CN113388652B - Preparation method of green efficient nanocellulose - Google Patents
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Abstract
The invention belongs to the technical field of biomass materials, and particularly relates to a preparation method of green efficient nanocellulose. The preparation method of the green efficient nanocellulose provided by the invention comprises the following steps: mixing biomass cellulose, a cellulose aqueous solution and a pectinase aqueous solution for enzymolysis treatment; the mass ratio of the total mass of the aqueous cellulase solution and the aqueous pectase solution to the biomass cellulose is (15-30): 1, the enzyme activity of the cellulase in the aqueous cellulase solution is 30-150U/mL, the enzyme activity of the pectase in the aqueous pectase solution is 300-1500U/mL, and the enzymolysis treatment time is 15-60 min. According to the preparation method of the nanocellulose, the biomass cellulose is treated by adopting the cellulose aqueous solution and the pectinase aqueous solution together, so that the production efficiency and the yield of the nanocellulose are remarkably improved, and the nanocellulose is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of biomass materials, and particularly relates to a preparation method of green efficient nanocellulose.
Background
Currently, nanocellulose is prepared mainly by an acid method, a mechanical method, TEMPO oxidation, a sodium hypochlorite method or a biological method (including a biological enzyme method). The acid utilized in the preparation of the nanocellulose by the acid method mainly comprises sulfuric acid, phosphoric acid, acetic acid and the like, and the environmental pollution is easy to cause when the acid liquor is discharged after reaction; mechanical methods include high-pressure grinding, ball milling, freeze grinding, ultrasonic treatment and the like, but the yield of the nanocellulose product prepared by the mechanical method is low; the TEMPO oxidation or sodium hypochlorite process is carried out by TEMPO, naClO/NaClO 2 The system prepares nano cellulose under acidic or alkaline conditions, and is the same as an acid method, and is easy to cause environmental pollution.
The biological method for preparing the nanocellulose comprises the steps of preparing the nanocellulose by using a cellulase method and degrading biomass materials by bacteria and producing the nanocellulose by using bacteria, and the biological method for preparing the nanocellulose is high in yield and environment-friendly, but the enzymolysis time generally needs 7-30 days, so that the production efficiency of the nanocellulose is low.
Disclosure of Invention
In view of the above, the invention provides a preparation method of green efficient nanocellulose, and the preparation method provided by the invention remarkably improves the production efficiency of nanocellulose.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of green efficient nanocellulose, which comprises the following steps:
mixing biomass cellulose, a cellulose enzyme aqueous solution and a pectase aqueous solution for enzymolysis treatment to obtain the nanocellulose;
when the mass ratio of the total mass of the aqueous cellulase solution and the aqueous pectase solution to the biomass cellulose is (15-30): 1, the enzyme activity of the cellulase in the aqueous cellulase solution is 30-150U/mL, the enzyme activity of the pectase in the aqueous pectase solution is 300-1500U/mL, and the enzymolysis treatment time is 15-60 min.
Preferably, the mass ratio of the aqueous cellulase solution to the aqueous pectinase solution is (1-4): 1.
Preferably, the mass content of cellulose in the biomass cellulose is more than or equal to 98%.
Preferably, the temperature of the enzymolysis treatment is 45-55 ℃.
Preferably, the enzymolysis treatment is carried out under the condition of stirring, and the rotating speed of stirring is 800-1200 r/min.
Preferably, the enzymolysis treatment is carried out to obtain a nano-cellulose colloidal solution, and the enzymolysis treatment is further carried out to freeze-dry the nano-cellulose colloidal solution to obtain nano-cellulose solid powder, wherein the freeze-drying temperature is-70 to-85 ℃, and the freeze-drying time is 24-48 hours.
Preferably, the freeze-drying is vacuum freeze-drying, and the vacuum degree of the vacuum freeze-drying is 0.08 to 0.1Pa.
Preferably, the solid content of the colloid solution of the nanofiber is 0.12-0.46%.
The invention provides a preparation method of green efficient nanocellulose, which comprises the following steps: mixing biomass cellulose, a cellulose aqueous solution and a pectinase aqueous solution for enzymolysis treatment to obtain the nanocellulose; when the mass ratio of the total mass of the aqueous cellulase solution and the aqueous pectase solution to the biomass cellulose is (15-30): 1, the enzyme activity of the cellulase in the aqueous cellulase solution is 30-150U/mL, the enzyme activity of the pectase in the aqueous pectase solution is 300-1500U/mL, and the enzymolysis treatment time is 15-60 min. Compared with single cellulase for enzymolysis, the preparation method provided by the invention adopts the aqueous solution of cellulase and the aqueous solution of pectase to jointly carry out enzymolysis on biomass cellulose, and utilizes the synergistic effect of the aqueous solution of cellulase and the aqueous solution of pectase, when the mass ratio of the total mass of the aqueous solution of cellulase and the aqueous solution of pectase to the biomass cellulose is (15-30): 1, and the enzyme activity of cellulase in the aqueous solution of cellulase is 30-150U/mL, and when the enzyme activity of pectase in the aqueous solution of pectase is 300-1500U/mL, the enzymolysis treatment time of the invention is only 15-60 min, thereby remarkably improving the production efficiency of nanocellulose.
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FIG. 1 is an electron micrograph of nanocellulose prepared in example 1 of the present invention;
FIG. 2 is an electron micrograph of nanocellulose prepared in example 2 of the present invention.
Detailed Description
The invention provides a preparation method of green efficient nanocellulose, which comprises the following steps:
mixing biomass cellulose, a cellulose aqueous solution and a pectinase aqueous solution for enzymolysis treatment to obtain the nanocellulose;
when the mass ratio of the total mass of the aqueous cellulase solution and the aqueous pectase solution to the biomass cellulose is (15-30): 1, the enzyme activity of the cellulase in the aqueous cellulase solution is 30-150U/mL, the enzyme activity of the pectase in the aqueous pectase solution is 300-1500U/mL, and the enzymolysis treatment time is 15-60 min.
In the present invention, the biomass cellulose is preferably wood cellulose, straw cellulose, bamboo cellulose or leaf cellulose, and the leaf cellulose is preferably poplar leaf cellulose, pagodatree leaf cellulose or bamboo leaf cellulose. In the invention, the mass content of cellulose in the biomass cellulose is preferably more than or equal to 98%.
In the present invention, the preparation method of biomass cellulose preferably comprises the steps of:
and sequentially removing lignin and hemicellulose from the biomass material to obtain the biomass cellulose.
In the present invention, the biomass material is preferably wood, straw, bamboo or plant leaves, and the plant leaves are preferably poplar leaves, pagodatree leaves or bamboo leaves. The biomass material is preferably subjected to a pretreatment according to the invention, in which the pretreatment preferably comprises: removing grease from the biomass material; in the present invention, the removal of oil from the biomass material is preferably: immersing (hereinafter referred to as first immersing) the biomass material in a polar solvent to remove grease from the biomass material; in the invention, the polar solvent is preferably absolute ethanol or a mixed solvent of ethanol and water, and the mass percent of ethanol in the mixed solvent of ethanol and water is preferably more than or equal to 95%; the method has no special requirement on the dosage of the polar solvent, and can completely submerge the biomass material; in the present invention, the temperature of the first impregnation is preferably 65 to 70 ℃, and the time of the first impregnation is preferably 6 to 8 hours.
The invention preferably carries out water washing on the pretreated biomass material, and has no special requirement on the specific implementation process of the water washing, and the invention preferably removes the residual polar solvent on the surface of the biomass material by water washing.
The biomass material is subjected to lignin removal; in the present invention, the lignin removal is preferably: the biomass material is immersed in an acidic sodium chlorite solution (hereinafter referred to as a second immersion) to remove lignin, and the amount of the acidic sodium chlorite solution is not particularly limited in the present invention, and the biomass material may be completely immersed. In the method, when the acidic sodium chlorite solution is adopted to remove lignin in the biomass material, the treatment times of the acidic sodium chlorite solution are preferably 3-5 times, the treatment time of each acidic sodium chlorite solution is preferably 1h, in the specific embodiment of the invention, the treatment times of the acidic sodium chlorite solution are 5 times, the mass percent of the acidic sodium chlorite solution is preferably 0.67% in the 1 st treatment, the mass percent of the acidic sodium chlorite solution is preferably 1.34% in the 2 nd treatment, the mass percent of the acidic sodium chlorite solution is preferably 2.01% in the 3 rd treatment, the mass percent of the acidic sodium chlorite solution is preferably 2.68% in the 4 th treatment, and the mass percent of the acidic sodium chlorite solution is preferably 3.35% in the 5 th treatment. In the present invention, the temperature of the second impregnation is preferably 75 to 80 ℃. In the present invention, the pH of the acidic sodium chlorite solution is preferably 3 to 4, and the pH of the acidic sodium chlorite solution is preferably adjusted by a pH adjusting agent, which in the present invention is preferably glacial acetic acid.
The biomass material after lignin removal is preferably subjected to water washing, no special requirements are imposed on the specific implementation process of the water washing, and the acidic sodium chlorite remained on the surface of the biomass material is removed through water washing.
After removing the lignin, hemicellulose is removed from the biomass material; in the present invention, the hemicellulose removal is preferably: immersing the biomass material with lignin removed in a strong alkali solution (hereinafter referred to as third immersing) to remove hemicellulose, wherein the dosage of the strong alkali solution is not particularly required, and the biomass material can be completely immersed; in the present invention, the alkali solution is preferably an alkali metal hydroxide solution, more preferably a sodium hydroxide solution, and in the present invention, the mass concentration of the sodium hydroxide solution is preferably 15 to 20%, more preferably 17.5%; in the present invention, the temperature of the third impregnation is preferably 20 to 25 ℃, and the time of the third impregnation is preferably 0.5 to 2 hours.
The biomass material after hemicellulose removal is preferably subjected to water washing and drying, no special requirements are imposed on the specific implementation process of the water washing, and the residual alkali solution on the surface of the biomass material is preferably removed by water washing; the invention has no special requirements on the specific implementation process of the drying; in the present invention, the moisture content of the dried biomass cellulose is preferably 10% or less.
There is no particular requirement for the source of the cellulase and pectinase in the present invention, which are purchased from Shanghai Ala Latin.
In an embodiment of the present invention, the water is preferably deionized or distilled water.
In the present invention, the mass ratio of the aqueous cellulase solution to the aqueous pectinase solution is preferably (1 to 4): 1, more preferably (1.5 to 3.5): 1.
In the present invention, the mass ratio of the total mass of the aqueous cellulase solution and the aqueous pectinase solution to the biomass cellulose is preferably (15 to 30): 1, more preferably (20 to 25): 1.
In the invention, the enzyme activity of the cellulase in the aqueous solution of the cellulase is 30-150U/mL, preferably 45-120U/mL.
In the invention, the enzyme activity of the pectase in the pectase aqueous solution is 300-1500U/mL, preferably 375-1200U/mL.
In a specific embodiment of the present invention, when the enzyme activity of the cellulase in the aqueous solution of cellulase is preferably 150U/mL, the enzyme activity of the pectase in the aqueous solution of pectase is preferably 1500U/mL.
The invention has no special requirements for the specific implementation of the first mixing.
In the present invention, the temperature of the enzymolysis treatment is preferably 45 to 55 ℃, more preferably 50 ℃; when the mass ratio of the total mass of the cellulose aqueous solution and the pectase aqueous solution to the biomass cellulose is (15-30): 1, the enzymolysis treatment time is 15-60 min, preferably 30-45 min; the enzymolysis treatment is preferably performed under stirring, and the stirring speed is preferably 800-1200 r/min, more preferably 850-1000 r/min. The specific implementation process of the stirring is not particularly required.
When the enzymolysis treatment is carried out, the cellulase and the pectase can produce synergistic effect.
After the enzymolysis treatment, the present invention preferably dries the obtained nanocellulose colloid solution.
The invention preferably carries out post-treatment on the enzymolysis reaction liquid after the enzymolysis treatment to obtain the colloid solution of the nanocellulose; in the present invention, the post-treatment preferably includes: sequentially inactivating biological enzymes, performing solid-liquid separation and washing; in the present invention, the biological enzyme inactivation is preferably: carrying out high-temperature treatment on the enzymolysis reaction liquid; the temperature of the high-temperature treatment is preferably 100-110 ℃, and the time of the high-temperature treatment is preferably 10-15 min. In the present invention, the solid-liquid separation is preferably a centrifugal separation, the rotational speed of the centrifugal separation is preferably 3500 to 5000r/min, the time of the centrifugal separation is preferably 10 to 15min, and the centrifugal separation gives a supernatant and a solid product. The solid product is preferably washed with water, the washing times are preferably 3-5 times, the water consumption of each washing is not particularly required, and the solid product can be dispersed to obtain a suspension; in the invention, the suspension obtained by water washing is preferably subjected to solid-liquid separation, wherein when supernatant and a solid product are obtained after the solid-liquid separation, the water washing and the solid-liquid separation are continued, and when a colloid solution of the nanocellulose is obtained after the solid-liquid separation, the water washing is finished when no solid precipitation exists.
The invention removes sugar substances in the nanocellulose through solid-liquid separation and water washing.
In the invention, the solid content of the colloid solution of the nanocellulose is preferably 0.13-0.46%; the residue rate of the colloid solution of the nanocellulose is preferably 0%; the colloidal solution of nanocellulose does not produce floc or precipitate when left for 1 month.
In the invention, the drying temperature is preferably-70 to-85 ℃, and the drying time is preferably 24 to 48 hours, more preferably 30 to 40 hours; in the present invention, the drying is performed in a vacuum atmosphere, and the vacuum degree of the vacuum atmosphere is preferably 0.08 to 0.1Pa.
The invention obtains the nano cellulose powdery solid through drying. In the invention, the diameter of the nanocellulose is preferably 10-50 nm, the yield of the nanocellulose is more than 85%, and the relative crystallinity is preferably 72-82%.
The preparation method provided by the invention can be used for rapidly and efficiently preparing the nanocellulose product, and has the advantages of high yield, green pollution-free performance and no harm to the environment.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Soaking pine needle powder in 95% ethanol for 8h at 70deg.C to remove oil, washing with water, oven drying, soaking in mixed solution of glacial acetic acid and sodium chlorite (pH 3-4) at 75deg.C for 5 times, and removing lignin 1h each time; soaking in 17.5% sodium hydroxide solution at 20deg.C for 1 hr to obtain pine needle cellulose, detecting pine needle cellulose by infrared spectrum, and comparing with infrared spectrum of microcrystalline cellulose, wherein cellulose content in pine needle cellulose is greater than 99%;
weighing 5g of cellulase and 95g of deionized water, and mixing to obtain a cellulase aqueous solution, wherein the activity of the cellulase is 150u/ml;
weighing 5g of pectase and 95g of deionized water, and mixing to obtain an aqueous pectase solution, wherein the activity of the pectase is 1500u/ml;
weighing 2g of pine needle cellulose, 15g of pectinase aqueous solution and 15g of cellulase aqueous solution, mixing, and performing enzymolysis at 50 ℃ for 60 mm with stirring speed of 1000r/min; immediately transferring the enzymolysis reaction liquid into a water bath kettle at 100 ℃ for treatment for 10min after the treatment time is over, and inactivating biological enzymes; centrifuging for 10min by using a centrifugal machine at the rotating speed of 4000r/min, and removing supernatant to leave a sediment product; uniformly mixing the precipitate with distilled water to obtain suspension, and centrifuging again with a centrifuge for 10min at 4000r/min; repeating the steps for 4 times to obtain a milky nano-cellulose colloid solution without solid products after centrifugation, wherein the solid content is 0.26%;
and (3) placing the nano cellulose colloid solution in a vacuum freeze dryer for freeze drying, wherein the vacuum degree is 0.08Pa, and the temperature is-80 ℃. The time is 48 hours; obtaining powdery solid of nano cellulose; the yield of the nanocellulose is 85%, and the relative crystallinity is 78.46%.
The nanocellulose powder obtained in example 1 was observed by using a field emission scanning electron microscope, and the obtained picture is shown in fig. 1, and the diameter of nanocellulose obtained in example 1 is 18-50 nm.
Example 2
Soaking poplar leaf powder in 95% ethanol at 70deg.C for 8 hr to remove oil, washing and oven drying, soaking in mixed solution of glacial acetic acid and sodium chlorite (pH 3-4) at 75deg.C for 5 times, and removing lignin 1 hr each time; washing, drying, soaking in 17.5% sodium hydroxide solution at 20deg.C for 1 hr to obtain poplar leaf cellulose, detecting poplar leaf cellulose by infrared spectrum, and comparing with microcrystalline cellulose with cellulose content greater than 99%;
weighing 5g of cellulase and 95g of deionized water, and mixing to obtain a cellulase aqueous solution, wherein the activity of the cellulase is 150u/ml;
weighing 5g of pectase and 95g of deionized water, and mixing to obtain an aqueous pectase solution, wherein the activity of the pectase is 1500u/ml;
1g of poplar leaf cellulose, 15g of pectinase aqueous solution and 15g of cellulase aqueous solution are weighed and mixed, and then subjected to enzymolysis at 50 ℃ for 60 mm, wherein the stirring speed is 1000r/min; immediately transferring the enzymolysis reaction liquid into a water bath kettle at 100 ℃ for treatment for 10min after the treatment time is over, and inactivating biological enzymes; centrifuging for 10min by using a centrifugal machine at the rotating speed of 4000r/min, and removing supernatant to leave a sediment product; uniformly mixing the precipitate with distilled water to obtain suspension, and centrifuging again with a centrifuge for 10min at 4000r/min; repeating the steps for 4 times to obtain a milky nano-cellulose colloid solution without solid products after centrifugation, wherein the solid content is 0.13%;
and (3) placing the nano cellulose colloid solution in a vacuum freeze dryer for freeze drying, wherein the vacuum degree is 0.08Pa, and the temperature is-80 ℃. The time is 48 hours; obtaining powdery solid of nano cellulose; the yield of the nanocellulose is 85%, and the relative crystallinity is 77.39%.
The nanocellulose powder obtained in example 2 was observed by using a field emission scanning electron microscope, and the obtained picture is shown in fig. 1, and the diameter of nanocellulose obtained in example 2 is 10-50 nm.
Example 3
Soaking bamboo powder in 95% ethanol for 8h at 70 ℃ to remove grease, washing and drying the bamboo powder, soaking the bamboo powder in a mixed solution of glacial acetic acid and sodium chlorite (pH value is 3-4) at 75 ℃ for 5 times, and removing lignin 1h each time; washing, drying, soaking in 17.5% sodium hydroxide solution at 20deg.C for 1 hr to obtain bamboo cellulose, detecting bamboo cellulose by infrared spectrum, and comparing with microcrystalline cellulose with cellulose content greater than 99%;
weighing 5g of cellulase and 95g of deionized water, and mixing to obtain a cellulase aqueous solution, wherein the activity of the cellulase is 150u/ml;
weighing 5g of pectase and 95g of deionized water, and mixing to obtain an aqueous pectase solution, wherein the activity of the pectase is 1500u/ml;
weighing 5g of bamboo cellulose, 75g of pectinase aqueous solution and 75g of cellulase aqueous solution, mixing, and performing enzymolysis at 50 ℃ for 60 mm with stirring speed of 1000r/min; immediately transferring the enzymolysis reaction liquid into a water bath kettle at 100 ℃ for treatment for 10min after the treatment time is over, and inactivating biological enzymes; centrifuging for 10min by using a centrifugal machine at the rotating speed of 4000r/min, and removing supernatant to leave a sediment product; uniformly mixing the precipitate with distilled water to obtain suspension, and centrifuging again with a centrifuge for 10min at 4000r/min; repeating the steps for 4 times to obtain a milky nano-cellulose colloid solution without solid products after centrifugation, wherein the solid content is 0.46%;
and (3) placing the nano cellulose colloid solution in a vacuum freeze dryer for freeze drying, wherein the vacuum degree is 0.08Pa, and the temperature is-80 ℃. The time is 48 hours; obtaining powdery solid of nano cellulose; the yield of the nanocellulose is 85%, and the relative crystallinity is 78.46%.
Comparative example 1
Soaking bamboo powder in 95% ethanol for 8h at 70 ℃ to remove grease, washing and drying the bamboo powder, soaking the bamboo powder in a mixed solution of glacial acetic acid and sodium hypochlorite (pH value is 3-4) at 75 ℃ for 5 times, and removing lignin 1h each time; washing, drying, soaking in 17.5% sodium hydroxide solution at 20deg.C for 1 hr to obtain bamboo cellulose, detecting bamboo cellulose by infrared spectrum, and comparing with microcrystalline cellulose with cellulose content greater than 99%;
weighing 5g of cellulase and 95g of deionized water, and mixing to obtain a cellulase aqueous solution, wherein the activity of the cellulase is 150u/ml;
weighing 2g of bamboo cellulose and 30g of cellulose aqueous solution, mixing, and carrying out enzymolysis treatment at 50 ℃ for 60 mm, wherein the stirring speed is 1000r/min; immediately transferring the enzymolysis reaction liquid into a water bath kettle at 100 ℃ for treatment for 10min after the treatment time is over, and inactivating biological enzymes; centrifuging for 10min by using a centrifugal machine at the rotating speed of 4000r/min, and removing supernatant to leave a sediment product; uniformly mixing the precipitate with distilled water to obtain suspension, and centrifuging again with a centrifuge for 10min at 4000r/min; the above procedure was repeated 4 times, but it was found that the washed system had solid precipitate all the time and a colloidal solution of nanocellulose could not be formed.
Comparative example 2
Soaking bamboo powder in 95% ethanol for 8h at 70 ℃ to remove grease, washing and drying the bamboo powder, soaking the bamboo powder in a mixed solution of glacial acetic acid and sodium chlorite (pH value is 3-4) at 75 ℃ for 5 times, and removing lignin 1h each time; washing, drying, soaking in 17.5% sodium hydroxide solution at 20deg.C for 1 hr to obtain bamboo cellulose, detecting bamboo cellulose by infrared spectrum, and comparing with microcrystalline cellulose with cellulose content greater than 99%;
weighing 5g of pectase and 95g of deionized water, and mixing to obtain an aqueous pectase solution, wherein the activity of the pectase is 1500u/ml;
weighing 2g of bamboo cellulose and 30g of pectinase aqueous solution, mixing, and carrying out enzymolysis treatment at 50 ℃ for 60 mm, wherein the stirring speed is 1000r/min; immediately transferring the enzymolysis reaction liquid into a water bath kettle at 100 ℃ for treatment for 10min after the treatment time is over, and inactivating biological enzymes; centrifuging for 10min by using a centrifugal machine at the rotating speed of 4000r/min, and removing supernatant to leave a sediment product; uniformly mixing the precipitate with distilled water to obtain suspension, and centrifuging again with a centrifuge for 10min at 4000r/min; the above procedure was repeated 4 times, but it was found that the washed system had solid precipitate all the time and a colloidal solution of nanocellulose could not be formed.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. The preparation method of the green efficient nanocellulose is characterized by comprising the following steps of:
mixing biomass cellulose, a cellulose aqueous solution and a pectinase aqueous solution for enzymolysis treatment to obtain the nanocellulose; the mass content of cellulose in the biomass cellulose is more than or equal to 98%;
the mass ratio of the total mass of the aqueous solution of cellulase and the aqueous solution of pectase to the biomass cellulose is (15-30): 1, the enzyme activity of the cellulase in the aqueous solution of cellulase is 30-150U/mL, the enzyme activity of the pectase in the aqueous solution of pectase is 300-1500U/mL, the enzymolysis treatment time is 15-60 min, the yield of the nano-cellulose is more than 85%, and the relative crystallinity of the nano-cellulose is 72% -82%; the mass ratio of the cellulose aqueous solution to the pectase aqueous solution is (1-4) 1; the enzymolysis treatment is carried out under the condition of stirring, and the rotating speed of the stirring is 800-1200 r/min.
2. The method according to claim 1, wherein the temperature of the enzymolysis treatment is 45 to 55 ℃.
3. The preparation method of the nano cellulose powder according to claim 1, wherein the enzymolysis treatment is carried out to obtain a nano cellulose colloidal solution, and the enzymolysis treatment is further carried out to freeze-dry the nano cellulose colloidal solution to obtain nano cellulose solid powder, wherein the freeze-drying temperature is-70 to-85 ℃, and the freeze-drying time is 24 to 48 hours.
4. The method according to claim 3, wherein the freeze-drying is vacuum freeze-drying, and the vacuum degree of the vacuum freeze-drying is 0.08 to 0.1Pa.
5. The method according to claim 4, wherein the solid content of the nanocellulose colloidal solution is 0.12% -0.46%.
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