PREPARATION METHOD AND APPLICATION OF POROUS HYDROGEL ADSORBENT BASED ON RADIX ASTRAGALI RESIDUE

Abstract

The present disclosure provides a preparation method of a porous hydrogel adsorbent based on Radix Astragali residues, including the following steps: subjecting residues of Chinese herbal medicine Radix Astragali as a precursor to bleaching with NaClO.sub.2, alkaline washing with KOH, and high power ultrasonic treatment, thereby obtaining a precursor solution of uniformly dispersed cellulose nanofibers (CNFs); adding the precursor solution of CNFs to a mixed solution of N,N′-methylene bisacrylamide (MBA), acrylic acid (AA) and ammonium persulfate (APS), shaking evenly, and initiating a polymerization reaction at a predetermined temperature to form a monolithic gel; and cleaning the monolithic gel, putting the cleaned monolithic gel into a dimethyl sulfoxide (DMSO) solution containing epichlorohydrin to allow reaction, and transferring the product of the reaction to an aqueous sodium hydroxide solution containing triethylene tetramine to allow reaction, thereby finally obtaining an amino-functionalized porous hydrogel adsorbent.

Claims

1. A preparation method of a porous hydrogel adsorbent based on Radix Astragali residues, comprising the following steps: subjecting residues of Chinese herbal medicine Radix Astragali as a precursor to bleaching with NaClO.sub.2, alkaline washing with KOH, and high power ultrasonic treatment, obtaining a precursor solution of uniformly dispersed cellulose nanofibers (CNFs); adding the precursor solution of CNFs to a mixed solution of N,N′-methylene bisacrylamide (MBA), acrylic acid (AA) and ammonium persulfate (APS), shaking evenly, and initiating a polymerization reaction at a predetermined temperature to form a monolithic gel; and cleaning the monolithic gel, putting the cleaned monolithic gel into a dimethyl sulfoxide (DMSO) solution containing epichlorohydrin to allow reaction, and transferring the product of the reaction to an aqueous sodium hydroxide solution containing triethylene tetramine to allow reaction, thereby finally obtaining an amino-functionalized porous hydrogel adsorbent.

2. The preparation method of a porous hydrogel adsorbent based on Radix Astragali residues according to claim 1, comprising the following steps: (1) preparation of the precursor solution of CNFs: adding Radix Astragali residue powder to a NaClO.sub.2 solution, stirring at a predetermined temperature to remove lignin in the Radix Astragali residues, removing supernatant after settling of particles, adding the treated Radix Astragali residue particles to a strongly alkaline KOH solution, stirring at a set temperature to remove hemicellulose in the Radix Astragali residues and obtain white Radix Astragali residue cellulose pulp, washing the pulp to obtain neutral pulp, preparing a cellulose suspension, and subjecting the cellulose suspension to high power ultrasonic treatment to obtain the precursor solution of uniformly dispersed CNFs; (2) preparation of CNFs/polyacrylic acid (PAA) hydrogel adsorbent: adding the CNFs to the mixed solution of N,N′-methylene bisacrylamide, acrylic acid and ammonium persulfate, shaking evenly, and initiating a free radical polymerization reaction in a drying oven to obtain the CNFs/PAA hydrogel adsorbent; and (3) preparation of an NH.sub.2-CNFs/PAA hydrogel adsorbent: cleaning the CNFs/PAA hydrogel to remove impurities, cutting the hydrogel into slices, putting the slices into the DMSO solution containing epichlorohydrin to allow reaction, and transferring the product of the reaction to the aqueous sodium hydroxide solution containing triethylene tetramine to allow reaction, thereby finally obtaining the porous hydrogel adsorbent NH.sub.2-CNFs/PAA.

3. The preparation method of a porous hydrogel adsorbent based on Radix Astragali residues according to claim 2, wherein step (1) comprises the following specific steps: adding 5 g of the Radix Astragali residue powder to 100 mL of the NaClO.sub.2 solution at a mass concentration of 1-10 wt %, stirring in a water bath kettle at a temperature of 70° C. to 80° C. for 2 to 3 hours, taking out the mixture for standing for 1 to 10 minutes after the yellow powder turns white, directly removing the supernatant, adding 100 mL of 1-10 wt % aqueous KOH solution to the precipitate, stirring for 1 to 3 hours at an adjusted water bath temperature of 85° C. to 95° C. to obtain a white suspension, transferring the white suspension to a Buchner funnel for filtration, washing until the supernatant in the Buchner funnel is neutral, transferring the filter cake to 100 mL of deionized water and shaking evenly, and performing ultrasonic treatment on the neutral white suspension using an ultrasonic cell disruptor with ultrasonic power of 1200 W*90% for 0.5 to 2 hours, thereby obtaining a thick precursor solution of uniformly dispersed CNFs.

4. The preparation method of a porous hydrogel adsorbent based on Radix Astragali residues according to claim 3, wherein the precursor solution of CNFs has a mass concentration of 0.5-10 wt %.

5. The preparation method of a porous hydrogel adsorbent based on Radix Astragali residues according to claim 4, wherein the precursor solution of CNFs has a mass concentration of 5 wt %.

6. The preparation method of a porous hydrogel adsorbent based on Radix Astragali residues according to claim 2, wherein step (2) comprises the following specific steps: weighing and putting 20 mg of MBA powder into a centrifuge tube, adding 600 μL of AA monomer to the centrifuge tube to dissolve the MBA which is used as a crosslinking agent, followed by sequentially adding 3 mL of the solution of CNFs and 5 mg of APS powder to the centrifuge tube, mixing evenly by shaking, placing the centrifuge tube in the drying oven at a temperature of 50° C. to 70° C. to allow reaction for 2 to 6 hours, thereby obtaining a columnar CNFs/PAA hydrogel adsorbent material.

7. The preparation method of a porous hydrogel adsorbent based on Radix Astragali residues according to claim 2, wherein step (3) comprises the following specific steps: washing the CNFs/PAA gel with deionized water to remove unreacted reagents on the surface thereof, followed by cutting the gel into slices, adding 0.6 mL of CNFs/PAA to 2 mL of the DMSO solution containing 0.1 g of NaOH and 0.15 mL of epichlorohydrin to allow reaction at a temperature of 50° C. to 70° C. for 0.5 to 2 hours, and adding the product of the reaction to 2 mL of the aqueous sodium hydroxide solution containing 0.2 mL of triethylene tetramine to allow reaction at a temperature of 50° C. to 70° C. for 1 to 4 hours, thereby obtaining the amino-functionalized porous hydrogel adsorbent NH.sub.2-CNFs/PAA.

8. The preparation method of a porous hydrogel adsorbent based on Radix Astragali residues according to claim 7, wherein the sodium hydroxide solution containing triethylene tetramine has a mass concentration of 2-20%.

9. A porous hydrogel adsorbent prepared by the preparation method according to claim 1, wherein the porous hydrogel comprises the following components: 2-8% by mass of the CNFs, 10-20% by mass of the PAA, 1-3 mol % of the MBA relative to the AA, and 0.1-0.5 mol % of the APS relative to the AA.

10. (canceled)

11. The porous hydrogel adsorbent according to claim 9, comprising the following steps: (1) preparation of the precursor solution of CNFs: adding Radix Astragali residue powder to a NaClO.sub.2 solution, stirring at a predetermined temperature to remove lignin in the Radix Astragali residues, removing supernatant after settling of particles, adding the treated Radix Astragali residue particles to a strongly alkaline KOH solution, stirring at a set temperature to remove hemicellulose in the Radix Astragali residues and obtain white Radix Astragali residue cellulose pulp, washing the pulp to obtain neutral pulp, preparing a cellulose suspension, and subjecting the cellulose suspension to high power ultrasonic treatment to obtain the precursor solution of uniformly dispersed CNFs; (2) preparation of CNFs/polyacrylic acid (PAA) hydrogel adsorbent: adding the CNFs to the mixed solution of N,N′-methylene bisacrylamide, acrylic acid and ammonium persulfate, shaking evenly, and initiating a free radical polymerization reaction in a drying oven to obtain the CNFs/PAA hydrogel adsorbent; and (3) preparation of an NH.sub.2-CNFs/PAA hydrogel adsorbent: cleaning the CNFs/PAA hydrogel to remove impurities, cutting the hydrogel into slices, putting the slices into the DMSO solution containing epichlorohydrin to allow reaction, and transferring the product of the reaction to the aqueous sodium hydroxide solution containing triethylene tetramine to allow reaction, thereby finally obtaining the porous hydrogel adsorbent NH.sub.2-CNFs/PAA.

12. The porous hydrogel adsorbent according to claim 11, wherein step (1) comprises the following specific steps: adding 5 g of the Radix Astragali residue powder to 100 mL of the NaClO.sub.2 solution at a mass concentration of 1-10 wt %, stirring in a water bath kettle at a temperature of 70° C. to 80° C. for 2 to 3 hours, taking out the mixture for standing for 1 to 10 minutes after the yellow powder turns white, directly removing the supernatant, adding 100 mL of 1-10 wt % aqueous KOH solution to the precipitate, stirring for 1 to 3 hours at an adjusted water bath temperature of 85° C. to 95° C. to obtain a white suspension, transferring the white suspension to a Buchner funnel for filtration, washing until the supernatant in the Buchner funnel is neutral, transferring the filter cake to 100 mL of deionized water and shaking evenly, and performing ultrasonic treatment on the neutral white suspension using an ultrasonic cell disruptor with ultrasonic power of 1200 W*90% for 0.5 to 2 hours, thereby obtaining a thick precursor solution of uniformly dispersed CNFs.

13. The porous hydrogel adsorbent according to claim 12, wherein the precursor solution of CNFs has a mass concentration of 0.5-10 wt %.

14. The porous hydrogel adsorbent according to claim 13, wherein the precursor solution of CNFs has a mass concentration of 5 wt %.

15. The porous hydrogel adsorbent according to claim 11, wherein step (2) comprises the following specific steps: weighing and putting 20 mg of MBA powder into a centrifuge tube, adding 600 μL of AA monomer to the centrifuge tube to dissolve the MBA which is used as a crosslinking agent, followed by sequentially adding 3 mL of the solution of CNFs and 5 mg of APS powder to the centrifuge tube, mixing evenly by shaking, placing the centrifuge tube in the drying oven at a temperature of 50° C. to 70° C. to allow reaction for 2 to 6 hours, thereby obtaining a columnar CNFs/PAA hydrogel adsorbent material.

16. The porous hydrogel adsorbent according to claim 11, wherein step (3) comprises the following specific steps: washing the CNFs/PAA gel with deionized water to remove unreacted reagents on the surface thereof, followed by cutting the gel into slices, adding 0.6 mL of CNFs/PAA to 2 mL of the DMSO solution containing 0.1 g of NaOH and 0.15 mL of epichlorohydrin to allow reaction at a temperature of 50° C. to 70° C. for 0.5 to 2 hours, and adding the product of the reaction to 2 mL of the aqueous sodium hydroxide solution containing 0.2 mL of triethylene tetramine to allow reaction at a temperature of 50° C. to 70° C. for 1 to 4 hours, thereby obtaining the amino-functionalized porous hydrogel adsorbent NH.sub.2-CNFs/PAA.

17. The porous hydrogel adsorbent according to claim 16, wherein the sodium hydroxide solution containing triethylene tetramine has a mass concentration of 2-20%.

18. Application of the porous hydrogel adsorbent according to claim 9, wherein the adsorbent is used in removal of heavy metals from wastewater.

19. Application of the porous hydrogel adsorbent according to claim 11, wherein the adsorbent is used in removal of heavy metals from wastewater.

20. Application of the porous hydrogel adsorbent according to claim 12, wherein the adsorbent is used in removal of heavy metals from wastewater.

21. Application of the porous hydrogel adsorbent according to claim 13, wherein the adsorbent is used in removal of heavy metals from wastewater.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0033] FIG. 1 shows scanning electron microscope (SEM) images of CNFs before and after ultrasonic treatment and of CNFs/PAA gel material after freeze-drying.

[0034] FIG. 2 is a graph showing the adsorption effects of CNFs/PAA gel affected by pH before and after modification (experimental conditions: C.sub.0=50 mg/L, t=10 h, T=298 K, m/V=1 g/L).

[0035] FIG. 3 is a graph showing the adsorption effects of CNFs/PAA gel affected by ionic strength before and after modification (experimental conditions: C.sub.0=50 mg/L, t=10 h, T=298 K, m/V=1 g/L).

[0036] FIG. 4 is an adsorption kinetic curve of CNFs/PAA gel to Pb(II) before and after modification at room temperature (experimental conditions: C.sub.0=50 mg/L, t=360 min, T=298 K, m/V=1 g/L).

[0037] FIG. 5 is an adsorption isothermal curve of CNFs/PAA gel to Pb(II) before and after modification at room temperature (experimental conditions-before modification: C.sub.0=20, 50, 100, 200, 300, 400 mg/L, t=24 h, T=298 K, m/V=1 g/L; experimental conditions-after modification: 100, 200, 300, 400, 600 mg/L, t=24 h, T=298 K, m/V=0.5 g/L).

[0038] FIG. 6 is a test chart of CNFs/PAA gel stability before and after modification (experimental conditions: C.sub.0=100 mg/L, t=10 h, T=298 K, m/V=1 g/L, 5 cycles).

[0039] The patent or application contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0040] The technical solutions in embodiments of the present disclosure will be clearly and completely described below. Apparently, the described embodiments are merely some rather than all of the embodiments of the present disclosure. All other embodiments derived from the embodiments of the present disclosure by a person of ordinary skill in the art without creative efforts should fall within the protection scope of the present disclosure.

[0041] The present disclosure will be further described below in combination with specific examples and the drawings.

Example 1: Preparation of Precursor Solutions of CNFs

[0042] (1) Bleaching with NaClO.sub.2: to dissolve different quantities of poorly soluble Radix Astragali residue powders by mass, firstly, NaClO.sub.2 solutions at different mass concentrations 1 wt %, 5 wt %, 8 wt %, and 10 wt %, each 100 mL, were put into four 250 mL beakers, denoted as I, II, III, and IV. The four beakers were placed in four water bath kettles. The temperature of all the water bath kettles was adjusted to 75° C., and then 0.5 g, 5 g, 8 g, 10 g of Radix Astragali residue powders corresponding to the mass concentrations of the NaClO.sub.2 solutions were added to the four beakers, and stirred fully for 3 to 4 hours.

[0043] (2) Alkaline washing with KOH: the beakers were taken out after the yellow powder turned white gradually and allowed to stand for 5 minutes. After the supernatant was removed, KOH solutions at different mass concentrations 1 wt %, 5 wt %, 8 wt %, and 10 wt %, each 100 mL, were added to the four beakers. The temperature of all the water bath kettles was adjusted to 90° C., and stirring was continued for 2 hours until the white particles were gradually transformed into white floccule to obtain white cellulose pulp. Experiments demonstrated that the Radix Astragali powder that had not been treated with bleaching agent NaClO.sub.2 could not be dissolved after being directly added to the strong alkali KOH and continuously stirred at 90° C. for several hours. The white cellulose pulps of four different concentrations were taken out of the water bath kettles, and after cooling to room temperature, transferred to four suction filters to remove excess KOH by suction filtration. During the process, the cellulose floccule was always maintained in a water swelling state (to prevent the formation of strong hydrogen-bond interaction (which would affect the subsequent dissolution of the cellulose) between the cellulose molecules due to too dry cellulose floccule after the suction filtration). The suction filtration was stopped after the pH of the supernatant in a Buchner funnel became neutral, and white cellulose filter cake was obtained.

[0044] (3) Ultrasonic treatment: four filter cakes different in mass (from 0.5 g, 5 g, 8 g, and 10 g of Radix Astragali residue powders) were transferred to four 250 mL tall beakers, also denoted as I, II, III, and IV. Each of the four tall beakers was added with 100 mL of deionized water and shaken to make the cellulose cake evenly dispersed. After standing for about 5 minutes, aggregation of the cellulose molecules occurred. The tall beakers were shaken again to make the cellulose molecules dispersed for a short time before the ultrasonic treatment. The tall beakers I, II, III, and IV were sequentially placed in a 1000 mL large beaker, and an appropriate amount of ice-water mixture was added to the large beaker to provide an ice bath environment. The tall beakers were fixed by using foam molds, and then the 1000 mL large beaker was transferred to a soundproof box of an ultrasonic cell disruptor and adjusted in height. Subsequently, high power ultrasonic treatment was started with the power of 1200 W*90% and lasted for 1 hour. During the ultrasonic treatment, the ice-water mixture in the large beaker was replaced timely to control the temperature within the normal working temperature range of the ultrasonic cell disruptor. After the ultrasonic treatment was completed, CNFs solutions at the mass concentrations of 0.5 wt %, 5 wt %, 8 wt %, and 10 wt % (measured based on the amount of the used raw material) were obtained in the tall beakers I, II, III, and IV, and all could be stable against aggregation for a long time.

[0045] Experiments demonstrated that when the tall beakers I, II, III, and IV were placed in an ordinary ultrasonic apparatus (maximum power 600 W) for ultrasonic treatment under the maximum ultrasonic power, the cellulose molecules could not be effectively dissolved in deionized water after ultrasonic treatment for a long time (>72 hours), indicating that the cell disruptor played a decisive role in the process of dissolving the cellulose molecules.

Example 2: Preparation of CNFs/PAA Hydrogel Adsorbent Materials

[0046] To each of four 5 mL centrifuge tubes, 20 mg of MBA powder was weighed and added, and 600 μL of acrylic acid monomer was added to each of the four centrifuge tubes by using a pipette to dissolve the crosslinking agent MBA. Then, 3 mL of CNFs solution was transferred from each of the tall beakers I, II, III, and IV to the corresponding centrifuge tube. Finally, 5 mg of APS powder was added to each of the four centrifuge tubes. The centrifuge tubes were shaken fully to make the mixtures therein mixed evenly. The four centrifuge tubes were placed in a drying oven at 60° C. for reaction for 4 hours, thereby obtaining four columnar CNFs/PAA dual-network hydrogel adsorbent materials, denoted as CNFs/PAA-1, CNFs/PAA-2, CNFs/PAA-3, and CNFs/PAA-4.

[0047] Preparation of H.sub.2O/PAA hydrogel material: to a 5 mL centrifuge tube, 20 mg of MBA powder, 3 mL of H.sub.2O, 600 μL of AA monomer, and 5 mg of APS powder were added, shaken evenly, and placed in the drying oven at 60° C. to allow reaction for 4 hours, thereby obtaining a columnar transparent H.sub.2O/PAA gel.

[0048] The four CNFs/PAA gels in Example 2 were compared with the H.sub.2O/PAA gel by using a universal tester, and the results showed that the mechanical properties of these gels were ranked as follows: H.sub.2O/PAA<CNFs/PAA-1<CNFs/PAA-2≈CNFs/PAA-3≈CNFs/PAA-4, indicating that with the introduction of CNFs, the mechanical properties of the gels were enhanced, and with increasing concentration of the CNFs solutions, the mechanical properties would gradually increase first and then become stable.

Example 3: Preparation of NH.SUB.2.-CNFs/PAAs

[0049] CNFs/PAA having a cellulose content of 5 wt % was selected as the material to be modified, cut into slices, and added to 2 mL of DMSO solution containing 0.1 g of NaOH and 0.15 mL of epichlorohydrin in a ratio of 2 mL DMSO per 0.6 mL to allow reaction at 60° C. for 1 hour. After the reaction was completed, the product of the reaction was to NaOH aqueous solutions containing 0.2 mL of triethylene tetramine at concentrations of 2 wt %, 7 wt %, 12 wt %, 16 wt %, and 20 wt %, each for 2 mL, to allow reaction at 60° C. for 2 hours, obtaining NH.sub.2-CNFs/PAA-1, NH.sub.2-CNFs/PAA-2, NH.sub.2-CNFs/PAA-3, NH.sub.2-CNFs/PAA-4, and NH.sub.2-CNFs/PAA-5, respectively. The resulting materials were ranked according to their mechanical properties in the following order: NH.sub.2-CNFs/PAA-1>NH.sub.2-CNFs/PAA-2≈NH.sub.2-CNFs/PAA-3≈NH.sub.2-CNFs/PAA-4>>NH.sub.2-CNFs/PAA-5. The adsorption capacities of the resulting materials were 525 mg/g, 900 mg/g, 900 mg/g, 900 mg/g, and 950 mg/g.

[0050] To sum up, to prepare the precursor solution of CNFs at the best concentration and the dual-network gel structure with the best mechanical properties and the best adsorption effect, the following three points need to be paid attention to: 1) the use of the bleaching agent before the alkaline washing; 2) the high power ultrasonic treatment of the cellulose pulp pretreated by bleaching and alkaline washing; and 3) the selection of the optimal concentration of the solution of CNFs and the optimal alkali concentration required for modification.

[0051] First, the key point 1, namely the use of the bleaching agent, is explained as follows: a large number of experiments have proved that the Radix Astragali residue powder cannot be effectively dissolved by using the direct one-step alkaline dissolution method. Therefore, to effectively dissolve it, this study uses bleaching-alkaline washing for the first time to pretreat the Radix Astragali residue powder. The Radix Astragali residue powder treated by bleaching (i.e., with NaClO.sub.2) can be initially dissolved in an alkaline solution (i.e., KOH). In the above experiment, the NaClO.sub.2 solutions at the concentrations of 1 wt %, 5 wt %, 8 wt %, and 10 wt % were used to bleach 0.5 g, 5 g, 8 g, and 10 g of Radix Astragali powders, respectively. After bleaching, the bleaching solutions were removed, and KOH solutions at the mass concentrations of 1 wt %, 5 wt %, 8 wt %, and 10 wt % were added. The bleaching effect can be achieved by correspondingly increasing the concentrations of the bleaching agent and the alkaline solution with increasing amount of the Radix Astragali powder. The cellulose obtained after bleaching and alkaline washing was prone to aggregation. The specific manifestation was that the above-mentioned cellulose pulps settled within 5 minutes regardless of the initial concentration. To resolve the technical difficulty of easy settlement of the cellulose pulp, this study introduced the high power ultrasound technology for the first time to perform cell disruption on the solutions of CNFs at different concentrations of 0.5 wt %, 5 wt %, 8 wt %, and 10 wt %, thereby obtaining stable solutions of uniformly dispersed CNFs. It was observed through experiments that the CNFs that had been subjected to bleaching, alkaline washing and high power ultrasonic treatment did not settle after a week or even a month. For the selection of the optimal cellulose solution concentration, by comparing the mechanical properties of the dual-network hydrogels synthesized with CNFs at different initial concentrations, it could be concluded that when the concentration of the solution of CNFs was greater than or equal to 5 wt %, the mechanical properties of the gel basically were longer improved with the increase of the concentration. When the concentration of the solution of CNFs was less than or equal to 5 wt %, the mechanical properties of the gel were improved significantly with the increase of the cellulose concentration. When the 5 wt % solution of CNFs was used, the raw material could be saved and the required strength and effect of the material could be achieved. Therefore, it was concluded that 5 wt % was the optimal concentration of the solution of CNFs for preparing the dual-network hydrogel adsorbent material. By comparing the properties of the dual-network hydrogels obtained by modifying the CNFs/PAA with different alkali concentrations, it could be concluded that with the increase of the alkali concentration, the adsorption performance of the gel was significantly improved, and the mechanical properties were slightly reduced. When the alkali concentration was greater than or equal to 7 wt %, the adsorption capacity gradually tended to be saturated. When the alkali concentration was greater than or equal to 16 wt %, the mechanical properties were significantly reduced, and the adsorption performance was not significantly improved. Therefore, it could be concluded that the NH.sub.2-CNFs/PAA obtained through modification with the alkali concentration of 7 wt %-16 wt % had the best overall performance.

[0052] FIG. 1 shows the SEM images of CNFs before and after ultrasonic treatment and of CNFs/PAA gel material after freeze-drying. From FIG. 1a (before ultrasonic treatment) and FIG. 1b (after ultrasonic treatment), it can be seen that the CNFs after the ultrasonic treatment were successfully dispersed from the original aggregation state. From FIG. 1c, it can be seen that the CNFs/PAA gel had a three-dimensional porous network structure, which was beneficial to the diffusion process of heavy metal ions in the solution in the gel system. Meanwhile, the adsorption sites on the polymer chains could be effectively exposed, allowing heavy metal ions to form a coordination structure with the gel and be adsorbed on the gel more easily.

[0053] FIG. 2 is a graph showing the adsorption effects of CNFs/PAA gel affected by pH before and after modification. It can be seen from FIG. 2 that for CNFs/PAA gel, when the pH value was less than or equal to 2, the CNFs/PAA gel had almost no effect on Pb (II). With the increase of pH, the adsorption of Pb (II) by the CNFs/PAA gel increased rapidly, and the adsorption rate of Pb (II) with C.sub.0 of 50 mg/L could be about 83%. For NH.sub.2-CNFs/PAA, when the pH was greater than 2, 100% adsorption could be achieved, indicating that the introduction of amino groups significantly improved the adsorption performance of the material.

[0054] FIG. 3 is a graph showing the adsorption performance of CNFs/PAA gel under different ionic strength conditions before and after modification. It can be seen from the figure that when the ionic strength was increased to 0.1 mol/L, it had a greater impact on the adsorption performance of the CNFs/PAA gel to Pb (II) before and after the modification. Further, the ionic strength had higher impact on the CNFs/PAA gel after the modification than before the modification, indicating that the introduction of amino groups successfully reduced the influences of environmental factors on the material. Moreover, the influence of divalent cations (such as Ca (II), Mg (II)) on adsorption was more significant than that of monovalent cations (such as K(I), Na(I)). The four metal ions were ranked according to their influences on the adsorption process as follows: Mg (II)>Ca (II)>K (I)≈Na (I). This ranking was consistent with their electronegativity ranking (Mg=1.31, Ca=1.00, Na=0.93, K=0.82). The ion with higher electronegativity could compete with Pb (II) for adsorption and electrostatic repulsion, thus reducing its activity coefficient. As a result, the adsorption capability of the CNFs/PAA gel to Pb (II) was reduced.

[0055] FIG. 4 is an adsorption kinetic curve of CNFs/PAA gel to Pb (II) before and after modification at room temperature. It can be seen from the figure that before and after the modification, the CNFs/PAA gel took about 200 and 30 minutes to reach the adsorption equilibrium to Pb (II), and the adsorption rates were about 95% and 100%, respectively. This was mainly attributed to the three-dimensional porous network structure of the surface of the CNFs/PAA gel, which was conducive to the diffusion of metal ions inside the gel and avoided blocking of adsorption sites. It can be seen from the figure that the kinetic adsorption process of the CNFs/PAA gel to Pb (II) conformed to the pseudo-first-order kinetic fitting, indicating that the adsorption process of the CNFs/PAA gel was only related to the concentration of metal ions in the solution. Competitive adsorption among ions could be ignored.

[0056] FIG. 5 is an adsorption isothermal curve of CNFs/PAA gel to Pb (II) before and after modification at room temperature. It can be seen from the figure that the adsorption capacity was increased with the increase of the concentration of metal ions in the solution, and the adsorption equilibrium was achieved at a higher concentration. Further fitting analysis of the adsorption thermodynamic data showed that the adsorption process of the CNFs/PAA gel followed the classic Langmuir model, indicating that the adsorption of heavy metal ions onto the CNFs/PAA gel was a single-layer adsorption process and tended to be a chemical adsorption process involving electron transfer. The fitting results of the Langmuir model showed that the maximum theoretical adsorption capacity of the CNFs/PAA gel to Pb (II) was 160 and 900 mg/g (298 K) before and after modification, respectively.

[0057] FIG. 6 is a test chart of CNFs/PAA gel stability before and after modification (experimental conditions: C.sub.0=100 mg/L, t=10 h, T=298 K, m/V=1 g/L, 5 cycles). It can be seen from the figure that the CNFs/PAA gel modified with amino groups had good reusability.