introduces tyrosine into bacterial cellulose microspheres, and uses blue light to excite curcumin and L-arginine to initiate the coupling of tyrosine free radicals on adjacent chains to form a double tyrosine structure, forming covalent cross-links, thereby achieving a double cross-linked network structure with bacterial cellulose microspheres and enhancing mechanical and adsorption properties. 3. By adding L-arginine, this invention can promote the cross-linking effect of curcumin and reduce the cross-linking time. 4. In this invention, peach gum has excellent gelling properties. After hydrolysis, its water solubility increases. It has an adsorption effect on organic pollutants in water. After being made into an aerogel, it forms a loose layered structure. This structure is conducive to promoting the diffusion of organic pollutants inside and facilitates the adsorption of double cross-linked tyrosine-bacterial cellulose microspheres. 5. The addition of activated sludge to the aerogel of this invention facilitates the rapid adsorption of organic pollutants, effectively improving the adsorption rate. Some pollutants are degraded by the pollutants, while the majority are further adsorbed by the double-crosslinked tyrosine-bacterial cellulose microspheres. 6. This invention employs a sodium bromide-2,2,6,6-tetramethylpiperidine oxide-sodium hypochlorite oxidation system to selectively oxidize aerogels, oxidizing some hydroxyl groups to carboxyl groups, reducing the degree of polymerization, increasing the content of oxygen-containing functional groups in the aerogels, thereby generating electrostatic forces and hydrogen bonds, and improving selective adsorption performance. Attached Figure Description Figure 1 This is a comparison chart of the adsorption amount of Congo red in Example 13 and Comparative Example 3 at different times. Detailed Implementation Example 1 The preparation method of double-crosslinked tyrosine-bacterial cellulose microspheres includes the following steps: S1: Transfer the P1 strain of *Acetobacter xylose* to seed culture medium, place it in a 30℃ incubator, adjust the rotation speed to 160r / min and culture for 24h, then dilute and spread it on solid plates, and continue to culture at 30℃ for 3d; S2: Use an inoculation loop to scrape two loops of colonies from a solid plate and transfer them to 30 mL of seed culture medium. After incubating in a 30°C incubator for 24 h, filter with sterile defatted cotton to obtain the seed liquid. S3: 2g of tyrosine and 250mL of AE fermentation medium were sterilized and mixed separately. The mixture was then inoculated into the seed culture at an inoculation rate of 8%. The mixture was continuously cultured in a constant temperature shaking incubator at 30℃ and 120r / min for 96h to obtain bacterial cellulose microspheres rich in tyrosine. S4: Water was added to the bacterial cellulose microspheres rich in tyrosine, followed by curcumin and L-arginine. The mixture was stirred for 10min. The amount of curcumin added was 0.8% of the bacterial cellulose microspheres rich in tyrosine. The mass ratio of curcumin to L-arginine was 3:1.5. S5: Place in a nitrogen atmosphere and react under 467nm blue LED light for 10 minutes; S6: Remove, soak and wash with running water, then wash with deionized water, dry, and screen to obtain double cross-linked tyrosine-bacterial cellulose microspheres. The particle size of the double-crosslinked tyrosine-bacterial cellulose microspheres is 0.1-1 mm. Example 2 The preparation method of double-crosslinked tyrosine-bacterial cellulose microspheres includes the following steps: S1: Transfer the P1 strain of *Acetobacter xylose* to seed culture medium, place it in a 30℃ incubator, adjust the rotation speed to 160r / min and culture for 24h, then dilute and spread it on solid plates, and continue to culture at 30℃ for 3d; S2: Use an inoculation loop to scrape two loops of colonies from a solid plate and transfer them to 30 mL of seed culture medium. After incubating in a 30°C incubator for 24 h, filter with sterile defatted cotton to obtain the seed liquid. S3: 3g of tyrosine and 250mL of AE fermentation medium were sterilized and mixed separately. The mixture was then inoculated into the seed culture at an inoculation rate of 8%. The mixture was continuously cultured in a constant temperature shaking incubator at 30℃ and 120r / min for 96h to obtain bacterial cellulose microspheres rich in tyrosine. S4: Water was added to the bacterial cellulose microspheres rich in tyrosine, followed by the addition of curcumin and L-arginine. The mixture was stirred for 10min. The amount of curcumin added was 0.8% of the bacterial cellulose microspheres rich in tyrosine. The mass ratio of curcumin to L-arginine was 3:1.5. S5: Place in a nitrogen atmosphere and react under 467nm blue LED light for 10 minutes; S6: Remove, soak and wash with running water, then wash with deionized water, dry, and screen to obtain double cross-linked tyrosine-bacterial cellulose microspheres. The particle size of the double-crosslinked tyrosine-bacterial cellulose microspheres is 0.1-1 mm. Example 3 The preparation method of double-crosslinked tyrosine-bacterial cellulose microspheres includes the following steps: S1: Transfer the P1 strain of *Acetobacter xylose* to seed culture medium, place it in a 30℃ incubator, adjust the rotation speed to 160r / min and culture for 24h, then dilute and spread it on solid plates, and continue to culture at 30℃ for 3d; S2: Use an inoculation loop to scrape two loops of colonies from a solid plate and transfer them to 30 mL of seed culture medium. After incubating in a 30°C incubator for 24 h, filter with sterile defatted cotton to obtain the seed liquid. S3: 4g of tyrosine and 250mL of AE fermentation medium were sterilized and mixed separately. The mixture was then inoculated into the seed culture at an inoculation rate of 8%. The mixture was continuously cultured in a constant temperature shaking incubator at 30℃ and 120r / min for 96h to obtain bacterial cellulose microspheres rich in tyrosine. S4: Water was added to the bacterial cellulose microspheres rich in tyrosine, followed by the addition of curcumin and L-arginine. The mixture was stirred for 10min. The amount of curcumin added was 0.8% of the bacterial cellulose microspheres rich in tyrosine. The mass ratio of curcumin to L-arginine was 3:1.5. S5: Place in a nitrogen atmosphere and react under 467nm blue LED light for 10 minutes; S6: Remove, soak and wash with running water, then wash with deionized water, dry, and screen to obtain double cross-linked tyrosine-bacterial cellulose microspheres. The particle size of the double-crosslinked tyrosine-bacterial cellulose microspheres is 0.1-1 mm. Example 4 The preparation method of double-crosslinked tyrosine-bacterial cellulose microspheres includes the following steps: S1: Transfer the P1 strain of *Acetobacter xylose* to seed culture medium, place it in a 30℃ incubator, adjust the rotation speed to 160r / min and culture for 24h, then dilute and spread it on solid plates, and continue to culture at 30℃ for 3d; S2: Use an inoculation loop to scrape two loops of colonies from a solid plate and transfer them to 30 mL of seed culture medium. After incubating in a 30°C incubator for 24 h, filter with sterile defatted cotton to obtain the seed liquid. S3: 5g of tyrosine and 250mL of AE fermentation medium were sterilized and mixed separately. The mixture was then inoculated into the seed culture at an inoculation rate of 8%. The mixture was continuously cultured in a constant temperature shaking incubator at 30℃ and 120r / min for 96h to obtain bacterial cellulose microspheres rich in tyrosine. S4: Water was added to the bacterial cellulose microspheres rich in tyrosine, followed by the addition of curcumin and L-arginine. The mixture was stirred for 10min. The amount of curcumin added was 0.8% of the bacterial cellulose microspheres rich in tyrosine. The mass ratio of curcumin to L-arginine was 3:1.5. S5: Place in a nitrogen atmosphere and react under 467nm blue LED light for 10 minutes; S6: Remove, soak and wash with running water, then wash with deionized water, dry, and screen to obtain double cross-linked tyrosine-bacterial cellulose microspheres. The particle size of the double-crosslinked tyrosine-bacterial cellulose microspheres is 0.1-1 mm. Example 5 The preparation method of double-crosslinked tyrosine-bacterial cellulose microspheres includes the following steps: S1: Transfer the P1 strain of *Acetobacter xylose* to seed culture medium, place it in a 30℃ incubator, adjust the rotation speed to 160r / min and culture for 24h, then dilute and spread it on solid plates, and continue to culture at 30℃ for 3d; S2: Use an inoculation loop to scrape two loops of colonies from a solid plate and transfer them to 30 mL of seed culture medium. After incubating in a 30°C incubator for 24 h, filter with sterile defatted cotton to obtain the seed liquid. S3: 4g of tyrosine and 250mL of AE fermentation medium were sterilized and mixed separately. The mixture was then inoculated into the seed culture at an inoculation rate of 8%. The mixture was continuously cultured in a constant temperature shaking incubator at 30℃ and 120r / min for 96h to obtain bacterial cellulose microspheres rich in tyrosine. S4: Water was added to the bacterial cellulose microspheres rich in tyrosine, followed by the addition of curcumin and L-arginine. The mixture was stirred for 10min. The amount of curcumin added was 0.5% of the bacterial cellulose microspheres rich in tyrosine. The mass ratio of curcumin to L-arginine was 3:1.5. S5: Place in a nitrogen atmosphere and react under 467nm blue LED light for 10 minutes; S6: Remove, soak and wash with running water, then wash with deionized water, dry, and screen to obtain double cross-linked tyrosine-bacterial cellulose microspheres. The particle size of the double-crosslinked tyrosine-bacterial cellulose microspheres is 0.1-1 mm. Example 6 The preparation method of double-crosslinked tyrosine-bacterial cellulose microspheres includes the following steps: S1: Transfer the P1 strain of *Acetobacter xylose* to seed culture medium, place it in a 30℃ incubator, adjust the rotation speed to 160r / min and culture for 24h, then dilute and spread it on solid plates, and continue to culture at 30℃ for 3d; S2: Use an inoculation loop to scrape two loops of colonies from a solid plate and transfer them to 30 mL of seed culture medium. After incubating in a 30°C incubator for 24 h, filter with sterile defatted cotton to obtain the seed liquid. S3: 4g of tyrosine and 250mL of AE fermentation medium were sterilized and mixed separately. The mixture was then inoculated into the seed culture at an inoculation rate of 8%. The mixture was continuously cultured in a constant temperature shaking incubator at 30℃ and 120r / min for 96h to obtain bacterial cellulose microspheres rich in tyrosine. S4: Water was added to the bacterial cellulose microspheres rich in tyrosine, followed by the addition of curcumin and L-arginine. The mixture was stirred for 10min. The amount of curcumin added was 1.0% of the bacterial cellulose microspheres rich in tyrosine. The mass ratio of curcumin to L-arginine was 3:1.5. S5: Place in a nitrogen atmosphere and react under 467nm blue LED light for 10 minutes; S6: Remove, soak and wash with running water, then wash with deionized water, dry, and screen to obtain double cross-linked tyrosine-bacterial cellulose microspheres. The particle size of the double-crosslinked tyrosine-bacterial cellulose microspheres is 0.1-1 mm. Example 7 The preparation method of double-crosslinked tyrosine-bacterial cellulose microspheres includes the following steps: S1: Transfer the P1 strain of *Acetobacter xylose* to seed culture medium, place it in a 30℃ incubator, adjust the rotation speed to 160r / min and culture for 24h, then dilute and spread it on solid plates, and continue to culture at 30℃ for 3d; S2: Use an inoculation loop to scrape two loops of colonies from a solid plate and transfer them to 30 mL of seed culture medium. After incubating in a 30°C incubator for 24 h, filter with sterile defatted cotton to obtain the seed liquid. S3: 4g of tyrosine and 250mL of AE fermentation medium were sterilized and mixed separately. The mixture was then inoculated into the seed culture at an inoculation rate of 8% and cultured continuously at 30℃ and 120r / min for 96h in a constant temperature shaking incubator to obtain tyrosine-rich bacterial cellulose microspheres. S4: Water was added to the tyrosine-rich bacterial cellulose microspheres, followed by curcumin and L-arginine. The mixture was stirred for 10min. The amount of curcumin added was 0.8% of the tyrosine-rich bacterial cellulose microspheres. The mass ratio of curcumin to L-arginine was 3:0.5. S5: Place in a nitrogen atmosphere and react under 467nm blue LED light for 10 minutes; S6: Remove, soak and wash with running water, then wash with deionized water, dry, and screen to obtain double cross-linked tyrosine-bacterial cellulose microspheres. The particle size of the double-crosslinked tyrosine-bacterial cellulose microspheres is 0.1-1 mm. Example 8 The preparation method of double-crosslinked tyrosine-bacterial cellulose microspheres includes the following steps: S1: Transfer the P1 strain of *Acetobacter xylose* to seed culture medium, place it in a 30℃ incubator, adjust the rotation speed to 160r / min and culture for 24h, then dilute and spread it on solid plates, and continue to culture at 30℃ for 3d; S2: Use an inoculation loop to scrape two loops of colonies from a solid plate and transfer them to 30 mL of seed culture medium. After incubating in a 30°C incubator for 24 h, filter with sterile defatted cotton to obtain the seed liquid. S3: 4g of tyrosine and 250mL of AE fermentation medium were sterilized and mixed separately. The mixture was then inoculated into the seed culture at an inoculation rate of 8% and cultured continuously at 30℃ and 120r / min for 96h in a constant temperature shaking incubator to obtain bacterial cellulose microspheres rich in tyrosine. S4: Water was added to the bacterial cellulose microspheres rich in tyrosine, followed by the addition of curcumin and L-arginine. The mixture was stirred for 10min. The amount of curcumin added was 0.8% of the bacterial cellulose microspheres rich in tyrosine. The mass ratio of curcumin to L-arginine was 3:1.0. S5: Place in a nitrogen atmosphere and react under 467nm blue LED light for 10 minutes; S6: Remove, soak and wash with running water, then wash with deionized water, dry, and screen to obtain double cross-linked tyrosine-bacterial cellulose microspheres. The particle size of the double-crosslinked tyrosine-bacterial cellulose microspheres is 0.1-1 mm. Example 9 The preparation method of double-crosslinked tyrosine-bacterial cellulose microspheres includes the following steps: S1: Transfer the P1 strain of *Acetobacter xylose* to seed culture medium, place it in a 30℃ incubator, adjust the rotation speed to 160r / min and culture for 24h, then dilute and spread it on solid plates, and continue to culture at 30℃ for 3d; S2: Use an inoculation loop to scrape two loops of colonies from a solid plate and transfer them to 30 mL of seed culture medium. After incubating in a 30°C incubator for 24 h, filter with sterile defatted cotton to obtain the seed liquid. S3: 4g of tyrosine and 250mL of AE fermentation medium were sterilized and mixed separately. The mixture was then inoculated into the seed culture at an inoculation rate of 8% and cultured continuously at 30℃ and 120r / min for 96h in a constant temperature shaking incubator to obtain bacterial cellulose microspheres rich in tyrosine. S4: Water was added to the bacterial cellulose microspheres rich in tyrosine, followed by curcumin and L-arginine. The mixture was stirred for 10min. The amount of curcumin added was 0.8% of the bacterial cellulose microspheres rich in tyrosine. The mass ratio of curcumin to L-arginine was 3:2.0. S5: Place in a nitrogen atmosphere and react under 467nm blue LED light for 10 minutes; S6: Remove, soak and wash with running water, then wash with deionized water, dry, and screen to obtain double cross-linked tyrosine-bacterial cellulose microspheres. The particle size of the double-crosslinked tyrosine-bacterial cellulose microspheres is 0.1-1 mm. Comparative Example 1 The difference between this comparative example and Example 3 is that tyrosine is not added, as detailed below: The preparation method of bacterial cellulose microspheres includes the following steps: S1: Transfer the P1 strain of *Acetobacter xylose* to seed culture medium, place it in a 30℃ incubator, adjust the rotation speed to 160r / min and culture for 24h, then dilute and spread it on solid plates, and continue to culture at 30℃ for 3d; S2: Use an inoculation loop to scrape two loops of colonies from a solid plate and transfer them to 30 mL of seed culture medium. After incubating in a 30°C incubator for 24 h, filter with sterile defatted cotton to obtain the seed liquid. S3: After sterilizing 250 mL of AE fermentation medium, inoculate the seed liquid at an inoculation rate of 8% and culture continuously at 30 °C and 120 r / min in a constant temperature shaking incubator for 96 h to obtain bacterial cellulose microspheres. S4: Remove the microspheres, soak and wash them in running water, then wash them with deionized water, dry them, and screen them to obtain bacterial cellulose microspheres. The particle size of the bacterial cellulose microspheres is 0.1-1 mm. Comparative Example 2 The difference between this comparative example and Example 3 is that L-arginine is not added, as detailed below: The preparation method of double-crosslinked tyrosine-bacterial cellulose microspheres includes the following steps: S1: Transfer the P1 strain of *Acetobacter xylose* to seed culture medium, place it in a 30℃ incubator, adjust the rotation speed to 160r / min and culture for 24h, then dilute and spread it on solid plates, and continue to culture at 30℃ for 3d; S2: Use an inoculation loop to scrape two loops of colonies from a solid plate and transfer them to 30 mL of seed culture medium. After incubating in a 30°C incubator for 24 h, filter with sterile defatted cotton to obtain the seed liquid. S3: 4g of tyrosine and 250mL of AE fermentation medium were sterilized and mixed separately, and the mixture was inoculated into the seed culture at an inoculation rate of 8%. The mixture was then continuously cultured in a constant temperature shaking incubator at 30℃ and 120r / min for 96h to obtain bacterial cellulose microspheres rich in tyrosine. S4: Water was added to the bacterial cellulose microspheres rich in tyrosine, and curcumin was added. The mixture was stirred for 10min. The amount of curcumin added was 0.8% of the bacterial cellulose microspheres rich in tyrosine. S5: Place in a nitrogen atmosphere and react under 467nm blue LED light for 10 minutes; S6: Remove, soak and wash with running water, then wash with deionized water, dry, and screen to obtain double cross-linked tyrosine-bacterial cellulose microspheres. The particle size of the double-crosslinked tyrosine-bacterial cellulose microspheres is 0.1-1 mm. The absorbance of Congo red (CR) at its maximum absorption wavelength of 500 nm was determined using a UV spectrophotometer via the residual liquid method. The adsorption capacity of the double-crosslinked tyrosine-bacterial cellulose microspheres for Congo red was calculated. The initial mass concentration of Congo red in the dye was 800 mg / L. The recovery rate of the double-crosslinked tyrosine-bacterial cellulose microspheres after use was also calculated. The results are shown in Table 1 below. Table 1 As shown in Table 1 above, although the adsorption capacity of the double cross-linked tyrosine-bacterial cellulose microspheres for Congo red is relatively high, their reusability is very poor, with a recovery rate of only about 25%. The double cross-linked tyrosine-bacterial cellulose microspheres prepared in Example 3 were used for subsequent experiments. Example 10 The preparation method of hydrolyzed peach gum is as follows: (1) After cleaning the peach gum, freeze-dry it, grind it in a mortar and pestle, and pass it through a 300-mesh sieve to obtain peach gum powder; (2) Mix 3g of peach gum powder, 0.02g of NaOH and 80mL of deionized water, and stir at 85℃ for 45min; (3) Add dilute hydrochloric acid until the solution is neutral, cool to room temperature, seal, and freeze dry to obtain hydrolyzed peach gum. Example 11 A method for preparing a superadsorption material includes the following steps: Step 1: Mix 6g of hydrolyzed peach gum, 3g of double cross-linked tyrosine-bacterial cellulose microspheres and 2g of activated sludge evenly to obtain a mixture, add 220g of deionized water and stir for 30min; Step 2: Dry in a 60℃ forced-air dryer for 24 hours; Step 3: After absorbing water in deionized water for 12 hours, freeze-dry to obtain an aerogel; Step 4: Place the aerogel in deionized water, add 0.2 mmol / g sodium bromide of the aerogel and 0.4 mmol / g 2,2,6,6-tetramethylpiperidine oxide of the aerogel, and stir for 10 min; Step 5: Add 15 mmol / g sodium hypochlorite of aerogel and add sodium hydroxide aqueous solution to maintain the pH between 10.0 and 10.5, and stir for 6 hours; Step 6: Pour in ethanol to terminate the reaction, and wash with 0.1 mol / L hydrochloric acid aqueous solution and deionized water successively until neutral; Step 7: Freeze-dry to obtain the superadsorbent material. Example 12 A method for preparing a superadsorption material includes the following steps: Step 1: Mix 6g of hydrolyzed peach gum, 4g of double cross-linked tyrosine-bacterial cellulose microspheres and 2g of activated sludge evenly to obtain a mixture, add 240g of deionized water and stir for 30min; Step 2: Dry in a 60℃ forced-air dryer for 24 hours; Step 3: After absorbing water in deionized water for 12 hours, freeze-dry to obtain an aerogel; Step 4: Place the aerogel in deionized water, add 0.2 mmol / g sodium bromide of the aerogel and 0.4 mmol / g 2,2,6,6-tetramethylpiperidine oxide of the aerogel, and stir for 10 min; Step 5: Add 15 mmol / g sodium hypochlorite of aerogel and add sodium hydroxide aqueous solution to maintain the pH between 10.0 and 10.5, and stir for 6 hours; Step 6: Pour in ethanol to terminate the reaction, and wash with 0.1 mol / L hydrochloric acid aqueous solution and deionized water successively until neutral; Step 7: Freeze-dry to obtain the superadsorbent material. Example 13 A method for preparing a superadsorption material includes the following steps: Step 1: Mix 6g of hydrolyzed peach gum, 5g of double cross-linked tyrosine-bacterial cellulose microspheres and 2g of activated sludge evenly to obtain a mixture, add 260g of deionized water and stir for 30min; Step 2: Dry in a 60℃ forced-air dryer for 24 hours; Step 3: After absorbing water in deionized water for 12 hours, freeze-dry to obtain an aerogel; Step 4: Place the aerogel in deionized water, add 0.2 mmol / g sodium bromide of the aerogel and 0.4 mmol / g 2,2,6,6-tetramethylpiperidine oxide of the aerogel, and stir for 10 min; Step 5: Add 15 mmol / g sodium hypochlorite of aerogel and add sodium hydroxide aqueous solution to maintain the pH between 10.0 and 10.5, and stir for 6 hours; Step 6: Pour in ethanol to terminate the reaction, and wash with 0.1 mol / L hydrochloric acid aqueous solution and deionized water successively until neutral; Step 7: Freeze-dry to obtain the superadsorbent material. Example 14 A method for preparing a superadsorption material includes the following steps: Step 1: Mix 6g of hydrolyzed peach gum, 5g of double cross-linked tyrosine-bacterial cellulose microspheres and 2g of activated sludge evenly to obtain a mixture, add 260g of deionized water and stir for 30min; Step 2: Dry in a 60℃ forced-air dryer for 24 hours; Step 3: After absorbing water in deionized water for 12 hours, freeze-dry to obtain an aerogel; Step 4: Place the aerogel in deionized water, add 0.2 mmol / g sodium bromide of the aerogel and 0.2 mmol / g 2,2,6,6-tetramethylpiperidine oxide of the aerogel, and stir for 10 min; Step 5: Add 15 mmol / g sodium hypochlorite of aerogel and add sodium hydroxide aqueous solution to maintain the pH between 10.0 and 10.5, and stir for 6 hours; Step 6: Pour in ethanol to terminate the reaction, and wash with 0.1 mol / L hydrochloric acid aqueous solution and deionized water successively until neutral; Step 7: Freeze-dry to obtain the superadsorbent material. Example 15 A method for preparing a superadsorption material includes the following steps: Step 1: Mix 6g of hydrolyzed peach gum, 5g of double cross-linked tyrosine-bacterial cellulose microspheres and 2g of activated sludge evenly to obtain a mixture, add 260g of deionized water and stir for 30min; Step 2: Dry in a 60℃ forced-air dryer for 24 hours; Step 3: After absorbing water in deionized water for 12 hours, freeze-dry to obtain an aerogel; Step 4: Place the aerogel in deionized water, add 0.2 mmol / g sodium bromide of the aerogel and 0.5 mmol / g 2,2,6,6-tetramethylpiperidine oxide of the aerogel, and stir for 10 min; Step 5: Add 15 mmol / g sodium hypochlorite of aerogel and add sodium hydroxide aqueous solution to maintain the pH between 10.0 and 10.5, and stir for 6 hours; Step 6: Pour in ethanol to terminate the reaction, and wash with 0.1 mol / L hydrochloric acid aqueous solution and deionized water successively until neutral; Step 7: Freeze-dry to obtain the superadsorbent material. Example 16 A method for preparing a superadsorption material includes the following steps: Step 1: Mix 6g of hydrolyzed peach gum, 5g of double cross-linked tyrosine-bacterial cellulose microspheres and 2g of activated sludge evenly to obtain a mixture, add 260g of deionized water and stir for 30min; Step 2: Dry in a 60℃ forced-air dryer for 24 hours; Step 3: After absorbing water in deionized water for 12 hours, freeze-dry to obtain an aerogel; Step 4: Place the aerogel in deionized water, add 0.2 mmol / g sodium bromide of the aerogel and 0.4 mmol / g 2,2,6,6-tetramethylpiperidine oxide of the aerogel, and stir for 10 min; Step 5: Add 10 mmol / g sodium hypochlorite of aerogel and add sodium hydroxide aqueous solution to maintain the pH between 10.0 and 10.5, and stir for 6 hours; Step 6: Pour in ethanol to terminate the reaction, and wash with 0.1 mol / L hydrochloric acid aqueous solution and deionized water successively until neutral; Step 7: Freeze-dry to obtain the superadsorbent material. Example 17 A method for preparing a superadsorption material includes the following steps: Step 1: Mix 6g of hydrolyzed peach gum, 5g of double cross-linked tyrosine-bacterial cellulose microspheres and 2g of activated sludge evenly to obtain a mixture, add 260g of deionized water and stir for 30min; Step 2: Dry in a 60℃ forced-air dryer for 24 hours; Step 3: After absorbing water in deionized water for 12 hours, freeze-dry to obtain an aerogel; Step 4: Place the aerogel in deionized water, add 0.2 mmol / g sodium bromide of the aerogel and 0.4 mmol / g 2,2,6,6-tetramethylpiperidine oxide of the aerogel, and stir for 10 min; Step 5: Add 20 mmol / g sodium hypochlorite of aerogel, and add sodium hydroxide aqueous solution to maintain the pH between 10.0 and 10.5, and stir for 6 hours; Step 6: Pour in ethanol to terminate the reaction, and wash with 0.1 mol / L hydrochloric acid aqueous solution and deionized water successively until neutral; Step 7: Freeze-dry to obtain the superadsorbent material. Comparative Example 3 The difference between this comparative example and Example 13 is that no activated sludge is added, as detailed below: A method for preparing a superadsorption material includes the following steps: Step 1: Mix 6g of hydrolyzed peach gum and 5g of double cross-linked tyrosine-bacterial cellulose microspheres evenly to obtain a mixture, add 260g of deionized water, and stir for 30 minutes; Step 2: Dry in a 60℃ forced-air dryer for 24 hours; Step 3: After absorbing water in deionized water for 12 hours, freeze-dry to obtain an aerogel; Step 4: Place the aerogel in deionized water, add 0.2 mmol / g sodium bromide of the aerogel and 0.4 mmol / g 2,2,6,6-tetramethylpiperidine oxide of the aerogel, and stir for 10 min; Step 5: Add 15 mmol / g sodium hypochlorite of aerogel and add sodium hydroxide aqueous solution to maintain the pH between 10.0 and 10.5, and stir for 6 hours; Step 6: Pour in ethanol to terminate the reaction, and wash with 0.1 mol / L hydrochloric acid aqueous solution and deionized water successively until neutral; Step 7: Freeze-dry to obtain the superadsorbent material. Comparative Example 4 The difference between this comparative example and Example 13 is that the sodium bromide-2,2,6,6-tetramethylpiperidine oxide-sodium hypochlorite oxidation system is not used, as detailed below: A method for preparing an aerogel includes the following steps: Step 1: Mix 6g of hydrolyzed peach gum, 5g of double cross-linked tyrosine-bacterial cellulose microspheres and 2g of activated sludge evenly to obtain a mixture, add 260g of deionized water and stir for 30min; Step 2: Dry in a 60℃ forced-air dryer for 24 hours; Step 3: After absorbing water in deionized water for 12 hours, freeze-dry to obtain aerogel. Performance testing: The absorbance of Congo red (CR) at its maximum absorption wavelength of 500 nm was determined using a UV spectrophotometer via the residual liquid method. The adsorption capacity of the double-crosslinked tyrosine-bacterial cellulose microspheres for Congo red was calculated. The initial mass concentration of Congo red in the dye was 800 mg / L. The adsorption capacities of Examples 13 and 3 (Comparative Example 3) at different times were measured. 3 L of an 800 mg / L Congo red solution (adjusted to pH = 4) was prepared, and 1 g of superadsorption material was added. The solution was placed in a shaking water bath at 55°C for adsorption. The absorbance of the filtrate was measured between 0 and 150 min, and the adsorption capacity of Congo red at different times was calculated. Figure 1 As shown: The recovery rate of the double-crosslinked tyrosine-bacterial cellulose microspheres after use was calculated, and the results are shown in Table 2 below. Table 2 Adsorption capacity (mg / g superadsorption material) Recovery rate (%) Example 11 827.9 92.6 Example 12 846.6 93.1 Example 13 864.5 93.0 Example 14 846.9 92.8 Example 15 864.9 92.9 Example 16 859.8 93.1 Example 17 860.0 93.0 Comparative Example 3 851.7 92.0 Comparative Example 4 801.3 92.6 The above embodiments are provided to clearly and completely describe the technical solution and represent some, but not all, implementations of the present invention. However, the implementations of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention should be considered equivalent substitutions and are included within the protection scope of the present invention.

Claims

1. A super absorbent material, characterized in that: The super absorbent material is an aerogel with double cross-linked tyrosine-bacterial cellulose microspheres fixed inside; The particle size of the double-crosslinked tyrosine-bacterial cellulose microspheres is 0.1-1 mm.

2. A super absorbent material according to claim 1, characterized in that: The preparation method of the double-crosslinked tyrosine-bacterial cellulose microspheres comprises the following steps: S1: Transfer the xylinobacterium Gluconacetobacter P1 strain to the seed culture medium, place it in a 30℃ incubator, adjust the speed to 160r / min and shake culture for 24h, then dilute and spread it on a solid plate, and continue to culture at 30℃ for 3d; S2: Use an inoculation loop to scrape two loops of colonies from the solid plate and transfer them to 30 mL of seed culture medium. After culturing in a 30°C incubator for 24 hours, filter with sterile cotton wool to obtain seed solution. S3: 2-5 g of tyrosine and 250 mL of AE fermentation medium were sterilized and mixed, and the seed solution was inoculated at an inoculation rate of 8%, and the mixture was continuously cultured in a constant temperature shaking incubator at 30° C. and 120 r / min for 48-96 h to obtain tyrosine-rich bacterial cellulose microspheres; S4: Take the tyrosine-rich bacterial cellulose microspheres, add water, add curcumin and L-arginine, and stir for 5-10 minutes; S5: Place in nitrogen atmosphere and react under 467nm blue light LED for 8-10 minutes; S6: taking out, immersing and washing with running water, then washing with deionized water, drying, and screening to obtain double-cross-linked tyrosine-bacterial cellulose microspheres.

3. A super absorbent material according to claim 2, characterized in that: The added amount of curcumin is 0.5-1.0% of the tyrosine-rich bacterial cellulose microspheres.

4. A super absorbent material according to claim 2, characterized in that: The mass ratio of the curcumin to L-arginine is 3:(0.5-2).

5. A method for preparing a super absorbent material according to any one of claims 1 to 4, characterized in that: The following steps are involved: Step 1: Mix the hydrolyzed peach gum, double-crosslinked tyrosine-bacterial cellulose microspheres and activated sludge to obtain a mixture, add deionized water 20 times the mass of the mixture, and stir for 30 minutes; Step 2: Dry in a 60°C air dryer for 24 hours; Step 3: Place the mixture in deionized water and absorb water for 12 hours, then freeze-dry it to obtain aerogel; Step 4: Place the aerogel in deionized water, add sodium bromide and 2,2,6,6-tetramethylpiperidinyl oxide and stir for 5-10 minutes; Step 5: Add sodium hypochlorite and sodium hydroxide aqueous solution to maintain the pH between 10.0 and 10.5, and stir for 6 hours; Step 6: Pour ethanol to terminate the reaction, and wash with 0.1 mol / s hydrochloric acid aqueous solution and deionized water in sequence until neutral; Step 7: Freeze-dry to obtain the super absorbent material.

6. The method for preparing a super absorbent material according to claim 5, characterized in that: The mass ratio of the hydrolyzed peach gum, double-cross-linked tyrosine-bacterial cellulose microspheres and activated sludge is 6:(3-5):

2.

7. The method for preparing a super absorbent material according to claim 5, characterized in that: The preparation method of described hydrolyzed peach gum is as follows: (1) Clean the peach gum, freeze-dry it, grind it with a mortar, and pass it through a 300-mesh sieve to obtain peach gum powder; (2) Mix 3 g peach gum powder, 0.02 g NaOH and 80 mL deionized water and stir at 85 °C for 45 min; (3) Add dilute hydrochloric acid until the solution is neutral, cool to room temperature, seal, and freeze-dry to obtain hydrolyzed peach gum.

8. The method for preparing a super absorbent material according to claim 5, characterized in that: In the step 4, the amount of sodium bromide added is 0.2 mmol / g aerogel, and the amount of 2,2,6,6-tetramethylpiperidinyl oxide added is 0.2-0.5 mmol / g aerogel.

9. The method for preparing a super absorbent material according to claim 5, characterized in that: The amount of sodium hypochlorite added in step 5 is 10-20 mmol / g aerogel.

10. Use of a super absorbent material according to any one of claims 1 to 4 in the adsorption of Congo red.

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