CN111116943A - Composite cellulose nanofibril hydrogel sphere and preparation method and application thereof - Google Patents
Composite cellulose nanofibril hydrogel sphere and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a composite cellulose nanofibril hydrogel sphere and a preparation method and application thereof, belonging to the field of cellulose nanofiber composite materials. The composite cellulose nanofibril hydrogel sphere is prepared by taking cellulose nanofibril, polyvinyl alcohol, a water-soluble polymer, water and mineral oil as raw materials, forming a water-in-oil emulsion through the emulsification of a surfactant, and initiating a crosslinking reaction through a crosslinking agent, wherein the shape of the hydrogel sphere is spherical, the particle size is 0.5-4 mm, and the water content is more than 90%. The composite cellulose hydrogel ball has good heavy metal ion adsorption capacity and organic pollutant adsorption capacity, has small influence on the rheological property of sewage, can be recovered in a filtering mode, does not contain free acid, and does not influence the pH value of the treated sewage. The preparation method of the composite cellulose hydrogel spheres is simple and convenient to operate and has small environmental pollution.
Description
Technical Field
The invention relates to a cellulose composite material, in particular to a composite cellulose nanofibril hydrogel sphere and a preparation method and application thereof.
Background
In sewage treatment, organic pollutants and heavy metal ions are two main pollutants. The existing removal methods generally comprise a biodegradation method, an oxidative degradation method, a chemical precipitation method, an ion exchange method, a membrane separation method, a solvent extraction method, a reverse osmosis method and the like, and the methods usually have higher cost or bring secondary pollution, so that the exploration of a new material which is low in cost, pollution-free and can effectively remove organic pollutants and heavy metal ions in sewage is a difficult problem to be solved urgently. In recent years, natural adsorbents are attracting much attention for removing organic pollutants and heavy metal ions, such as cellulose, starch, chitosan and the like, and the materials are rich in sources, low in cost, renewable and degradable. Cellulose is an organic green material with the most abundant natural reserves, but due to the crystallinity and the association among chains, the cellulose has compact structure and poor water swelling property, and cannot be directly applied to adsorption in a water system. Generally, carboxyl is introduced by a graft modification method to improve hydrophilicity, and a hydrogel adsorbent prepared by graft copolymerization of modified cellulose and acrylic acid is commonly used for adsorption of heavy metal ions in a water system and has a good adsorption effect, but the method is complicated and the grafting efficiency is not high. In addition, the traditional gel adsorbent is irregular particles, has large flow resistance in a water environment, has obvious adverse effect on the rheological property of sewage, and is not beneficial to practical application. Therefore, it is necessary to develop an adsorbing material which has strong adsorption capacity on organic pollutants and heavy metal ions, is simple and convenient in preparation method, is environment-friendly and has little influence on rheological property of fluid.
Disclosure of Invention
The invention mainly aims to provide a composite cellulose nanofibril hydrogel sphere which has strong adsorption capacity on heavy metal ions and organic pollutants and is simple in preparation method, and a preparation method and application thereof.
The purpose of the invention is realized by the following technical scheme:
the composite cellulose nanofibril hydrogel sphere is prepared by taking cellulose nanofibril, polyvinyl alcohol, a water-soluble polymer, water and mineral oil as raw materials, forming a water-in-oil emulsion through the emulsification of a surfactant, and initiating a crosslinking reaction through a crosslinking agent, wherein the shape of the hydrogel sphere is spherical, the particle size is 0.5-4 mm, and the water content is more than 90%;
the water-soluble polymer is polymerized by three monomers of acrylic acid, methacrylic acid and 2-acrylamide-2-methylpropanesulfonic acid in an arbitrary proportion through a free radical initiated polymerization mode. The water-soluble polymer can release protons, and catalyze crosslinking reaction without additionally introducing acid in the reaction process. The water-soluble polymer is important to the particle size, the strength and the product adsorption performance of hydrogel spheres, and in a large number of research experiments, if no water-soluble polymer participates in the process of sphere forming, the particle size of the obtained product is difficult to control, aggregation is easy to occur, and the obtained gel product has low strength and poor toughness. In addition, the water-soluble polymer can remarkably improve the adsorption capacity of the hydrogel ball to heavy metal ions and organic pollutants.
The cross-linking agent is any one of glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde and adipaldehyde; the mineral oil is any one of diesel oil, white oil and liquid paraffin.
The HLB value of the surfactant is less than 8.
Preferably, the surfactant is any one of span 60, span 80 and span 85.
The cellulose nano-fibrils are made of cellulose materials with the diameter of 3-80 nm and the length of more than 1 micron.
The cellulose nano-fibrils have low cost and certain biodegradability, and the hydrogel spheres have good adsorption capacity on heavy metal ions or organic pollutants.
The preparation method of the composite cellulose nanofibril hydrogel sphere comprises the following steps:
(1) mixing 1 part by mass of polyvinyl alcohol, 0.1-0.5 part by mass of water-soluble polymer and 10-20 parts by mass of distilled water at 15-35 ℃, stirring for 2-5 hours at 80-95 ℃, naturally cooling to 15-35 ℃, adding 80 parts by mass of cellulose nanofibril water suspension, stirring for 5-30 minutes at 15-35 ℃, adding a uniform mixed solution composed of 6-10 parts by mass of surfactant and 300-500 parts by mass of mineral oil, continuously stirring for 5-10 minutes at 15-35 ℃, adding 1-10 parts by mass of a cross-linking agent aqueous solution with the mass fraction of 1.5%, continuously stirring for 0.25-1 hour at 15-35 ℃, controlling the temperature to be 45-75 ℃, stirring for 4-12 hours, and finishing the reaction;
(2) filtering the reaction solution obtained in the step (1) by using a fine sieve, soaking and filtering the obtained hydrogel spheres for 5-30 min by using 50-200 parts by mass of ethyl acetate, then filtering, soaking and filtering the obtained hydrogel spheres for 5-30 min by using 50-200 parts by mass of ethanol, then filtering, finally soaking and filtering the obtained hydrogel spheres for 5-30 min by using 50-200 parts by mass of distilled water, and then filtering to finally obtain a composite cellulose nanofibril hydrogel sphere product;
the cellulose nano-fibril water suspension in the step (1) consists of cellulose nano-fibrils and water, wherein the content of the cellulose nano-fibrils is 1.0-3.0 wt%;
the aperture size of the fine sieve in the step (2) is 0.1-0.5 mm.
Preferably, the stirring is mechanical stirring, and the stirring speed is 100-400 r/min.
The oil phase obtained by filtering the reaction solution in the step (2) consists of mineral oil and surfactant, and can be used for preparing the composite cellulose nanofibril hydrogel spheres again; the ethyl acetate and ethanol used in the step (2) can be recovered by atmospheric distillation and then reused.
The application of the composite cellulose nanofibril hydrogel sphere is used for adsorbing heavy metal ions or organic pollutants in sewage. The organic pollutants are organic phenols and organic amines.
Has the advantages that:
(1) the composite cellulose hydrogel spherical particles are uniform in diameter distribution, are distributed between 0.5mm and 4mm, have good heavy metal ion adsorption capacity and organic pollutant adsorption capacity, have small influence on rheological property of sewage, and can be recovered in a filtering mode.
(2) The preparation method of the composite cellulose hydrogel sphere is simple and convenient, has little pollution to the environment, and the mineral oil, the surfactant, the ethyl acetate, the ethanol and the like which are involved in the reaction can be reused.
(3) The composite cellulose hydrogel ball does not contain free acid, and does not influence the pH value of the treated sewage.
Detailed Description
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention.
Example 1
Mixing 1g of polyvinyl alcohol, 0.1g of polymethacrylic acid with the molecular weight of 1500000 and 10g of distilled water at the temperature of 15 ℃, stirring for 2 hours at the temperature of 80 ℃, stirring at the speed of 200r/min, naturally cooling to 15 ℃, adding 80g of cellulose nanofibril aqueous suspension with the mass fraction of 1%, stirring at the temperature of 15 ℃ for 5 minutes at the speed of 200r/min, adding a uniform mixed solution consisting of 6g of span 80 and 300g of liquid paraffin, stirring at the temperature of 15 ℃ for 5 minutes at the speed of 200r/min, adding 1g of hexanedial aqueous solution with the mass fraction of 1.5%, stirring at the temperature of 15 ℃ for 0.25 hours, stirring at the temperature of 45 ℃ for 4 hours at the speed of 200r/min, filtering the reaction solution by a 60-mesh fine sieve, soaking the filtered hydrogel spheres by 50g of ethyl acetate for 5 minutes, filtering, soaking the filtered hydrogel spheres with 50g of ethanol for 5min, filtering, soaking the filtered hydrogel spheres with 50g of distilled water for 5min, filtering, and finally obtaining the composite cellulose nanofibril hydrogel sphere product. The particle size of the obtained hydrogel spheres is 3.0-4.0 mm, and the water content is 96% when the hydrogel spheres with known mass are dried and weighed. The hydrogel balls and the clean water are mixed according to the mass ratio of 1: 24, the reading of the hydrogel balls and the clean water is 7 under the condition that the rotational speed of a viscometer rotor is 600r/min by using a six-speed viscometer, and the reading of the clean water under the condition that the rotational speed of the rotor is 600r/min by using the six-speed viscometer is 3, so that the influence of the hydrogel balls and the clean water on the viscosity of the water is small.
Example 2
Mixing 1g polyvinyl alcohol, 0.5g polyacrylic acid with molecular weight of 1000000 and 20g distilled water at 35 ℃, stirring for 5h at 95 ℃ at the stirring speed of 300r/min, naturally cooling to 35 ℃, adding 80g cellulose nanofibril water suspension with the mass fraction of 3%, stirring for 30min at 35 ℃, adding a uniform mixed solution consisting of 10g span 60 and 500g liquid paraffin, continuing to stir for 10min at 35 ℃, at the stirring speed of 300r/min, adding 10g glutaraldehyde water solution with the mass fraction of 1.5%, continuing to stir for 0.25h at 35 ℃, at the stirring speed of 300r/min, then controlling the temperature to stir for 4h at 45 ℃, at the stirring speed of 300r/min, then filtering the reaction solution by a 100-mesh fine screen, soaking the obtained hydrogel spheres for 5min by 50g ethyl acetate, then filtering, soaking the filtered hydrogel spheres with 50g of ethanol for 5min, then filtering, finally soaking the filtered hydrogel spheres with 50g of distilled water for 5min, then filtering, and finally obtaining the composite cellulose nanofibril hydrogel sphere product. The particle size of the obtained hydrogel spheres is 1.0-2.5 mm, and the water content is 96% when the hydrogel spheres with known mass are dried and weighed. The hydrogel ball is mixed with clean water according to the mass ratio of 1: 24, and the reading of the hydrogel ball is 6 by a six-speed viscometer at the rotation speed of a viscometer rotor of 600r/min, which shows that the hydrogel ball has small influence on the viscosity of the water.
Example 3
Mixing 1g of polyvinyl alcohol, 0.3g of acrylic acid/methacrylic acid copolymer (the molar ratio of acrylic acid to methacrylic acid monomer is 3: 1) with the molecular weight of 500000 and 15g of distilled water at 25 ℃, then stirring for 2h at 80 ℃ at the stirring speed of 150r/min, then naturally cooling to 25 ℃, adding 80g of cellulose nanofibril aqueous suspension with the mass fraction of 3%, stirring for 5min at 25 ℃, at the stirring speed of 150r/min, then adding a uniform mixed solution consisting of 6g of span 80 and 300g of liquid paraffin, continuing to stir for 5min at 25 ℃ at the stirring speed of 150r/min, then adding 3g of glyoxal aqueous solution with the mass fraction of 1.5%, continuing to stir for 1h at 25 ℃, at the stirring speed of 150r/min, then controlling the temperature to stir at 45 ℃ for 12h, at the stirring speed of 150r/min, and then filtering the reaction solution by using a 100-mesh fine sieve, soaking the filtered hydrogel spheres in 100g of ethyl acetate for 10min, then filtering, soaking the filtered hydrogel spheres in 100g of ethanol for 10min, then filtering, finally soaking the filtered hydrogel spheres in 100g of distilled water for 10min, then filtering, and finally obtaining the composite cellulose nanofibril hydrogel sphere product. The particle size of the obtained hydrogel spheres is 1.0-2.5 mm, and the water content is 95% by drying and weighing the hydrogel spheres with known mass. The hydrogel ball is mixed with clean water according to the mass ratio of 1: 24, and the reading of the hydrogel ball is 6 by a six-speed viscometer at the rotation speed of a viscometer rotor of 600r/min, which shows that the hydrogel ball has small influence on the viscosity of the water.
Example 4
Mixing 1g of polyvinyl alcohol, 0.5g of polymethacrylic acid with the molecular weight of 1000000 and 15g of distilled water at the temperature of 25 ℃, stirring for 2 hours at the temperature of 80 ℃, stirring at the speed of 150r/min, naturally cooling to 25 ℃, adding 80g of cellulose nanofibril aqueous suspension with the mass fraction of 3%, stirring at the temperature of 25 ℃ for 5 minutes at the speed of 150r/min, adding a uniform mixed solution consisting of 6g of span 85 and 500g of white oil, stirring at the temperature of 25 ℃ for 5 minutes at the speed of 150r/min, adding 5g of glutaraldehyde aqueous solution with the mass fraction of 1.5%, stirring at the temperature of 25 ℃ for 1 hour at the speed of 150r/min, controlling the temperature to stir at the temperature of 65 ℃ for 10 hours at the speed of 150r/min, filtering the reaction solution by a 100-mesh fine sieve, soaking the obtained hydrogel spheres by filtering with 50g of ethyl acetate for 5 minutes, then filtering, soaking the filtered hydrogel spheres with 50g of ethanol for 5min, then filtering, finally soaking the filtered hydrogel spheres with 50g of distilled water for 5min, then filtering, and finally obtaining the composite cellulose nanofibril hydrogel sphere product. The particle size of the obtained hydrogel spheres is 2.5-3.5 mm, and the water content is 95% by drying and weighing the hydrogel spheres with known mass. The hydrogel ball is mixed with clean water according to the mass ratio of 1: 24, and the reading of the hydrogel ball is 6 by a six-speed viscometer at the rotation speed of a viscometer rotor of 600r/min, which shows that the hydrogel ball has small influence on the viscosity of the water.
Example 5
Mixing 1g of polyvinyl alcohol, 0.5g of acrylic acid/methacrylic acid/2-acrylamide-2-methylpropanesulfonic acid copolymer (the molar ratio of three monomers of acrylic acid, methacrylic acid and 2-acrylamide-2-methylpropanesulfonic acid is 10: 5: 1) with the molecular weight of 500000 and 15g of distilled water at the temperature of 25 ℃, then stirring for 2 hours at the temperature of 80 ℃, stirring at the speed of 350r/min, then naturally cooling to 25 ℃, adding 80g of cellulose nanofibril aqueous suspension with the mass fraction of 3%, stirring at the temperature of 25 ℃ for 5 minutes, stirring at the speed of 350r/min, then adding 8g of uniform mixed solution consisting of span 80 and 500g of diesel oil, continuing to stir for 5 minutes at the temperature of 25 ℃, then adding 7g of hexanedial aqueous solution with the mass fraction of 1.5%, continuing to stir for 1 hour at the temperature of 25 ℃, stirring at 350r/min, controlling the temperature to be 45 ℃, stirring for 4 hours at 350r/min, filtering the reaction solution by using a 100-mesh fine sieve, soaking the filtered hydrogel spheres for 15 minutes by using 50g of ethyl acetate, filtering, soaking the filtered hydrogel spheres for 15 minutes by using 50g of ethanol, filtering, soaking the filtered hydrogel spheres for 15 minutes by using 50g of distilled water, and filtering to obtain the composite cellulose nanofibril hydrogel sphere product. The particle size of the obtained hydrogel spheres is 1.0-2.5 mm, and the water content is 95% by drying and weighing the hydrogel spheres with known mass. The hydrogel ball is mixed with clean water according to the mass ratio of 1: 24, and the reading of the hydrogel ball is 6 by a six-speed viscometer at the rotation speed of a viscometer rotor of 600r/min, which shows that the hydrogel ball has small influence on the viscosity of the water.
Example 6
Mixing 1g polyvinyl alcohol, 0.3g polymethacrylic acid with molecular weight of 1000000 and 10g distilled water at 25 ℃, stirring for 4h at 90 ℃, stirring at 200r/min, naturally cooling to 25 ℃, adding 80g cellulose nanofibril water suspension with mass fraction of 3%, stirring for 5min at 25 ℃, adding a uniform mixed solution composed of 8g span 80 and 500g liquid paraffin, stirring for 5min at 25 ℃, adding 10g succinaldehyde water solution with mass fraction of 1.5%, stirring for 1h at 25 ℃, stirring at 200r/min, controlling temperature and stirring for 4h at 45 ℃, stirring at 200r/min, filtering the reaction solution by using a 80-mesh fine screen, soaking the filtered hydrogel ball with 100g ethyl acetate for 20min, then filtering, then soaking the filtered hydrogel spheres with 100g of ethanol for 20min, then filtering, finally soaking the filtered hydrogel spheres with 100g of distilled water for 20min, then filtering, and finally obtaining the composite cellulose nanofibril hydrogel sphere product. The particle size of the obtained hydrogel spheres is 2.5-4.0 mm, and the water content is 96% when the hydrogel spheres with known mass are dried and weighed. The hydrogel ball is mixed with clean water according to the mass ratio of 1: 24, and the reading of the hydrogel ball is 7 by a six-speed viscometer at the rotation speed of a viscometer rotor of 600r/min, which shows that the hydrogel ball has small influence on the viscosity of the water.
Example 7
Mixing 1g of polyvinyl alcohol, 0.3g of polymethacrylic acid with the molecular weight of 500000 and 10g of distilled water at the temperature of 25 ℃, stirring for 2 hours at the temperature of 95 ℃, stirring at the speed of 300r/min, naturally cooling to 25 ℃, adding 80g of cellulose nanofibril aqueous suspension with the mass fraction of 3%, stirring at the temperature of 25 ℃ for 5 minutes at the speed of 300r/min, adding a uniform mixed solution consisting of 8g of span 80 and 400g of liquid paraffin, stirring at the temperature of 25 ℃ for 8 minutes, adding 6g of glutaraldehyde aqueous solution with the mass fraction of 1.5%, stirring at the temperature of 25 ℃ for 0.5 hour at the speed of 300r/min, controlling the temperature to stir at 45 ℃ for 4 hours at the speed of 300r/min, filtering the reaction solution by using a 80-mesh fine screen, soaking the obtained hydrogel ball in 100g of ethyl acetate for filtering for 15 minutes, then filtering, soaking the filtered hydrogel spheres for 15min by using 100g of ethanol, then filtering, finally soaking the filtered hydrogel spheres for 15min by using 100g of distilled water, and then filtering to finally obtain the composite cellulose nanofibril hydrogel sphere product. The particle size of the obtained hydrogel spheres is 1.0-3.0 mm, and the water content is 96% when the hydrogel spheres with known mass are dried and weighed. The hydrogel ball is mixed with clean water according to the mass ratio of 1: 24, and the reading of the hydrogel ball is 7 by a six-speed viscometer at the rotation speed of a viscometer rotor of 600r/min, which shows that the hydrogel ball has small influence on the viscosity of the water.
The following are the adsorption test results of the hydrogel spheres obtained in the above examples for heavy metal ions and organic pollutants.
The test method comprises the following steps:
(1) composite cellulose nanofibril hydrogel sphere for heavy metal Cu2+Adsorption of (2)
1g/L of Cu is prepared in advance2+And (4) stock solution. All adsorption experiments were performed by shaking in a constant temperature shaker at a constant rotation speed (160r/min) for 24h while maintaining the temperature in the shaker at 25 ℃. 100mg of hydrogel spheres are weighed and placed in 20mL of Cu with the concentration of 1g/L2+In the ionic solution, the solution is shaken for 24 hours. Finally, testing Cu in the solution before and after adsorption by an atomic absorption instrument2+Ion concentration and calculating gel sphere to Cu from the difference between the initial and final concentrations2+The amount of adsorption of (3).
(2) Adsorption of composite cellulose nanofibril hydrogel spheres on phenol and aniline
Respectively preparing 1g/L of phenol stock solution and aniline stock solution, and oscillating the solutions in a constant-temperature shaking table at a fixed rotating speed (160r/min) for 24 hours in adsorption experiments while keeping the temperature in the shaking table at 25 ℃.
Weighing 100mg of hydrogel spheres, placing the hydrogel spheres in 20mL of 1g/L phenol or aniline solution, oscillating for 24h, finally testing the concentration of phenol or aniline in the solution before and after adsorption by an ultraviolet spectrophotometer, and calculating the adsorption amount of the hydrogel on the phenol or aniline according to the difference between the initial concentration and the final concentration.
The results of the experiment are as follows:
TABLE 1 hydrogel sphere pair Cu2+Adsorption data of phenol, aniline and other substances
| Sample (I) | Q1(mmol/g) | Q2(mmol/g) | Q3(mmol/g) |
| Example 1 | 2.85 | 1.73 | 1.94 |
| Example 2 | 2.79 | 1.58 | 1.83 |
| Example 3 | 2.94 | 1.76 | 1.95 |
| Example 4 | 2.88 | 1.68 | 1.85 |
| Example 5 | 2.97 | 1.79 | 1.77 |
| Example 6 | 3.01 | 1.82 | 2.01 |
| Example 7 | 2.83 | 1.68 | 1.83 |
In Table 1, Q1 is hydrogel sphere vs Cu2+Q2 is the adsorption capacity of the hydrogel sphere to phenol, and Q3 is the adsorption capacity of the hydrogel sphere to aniline.
The adsorption experiment results show that the hydrogel spheres have a remarkable adsorption effect on heavy metal ions, organic phenols or organic amines.
Claims (6)
1. A composite cellulose nanofibril hydrogel sphere is characterized in that: the hydrogel ball is prepared by taking cellulose nanofibrils, polyvinyl alcohol, a water-soluble polymer, water and mineral oil as raw materials, forming a water-in-oil emulsion through the emulsification of a surfactant, and initiating a crosslinking reaction through a crosslinking agent, wherein the hydrogel ball is spherical in shape, the particle size is 0.5-4 mm, and the water content is more than 90%;
the water-soluble polymer is polymerized by three monomers of acrylic acid, methacrylic acid and 2-acrylamide-2-methylpropanesulfonic acid in an arbitrary proportion by a free radical initiated polymerization mode;
the cross-linking agent is any one of glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde and adipaldehyde;
the HLB value of the surfactant is less than 8;
the mineral oil is any one of diesel oil, white oil and liquid paraffin.
2. The composite cellulose nanofibril hydrogel sphere according to claim 1, characterized in that: the cellulose nano-fibrils are made of cellulose materials with the diameter of 3-80 nm and the length of more than 1 micron.
3. The composite cellulose nanofibril hydrogel sphere according to claim 1, characterized in that: the surfactant is any one of span 60, span 80 and span 85.
4. A method of preparing composite cellulose nanofibril hydrogel spheres according to any of claims 1 to 3, characterized in that: the method comprises the following steps:
(1) mixing 1 part by mass of polyvinyl alcohol, 0.1-0.5 part by mass of water-soluble polymer and 10-20 parts by mass of distilled water at 15-35 ℃, stirring for 2-5 hours at 80-95 ℃, naturally cooling to 15-35 ℃, adding 80 parts by mass of cellulose nanofibril water suspension, stirring for 5-30 minutes at 15-35 ℃, adding a uniform mixed solution composed of 6-10 parts by mass of surfactant and 300-500 parts by mass of mineral oil, continuously stirring for 5-10 minutes at 15-35 ℃, adding 1-10 parts by mass of a cross-linking agent aqueous solution with the mass fraction of 1.5%, continuously stirring for 0.25-1 hour at 15-35 ℃, controlling the temperature to be 45-75 ℃, stirring for 4-12 hours, and finishing the reaction;
(2) filtering the reaction solution obtained in the step (1) by using a fine sieve, soaking and filtering the obtained hydrogel spheres for 5-30 min by using 50-200 parts by mass of ethyl acetate, then filtering, soaking and filtering the obtained hydrogel spheres for 5-30 min by using 50-200 parts by mass of ethanol, then filtering, finally soaking and filtering the obtained hydrogel spheres for 5-30 min by using 50-200 parts by mass of distilled water, and then filtering to finally obtain a composite cellulose nanofibril hydrogel sphere product;
the cellulose nano-fibril aqueous suspension consists of cellulose nano-fibrils and water, wherein the content of the cellulose nano-fibrils is 1.0-3.0 wt%;
the aperture size of the fine screen is 0.1-0.5 mm.
5. The method of claim 4, wherein the method comprises the steps of: the stirring is mechanical stirring, and the stirring speed is 100-400 r/min.
6. Use of composite cellulose nanofibril hydrogel spheres according to any of claims 1 to 3, characterized in that: used for adsorbing heavy metal ions or organic pollutants in the sewage;
the organic pollutants are organic phenols and organic amines.
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