CN111793139A - Nano cellulose and preparation method thereof - Google Patents
Nano cellulose and preparation method thereof Download PDFInfo
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- CN111793139A CN111793139A CN201910281926.5A CN201910281926A CN111793139A CN 111793139 A CN111793139 A CN 111793139A CN 201910281926 A CN201910281926 A CN 201910281926A CN 111793139 A CN111793139 A CN 111793139A
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Abstract
The application discloses nanocellulose and a preparation method thereof, wherein the water contact angle of the nanocellulose is less than 20 degrees. The method relates to the preparation of nanocellulose in an organic acid system, comprising at least the following steps: (1) reacting a cellulose raw material with an organic acid solvent and water to obtain a solid reactant, and washing the solid reactant to be neutral; (2) and drying the obtained solid reactant to obtain the nano-cellulose. The method for preparing the nano-cellulose by hydrolyzing the cellulose with the organic acid has the advantages of simple operation, mild reaction conditions and low energy consumption, and the separated and recovered reaction solution can be recycled, thereby reducing the pollution to the environment and opening up a new path for industrially producing the nano-cellulose.
Description
Technical Field
The application relates to nano-cellulose and a preparation method thereof, belonging to the field of materials.
Background
Cellulose is the most abundant renewable biomass resource on the earth, accounts for about 40-50% of the total mass of biomass, and is a linear natural high molecular compound formed by connecting beta-D-glucopyranosyl with beta-1, 4-glycosidic bonds, and the high molecular compound further forms cellulose bundles through covalent bonds and hydrogen bonds, and mainly consists of two parts, namely a crystalline region and an amorphous region. Compared with artificially synthesized macromolecules, the cellulose has the advantages of wide sources, environmental friendliness, biocompatibility, biodegradability, renewability and the like. The nano-cellulose is a novel biomass nano-material with nano-size and high specific surface area, not only has excellent properties of cellulose, but also has excellent properties of high purity, high crystallinity, high modulus, high strength, ultra-fine structure, high transparency and the like, so that the nano-cellulose is widely applied to the fields of medicines, cosmetics, food packaging, paint coating, composite materials, building materials and the like, and becomes a research hotspot in the field of nano-materials.
At present, the preparation method of the nano-cellulose mainly comprises a mechanical method, a biological method and a chemical method. The mechanical method is mainly to separate nano-sized fibers by treating cellulose with mechanical equipment such as a homogenizer to perform cutting and fibrillation. The mechanical method for preparing the nano-cellulose has little influence on the environment, but has special requirements on equipment and high energy consumption. The biological method is to use biological enzyme to treat cellulose, has the advantages of mild treatment conditions and the like, but has long preparation period and complex process. The chemical method mainly refers to a method for preparing nano-cellulose by treating cellulose with a chemical reagent, and the chemical reagent commonly used at present is a high-concentration inorganic acid, such as sulfuric acid, hydrochloric acid, phosphoric acid and the like. In an inorganic acid system, cellulose has a serious hydrolysis problem, the recovery rate is low, the inorganic acid has strong corrosivity to reaction equipment, hydrolysis products are difficult to treat, and reaction liquid is difficult to recycle. Therefore, the invention provides a method for preparing the green high-efficiency low-energy-consumption nano-cellulose, which is the basis for further realizing the wide application of the nano-cellulose in the fields of materials and the like.
The invention discloses a nano-cellulose and a preparation method thereof. Compared with the existing technology, the method has the advantages of simple operation and low energy consumption, and the separated and recovered reaction solution can be recycled, thereby reducing the pollution to the environment and opening up a new path for large-scale industrial production of the nano-cellulose.
Disclosure of Invention
One aspect of the present invention provides a nanocellulose having a water contact angle of less than 20 °.
In a preferred embodiment, the nanocellulose has a water contact angle of less than 15 °, more preferably less than 13 °.
In a preferred embodiment, the nanocellulose has an X-ray diffraction pattern comprising at least two diffraction peaks:
diffraction peak a, 2 θ is between 12 ° and 18 °;
diffraction peak B, 2 θ was between 21 ° and 24 °.
Another aspect of the present invention provides a method for preparing nanocellulose in an organic acid system, said method comprising at least the steps of:
(1) reacting a cellulose raw material with an organic acid solvent and water to obtain a solid reactant, and washing the solid reactant to be neutral;
(2) and drying the obtained solid reactant to obtain the nano-cellulose.
In a preferred embodiment, the method further comprises the step of reusing the reaction solution.
In a preferred embodiment, the cellulosic feedstock is derived from wood chips and/or straw;
the cellulose raw material is selected from at least one of cellulose pulp, nano-cellulose and microcrystalline cellulose.
In a preferred embodiment, the wood chips comprise at least one of pine, beech, birch;
the straw comprises at least one of corn straw and wheat straw.
In a preferred embodiment, the organic acid solvent comprises at least one of formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, tartaric acid, lactic acid, oxalic acid, maleic acid, and benzoic acid.
In a preferred embodiment, in the step (1), the ratio of the mass of the cellulose raw material to the total volume of the organic acid solvent and water is 1 g: (1-50) mL.
In a preferred embodiment, in the step (1), the mass ratio of the organic acid solvent to water is (0.01-1): 1.
In a preferred embodiment, in the recycling of the reaction solution, the ratio of the mass of the cellulose raw material to the total volume of the reaction solution recovered by separation is 1 g: (1-50) mL.
In a preferred embodiment, said step (1) is carried out in a reaction vessel at 80-220 ℃ for 1 to 40 hours at a reaction pressure of 0.1-40 bar.
Another aspect of the present invention provides the use of the above nanocellulose or nanocellulose prepared according to the above method in the field of daily chemicals.
In a further aspect of the invention there is provided the use of a nanocellulose as described above or prepared according to the method described above in a mask product.
The beneficial effects that this application can produce include:
1) the method adopts low-concentration organic acid for treatment, and the reaction system has weak acidity and low reaction pressure, so that the method has low requirements on reaction equipment and has great industrialization potential.
2) The method has the advantages of simple operation, low energy consumption and green process, and is an environment-friendly process.
3) The organic acid reaction solution used in the invention can be separated and further recycled, and the cost of the preparation process is reduced.
4) The nano fibrils prepared by the method have uniform diameter distribution and good hydrophilicity, and are suitable for the field of daily chemicals or facial mask products.
Drawings
Fig. 1 is an electron micrograph of the nanocellulose prepared in example 1.
Fig. 2A and 2B show the results of the suspension property test of the nanocellulose prepared in example 1.
Fig. 3A and 3B show the water contact angle test results for untreated cellulose pulp stock and nanocellulose in example 1, respectively.
Figure 4 shows XRD results of crystallinity analysis of the nanocellulose and cellulose pulp raw materials prepared in example 1.
FIG. 5 shows the FTIR results of infrared spectra of the nanocellulose and cellulose pulp feedstocks prepared in example 1.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Example 1
0.5g of pine cellulose pulp was weighed into a reaction vessel, while formic acid and water, containing 0.5g of formic acid and 9.5g of water in a total volume of 9.6ml, were added, and stirred to mix thoroughly. Sealing the reaction kettle, closing the gas inlet and the gas outlet, heating to 180 ℃ by adopting an electric heating mode under the magnetic stirring of 600rpm, and reacting for 600 min. After the reaction is finished, cooling the reaction kettle to room temperature by ice water, stopping stirring, performing centrifugal separation on reaction liquid to obtain a solid nano cellulose part and recovered reaction liquid, and washing the solid for 3 times by deionized water until the solid is neutral. And (3) drying the nano-cellulose solid for 36 hours at 30 ℃ in a vacuum box with the vacuum degree of-0.1 MPa to obtain a nano-cellulose product. The recovered reaction solution can be further recycled to prepare the nano-cellulose.
The nanocellulose labeled #1 sample was obtained with a yield of 87.3% and nanocellulose crystallinity of 91.0%.
Electron microscopy testing of #1 nanocellulose
The electron micrograph of the nanocellulose is shown in fig. 1, and it can be seen from fig. 1 that the diameter of the obtained nanocellulose is uniform.
Suspension test of #1 nanocellulose
As can be seen from fig. 2A and 2B, the prepared sample still has better suspensibility after standing for two days.
Water contact Angle test of #1 nanocellulose
Fig. 3A and 3B show the water contact angle test for conventional cellulose pulp and nanocellulose in example 1, respectively. The test results showed that the water contact angle of the conventional cellulose pulp was 23 deg., whereas the water contact angle of the nanocellulose in example 1 was only 13 deg., which showed that the nanocellulose in example 1 had good hydrophilicity.
Crystallinity test of #1 nanocellulose
Fig. 4 shows the crystallinity test of conventional cellulose pulp and nanocellulose in example 1. The test results showed that the crystallinity of the conventional cellulose pulp was 89%, while the crystallinity of the nanocellulose in example 1 was 91%, which showed that the nanocellulose in example 1 had a higher crystallinity.
FTIR testing of #1 nanocellulose
Fig. 5 shows FTIR testing of conventional cellulose pulp and nanocellulose in example 1. The test results show that the prepared nanocellulose has similar infrared absorption spectrum with the cellulose pulp raw material, so that the nanocellulose retains the radical structure in the cellulose pulp.
Example 2
1g of pine cellulose pulp was weighed into a reaction vessel, and acetic acid and water, which contained 1.5g of acetic acid and 20.1g of water in a total volume of 21.0ml, were added simultaneously, and stirred to mix well. Sealing the reaction kettle, closing the gas inlet and the gas outlet, heating to 160 ℃ by adopting an electric heating mode under the magnetic stirring of 800rpm, and reacting for 1000 min. After the reaction is finished, cooling the reaction kettle to room temperature by ice water, stopping stirring, performing centrifugal separation on the reaction liquid to obtain a solid nano cellulose part and a recovered reaction liquid, and washing the solid for 5 times by deionized water until the solid is neutral. Drying the nano-cellulose solid in a freeze drying oven with the vacuum degree of-0.1 MPa at the temperature of-20 ℃ for 12h to obtain a nano-cellulose product. The recovered reaction solution can be further recycled to prepare the nano-cellulose.
The yield of the nanocellulose was 75.6% and the crystallinity of the nanocellulose was 88.1%.
Example 3
0.6g of pine cellulose pulp was weighed into a reaction vessel, while adding propionic acid and water, the total volume of which was 10.4ml and which contained 0.8g of propionic acid and 10.0g of water, and stirred to mix thoroughly. Sealing the reaction kettle, closing the gas inlet and the gas outlet, heating to 150 ℃ by adopting an electric heating mode under the magnetic stirring of 800rpm, and reacting for 800 min. After the reaction is finished, cooling the reaction kettle to room temperature by ice water, stopping stirring, performing centrifugal separation on reaction liquid to obtain a solid nano cellulose part and recovered reaction liquid, and washing the solid for 4 times by deionized water until the solid is neutral. Drying the nano-cellulose solid in a freeze drying oven with the vacuum degree of-0.1 MPa at the temperature of-20 ℃ for 12h to obtain a nano-cellulose product. The recovered reaction solution can be further recycled to prepare the nano-cellulose.
The yield of the nano-cellulose is 89.7%, and the crystallinity of the nano-cellulose is 90.6%.
Example 4
2g of pine cellulose pulp was weighed into a reaction vessel, and while adding butyric acid and water, the total volume of butyric acid and water was 43.1ml, containing 2.4g of butyric acid and 42.0g of water, and stirred to be sufficiently mixed. Sealing the reaction kettle, closing the gas inlet and the gas outlet, heating to 170 ℃ by adopting an electric heating mode under the magnetic stirring of 700rpm, and reacting for 900 min. After the reaction is finished, cooling the reaction kettle to room temperature by ice water, stopping stirring, performing centrifugal separation on reaction liquid to obtain a solid nano cellulose part and recovered reaction liquid, and washing the solid for 4 times by deionized water until the solid is neutral. And (3) drying the nano-cellulose solid for 36 hours at 30 ℃ in a vacuum box with the vacuum degree of-0.1 MPa to obtain a nano-cellulose product. The recovered reaction solution can be further recycled to prepare the nano-cellulose.
The yield of the nano-cellulose is 85.2%, and the crystallinity of the nano-cellulose is 89.4%.
Example 5
0.5g of pine cellulose pulp was weighed into a reaction vessel, and oxalic acid and water, which contained 0.4g of oxalic acid and 9.4g of water in a total volume of 9.6ml, were added simultaneously, and stirred to mix well. Sealing the reaction kettle, closing the gas inlet and the gas outlet, heating to 180 ℃ by adopting an electric heating mode under the magnetic stirring of 600rpm, and reacting for 900 min. After the reaction is finished, cooling the reaction kettle to room temperature by ice water, stopping stirring, performing centrifugal separation on the reaction liquid to obtain a solid nano cellulose part and a recovered reaction liquid, and washing the solid for 5 times by deionized water until the solid is neutral. And (3) drying the nano-cellulose solid for 36 hours at 30 ℃ in a vacuum box with the vacuum degree of-0.1 MPa to obtain a nano-cellulose product. The recovered reaction solution can be further recycled to prepare the nano-cellulose.
The yield of the nanocellulose was 74.9%, and the crystallinity of the nanocellulose was 89.6%.
Example 6
0.6g of pine cellulose pulp was weighed into a reaction vessel, and malonic acid and water, which contained 0.6g of malonic acid and 9.8g of water in a total volume of 10.2ml, were added simultaneously, and stirred to be mixed well. Sealing the reaction kettle, closing the gas inlet and the gas outlet, heating to 140 ℃ by adopting an electric heating mode under the magnetic stirring of 500rpm, and reacting for 1100 min. After the reaction is finished, cooling the reaction kettle to room temperature by ice water, stopping stirring, performing centrifugal separation on reaction liquid to obtain a solid nano cellulose part and recovered reaction liquid, and washing the solid for 6 times by deionized water until the solid is neutral. Drying the nano-cellulose solid in a freeze drying oven with the vacuum degree of-0.1 MPa at the temperature of-20 ℃ for 12h to obtain a nano-cellulose product. The recovered reaction solution can be further recycled to prepare the nano-cellulose.
The yield of the nano-cellulose is 81.5%, and the crystallinity of the nano-cellulose is 90.4%.
Example 7
Weighing 1.1g of pine cellulose pulp, adding succinic acid and water into a reaction kettle, simultaneously adding succinic acid and water, wherein the total volume of the succinic acid and the water is 21.3ml, and the succinic acid and the water contain 1.2g of succinic acid and 20.5g of water, and stirring to fully mix. Sealing the reaction kettle, closing the gas inlet and the gas outlet, heating to 150 ℃ by adopting an electric heating mode under the magnetic stirring of 900rpm, and reacting for 900 min. After the reaction is finished, cooling the reaction kettle to room temperature by ice water, stopping stirring, performing centrifugal separation on the reaction liquid to obtain a solid nano cellulose part and a recovered reaction liquid, and washing the solid for 5 times by deionized water until the solid is neutral. Drying the nano-cellulose solid in a freeze drying oven with the vacuum degree of-0.1 MPa at the temperature of-20 ℃ for 12h to obtain a nano-cellulose product. The recovered reaction solution can be further recycled to prepare the nano-cellulose.
The yield of the nano-cellulose is 80.4%, and the crystallinity of the nano-cellulose is 89.7%.
Example 8
2g of pine cellulose pulp was weighed into a reaction vessel, and tartaric acid and water, the total volume of which was 43.8ml and which contained 2.2g of tartaric acid and 42.2g of water, were added simultaneously, and stirred to mix thoroughly. Sealing the reaction kettle, closing the gas inlet and the gas outlet, heating to 160 ℃ by adopting an electric heating mode under the magnetic stirring of 900rpm, and reacting for 800 min. After the reaction is finished, cooling the reaction kettle to room temperature by ice water, stopping stirring, performing centrifugal separation on the reaction liquid to obtain a solid nano cellulose part and a recovered reaction liquid, and washing the solid for 5 times by deionized water until the solid is neutral. Drying the nano-cellulose solid in a freeze drying oven with the vacuum degree of-0.1 MPa at the temperature of-20 ℃ for 12h to obtain a nano-cellulose product. The recovered reaction solution can be further recycled to prepare the nano-cellulose.
The yield of the nanocellulose is 79.6%, and the crystallinity of the nanocellulose is 91.5%.
Example 9
1.2g of pine cellulose pulp was weighed into a reaction vessel, and lactic acid and water, the total volume of which was 19.6ml and which contained 1.4g of lactic acid and 18.8g of water, were added simultaneously, and stirred to mix thoroughly. Sealing the reaction kettle, closing the gas inlet and the gas outlet, heating to 170 ℃ by adopting an electric heating mode under the magnetic stirring of 800rpm, and reacting for 1000 min. After the reaction is finished, cooling the reaction kettle to room temperature by ice water, stopping stirring, performing centrifugal separation on the reaction liquid to obtain a solid nano cellulose part and a recovered reaction liquid, and washing the solid with deionized water for 7 times until the solid is neutral. Drying the nano-cellulose solid in a freeze drying oven with the vacuum degree of-0.1 MPa at the temperature of-20 ℃ for 12h to obtain a nano-cellulose product. The recovered reaction solution can be further recycled to prepare the nano-cellulose.
The yield of the nano-cellulose is 73.8%, and the crystallinity of the nano-cellulose is 90.6%.
Example 10
0.6g of pine cellulose pulp was weighed into a reaction vessel, while adding oxalic acid and water, the total volume of which was 9.9ml and which contained 0.5g of oxalic acid and 9.6g of water, and stirred to mix thoroughly. Sealing the reaction kettle, closing the gas inlet and the gas outlet, heating to 150 ℃ by adopting an electric heating mode under the magnetic stirring of 800rpm, and reacting for 850 min. After the reaction is finished, cooling the reaction kettle to room temperature by ice water, stopping stirring, performing centrifugal separation on the reaction liquid to obtain a solid nano cellulose part and a recovered reaction liquid, and washing the solid with deionized water for 7 times until the solid is neutral. Drying the nano-cellulose solid in a freeze drying oven with the vacuum degree of-0.1 MPa at the temperature of-20 ℃ for 12h to obtain a nano-cellulose product. The recovered reaction solution can be further recycled to prepare the nano-cellulose.
The yield of the nano-cellulose is 81.2%, and the crystallinity of the nano-cellulose is 89.9%.
Example 11
0.8g of pine cellulose pulp was weighed into a reaction vessel, and maleic acid and water, which contained 0.8g of maleic acid and 9.9g of water in a total volume of 10.5ml, were added simultaneously, and stirred to mix well. Sealing the reaction kettle, closing the gas inlet and the gas outlet, heating to 170 ℃ by adopting an electric heating mode under the magnetic stirring of 700rpm, and reacting for 800 min. After the reaction is finished, cooling the reaction kettle to room temperature by ice water, stopping stirring, performing centrifugal separation on the reaction liquid to obtain a solid nano cellulose part and a recovered reaction liquid, and washing the solid with deionized water for 7 times until the solid is neutral. Drying the nano-cellulose solid in a freeze drying oven with the vacuum degree of-0.1 MPa at the temperature of-20 ℃ for 12h to obtain a nano-cellulose product. The recovered reaction solution can be further recycled to prepare the nano-cellulose.
The yield of the nanocellulose was 78.6% and the crystallinity of the nanocellulose was 89.5%.
Example 12
1.3g of pine cellulose pulp was weighed into a reaction vessel, and benzoic acid and water, which contained 10.0g of benzoic acid and 11.5g of water in a total volume of 20.7ml, were added simultaneously, and stirred to mix well. Sealing the reaction kettle, closing the gas inlet and the gas outlet, heating to 100 ℃ by adopting an electric heating mode under the magnetic stirring of 800rpm, and reacting for 1200 min. After the reaction is finished, cooling the reaction kettle to room temperature by ice water, stopping stirring, performing centrifugal separation on the reaction liquid to obtain a solid nano cellulose part and a recovered reaction liquid, and washing the solid with deionized water for 7 times until the solid is neutral. Drying the nano-cellulose solid in a freeze drying oven with the vacuum degree of-0.1 MPa at the temperature of-20 ℃ for 12h to obtain a nano-cellulose product. The recovered reaction solution can be further recycled to prepare the nano-cellulose.
The yield of the nanocellulose was 75.8% and the crystallinity of the nanocellulose was 88.9%.
The experimental procedure of example 13 was the same as that of example 1, except that the cellulose material was changed to cellulose pulp of corn stover, the reaction temperature was changed to 150 ℃ and the reaction time was changed to 700 min.
The experimental procedure of example 14 was the same as that of example 2, and it was necessary to change the cellulose raw material to cellulose pulp of corn stover, the reaction temperature was changed to 170 ℃ and the reaction time was changed to 850 min.
Example 15 the experimental procedure was the same as in example 3, requiring the cellulose feedstock to be changed to cellulose pulp from corn stover.
The experimental procedure of example 16 was the same as in example 4, requiring the cellulose material to be changed to cellulose pulp of corn stover and the reaction time to be changed to 700 min.
The experimental procedure of example 17 was the same as that of example 5, and it was necessary to change the cellulose raw material to cellulose pulp of corn stover, the reaction temperature was changed to 190 ℃ and the reaction time was changed to 400 min.
The experimental procedure of example 18 was the same as that of example 6, and it was necessary to change the cellulose raw material to cellulose pulp of corn stover, the reaction temperature was changed to 130 ℃, and the reaction time was changed to 2200 min.
The experimental procedure of example 19 was the same as that of example 7, and it was required to change the cellulose raw material to cellulose pulp of corn stover and the reaction time to 1050 min.
Example 20 the experimental procedure was the same as in example 8, requiring the cellulose stock to be changed to cellulose pulp from corn stover.
The experimental procedure of example 21 was the same as in example 9, requiring the cellulose material to be changed to cellulose pulp of corn stover and the reaction temperature to be changed to 180 ℃.
The experimental procedure of example 22 was the same as in example 10, and it was necessary to change the cellulose raw material to cellulose pulp of corn stover and the reaction time to 1200 min.
The experimental procedure of example 23 was the same as that of example 11, and it was necessary to change the cellulose raw material to cellulose pulp of corn stover, the reaction temperature was changed to 160 deg.C, and the reaction time was changed to 950 min.
The experimental procedure of example 24 was the same as that of example 12, except that the cellulose material was changed to cellulose pulp of corn stover, the reaction temperature was changed to 130 ℃ and the reaction time was changed to 1000 min.
The experimental procedure of example 25 was the same as in example 1, except that the cellulose material was changed to a cellulose pulp of wheat straw and the reaction temperature was changed to 190 ℃.
The experimental procedure of example 26 was the same as that of example 2, and the cellulose material was changed to a cellulose pulp of wheat straw, and the reaction time was changed to 1300 min.
The experimental procedure of example 27 was the same as in example 3, except that the cellulose material was changed to a cellulose pulp of wheat straw, and the reaction time was changed to 1000 min.
The experimental procedure of example 28 was the same as that of example 4, and it was necessary to change the cellulose raw material to cellulose pulp of wheat straw, the reaction temperature was changed to 160 ℃ and the reaction time was changed to 1500 min.
The experimental procedure of example 29 was the same as in example 5, requiring the cellulose material to be changed to cellulose pulp of wheat straw and the reaction temperature to be changed to 170 ℃.
The experimental procedure of example 30 was the same as that of example 6, and it was necessary to change the cellulose raw material to cellulose pulp of wheat straw and the reaction time to 1500 min.
The experimental procedure of example 31 was the same as that of example 7, except that the cellulose material was changed to cellulose pulp of wheat straw, the reaction temperature was changed to 180 ℃ and the reaction time was changed to 600 min.
Example 32 the experimental procedure was the same as in example 8, requiring the cellulose pulp of wheat straw to be changed from the cellulose raw material.
The experimental procedure of example 33 was the same as that of example 9, it was necessary to change the cellulose raw material to cellulose pulp of wheat straw and the reaction temperature to 180 ℃.
The experimental procedure of example 34 was the same as that of example 10, and it was necessary to change the cellulose raw material to cellulose pulp of wheat straw and the reaction time to 1000 min.
The experimental procedure of example 35 was the same as that of example 11, except that the cellulose material was changed to cellulose pulp of wheat straw, the reaction temperature was changed to 150 ℃ and the reaction time was changed to 1400 min.
The experimental procedure of example 36 was the same as that of example 12, except that the cellulose material was changed to cellulose pulp of wheat straw, the reaction temperature was changed to 130 ℃ and the reaction time was changed to 1100 min.
The experimental procedure of example 37 was the same as in example 1, requiring the cellulose raw material to be changed to cellulose pulp of beech and the reaction temperature to be changed to 150 ℃.
The experimental procedure of example 38 was the same as in example 2, requiring the cellulose raw material to be changed to cellulose pulp of beech and the reaction time to be changed to 1050 min.
The experimental procedure of example 39 was the same as in example 3, requiring the cellulose raw material to be changed to cellulose pulp of beech and the reaction time to be changed to 900 min.
The experimental procedure of example 40 was the same as in example 4, and it was necessary to change the cellulose raw material to cellulose pulp of beech, the reaction temperature to 200 ℃ and the reaction time to 400 min.
The experimental procedure of example 41 was the same as in example 5, requiring the cellulose raw material to be changed to cellulose pulp of beech and the reaction temperature to be changed to 170 ℃.
The experimental procedure of example 42 was the same as in example 6, requiring the cellulose raw material to be changed to cellulose pulp of beech and the reaction time to be 1250 min.
The experimental procedure of example 43 was the same as in example 7, and it was necessary to change the cellulose raw material to cellulose pulp of beech, the reaction temperature to 180 ℃ and the reaction time to 600 min.
The experimental procedure of example 44 is the same as that of example 8, requiring the cellulose raw material to be changed to cellulose pulp of beech.
The experimental procedure of example 45 was the same as that of example 9, it was necessary to change the cellulose raw material to cellulose pulp of beech and the reaction temperature to 160 ℃.
The experimental procedure of example 46 was the same as in example 10, requiring the cellulose raw material to be changed to cellulose pulp of beech and the reaction time to be changed to 1050 min.
The experimental procedure of example 47 was the same as in example 11, and it was necessary to change the cellulose raw material to cellulose pulp of beech, the reaction temperature to 150 ℃ and the reaction time to 1200 min.
The experimental procedure of example 48 was the same as that of example 12, and it was necessary to change the cellulose raw material to cellulose pulp of beech, the reaction temperature was changed to 140 ℃ and the reaction time was changed to 900 min.
The experimental procedure of example 49 was the same as in example 1, except that the cellulose raw material was changed to cellulose pulp of birch, and the reaction temperature was changed to 160 ℃.
The experimental procedure of example 50 was the same as in example 2, and the cellulose raw material was changed to cellulose pulp of birch, and the reaction time was changed to 950 min.
The experimental procedure of example 51 was the same as in example 3, except that the cellulose raw material was changed to cellulose pulp of birch, and the reaction time was changed to 1000 min.
The experimental procedure of example 52 was the same as in example 4, except that the cellulose material was changed to cellulose pulp of birch, the reaction temperature was changed to 180 ℃ and the reaction time was changed to 600 min.
The experimental procedure of example 53 was the same as in example 5, the cellulose raw material was changed to cellulose pulp of birch, and the reaction temperature was changed to 190 ℃.
The experimental procedure of example 54 was the same as in example 6, except that the cellulose raw material was changed to cellulose pulp of birch, and the reaction time was changed to 1500 min.
The experimental procedure of example 55 was the same as that of example 7, except that the cellulose raw material was changed to cellulose pulp of birch, the reaction temperature was changed to 180 ℃ and the reaction time was changed to 600 min.
The experimental procedure of example 56 was the same as in example 8, requiring the cellulose stock to be changed to birch cellulose pulp.
The experimental procedure of example 57 was the same as that of example 9, it was necessary to change the cellulose raw material to cellulose pulp of birch, and the reaction temperature was changed to 160 ℃.
The experimental procedure of example 58 was the same as in example 10, except that the cellulose raw material was changed to cellulose pulp of birch, and the reaction time was changed to 1100 min.
The experimental procedure of example 59 was the same as that of example 11, except that the cellulose raw material was changed to cellulose pulp of birch, the reaction temperature was changed to 150 ℃ and the reaction time was changed to 1200 min.
The experimental procedure of example 60 was the same as that of example 12, except that the cellulose raw material was changed to cellulose pulp of birch, the reaction temperature was changed to 110 ℃ and the reaction time was changed to 1200 min.
The experimental procedure of example 61 was the same as in example 1, except that the cellulose raw material was changed to microcrystalline cellulose and the reaction temperature was changed to 190 ℃.
The experimental procedure of example 62 was the same as that of example 2, except that the cellulose raw material was changed to microcrystalline cellulose and the reaction time was changed to 960 min.
The experimental procedure of example 63 was the same as in example 3, except that the cellulose material was changed to microcrystalline cellulose and the reaction time was changed to 1050 min.
The experimental procedure of example 64 was the same as that of example 4, except that the cellulose material was changed to microcrystalline cellulose, the reaction temperature was changed to 160 ℃ and the reaction time was changed to 1200 min.
The experimental procedure of example 65 was the same as that of example 5, except that the cellulose raw material was changed to microcrystalline cellulose and the reaction temperature was changed to 170 ℃.
The experimental procedure of example 66 was the same as that of example 6, except that the cellulose raw material was changed to microcrystalline cellulose and the reaction time was changed to 1500 min.
The experimental procedure of example 67 was the same as that of example 7, except that the cellulose raw material was changed to microcrystalline cellulose, the reaction temperature was changed to 170 ℃ and the reaction time was changed to 600 min.
The experimental procedure of example 68 was the same as in example 8, requiring the cellulose raw material to be changed to microcrystalline cellulose.
The experimental procedure of example 69 was the same as that of example 9, except that the cellulose raw material was changed to microcrystalline cellulose and the reaction temperature was changed to 160 ℃.
The experimental procedure of example 70 was the same as that of example 10, except that the cellulose raw material was changed to microcrystalline cellulose and the reaction time was changed to 1000 min.
The experimental procedure of example 71 was the same as that of example 11, except that the cellulose raw material was changed to microcrystalline cellulose, the reaction temperature was changed to 140 ℃ and the reaction time was changed to 1900 min.
The experimental procedure of example 72 was the same as that of example 12, except that the cellulose raw material was changed to microcrystalline cellulose, the reaction temperature was changed to 150 ℃ and the reaction time was changed to 800 min.
The specific experimental conditions and results in the examples are summarized in table 1.
TABLE 1 Experimental conditions and results
The products of the nanocellulose membranes obtained according to examples 2-72, tested, had similar characteristics to # 1.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A nanocellulose, characterized in that said nanocellulose has a water contact angle of less than 20 °.
2. The nanocellulose of claim 1, wherein said nanocellulose has an X-ray diffraction pattern comprising at least two diffraction peaks:
diffraction peak a, 2 θ is between 12 ° and 18 °;
diffraction peak B, 2 θ was between 21 ° and 24 °.
3. A method for preparing nanocellulose in an organic acid system, characterized in that it comprises at least the following steps:
(1) reacting a cellulose raw material with an organic acid solvent and water to obtain a solid reactant, and washing the solid reactant to be neutral;
(2) drying the obtained solid reactant to obtain the nano-cellulose;
preferably, the method further comprises the step of reusing the reaction solution.
4. The method according to claim 3, characterized in that the cellulosic raw material is derived from wood chips and/or straw;
the cellulose raw material is selected from at least one of cellulose pulp, nano-cellulose and microcrystalline cellulose;
preferably, the wood chips comprise at least one of pine, beech, birch;
the straw comprises at least one of corn straw and wheat straw.
5. The method of claim 3, wherein the organic acid solvent comprises at least one of formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, tartaric acid, lactic acid, oxalic acid, maleic acid, and benzoic acid.
6. The method according to claim 3, wherein in the step (1), the ratio of the mass of the cellulose raw material to the total volume of the organic acid solvent and water is 1 g: (1-50) mL;
preferably, in the step (1), the mass ratio of the organic acid solvent to water is (0.01-1): 1.
7. The method according to claim 3, wherein the ratio of the mass of the cellulose raw material to the total volume of the reaction solution recovered by separation in the recycling of the reaction solution is 1 g: (1-50) mL.
8. The method as claimed in claim 3, wherein the step (1) is carried out in a reaction kettle at 80-220 ℃ for 1-40 hours at a reaction pressure of 0.1-40 bar.
9. Use of nanocellulose according to claim 1 or 2 or prepared according to the method of any one of claims 3 to 8 in the field of daily chemicals.
10. Use of nanocellulose according to claim 1 or 2 or prepared according to the method of any one of claims 3 to 8 in a mask product.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104711305A (en) * | 2015-03-25 | 2015-06-17 | 洪思仪 | Method for preparing cellulose nanocrystals through enzyme hydrolysis of bacterial celluloses |
| CN106084071A (en) * | 2016-08-11 | 2016-11-09 | 中国科学院青岛生物能源与过程研究所 | A kind of method preparing nano-cellulose sustainably |
| CN106084070A (en) * | 2016-06-03 | 2016-11-09 | 华南理工大学 | A kind of high-performance nano cellulose and environment-friendly preparation method thereof thereof and application |
| CN107383212A (en) * | 2017-08-07 | 2017-11-24 | 武汉大学 | A kind of hydrophobically modified method of nano-cellulose |
| CN107602711A (en) * | 2017-09-14 | 2018-01-19 | 北京理工大学 | A kind of modified cellulose nano whisker, fiber and preparation method thereof |
| CN109438580A (en) * | 2018-11-27 | 2019-03-08 | 陕西科技大学 | Method for preparing nano cellulose crystal from ultralow acid hydrolysis fiber |
-
2019
- 2019-04-09 CN CN201910281926.5A patent/CN111793139B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104711305A (en) * | 2015-03-25 | 2015-06-17 | 洪思仪 | Method for preparing cellulose nanocrystals through enzyme hydrolysis of bacterial celluloses |
| CN106084070A (en) * | 2016-06-03 | 2016-11-09 | 华南理工大学 | A kind of high-performance nano cellulose and environment-friendly preparation method thereof thereof and application |
| CN106084071A (en) * | 2016-08-11 | 2016-11-09 | 中国科学院青岛生物能源与过程研究所 | A kind of method preparing nano-cellulose sustainably |
| CN107383212A (en) * | 2017-08-07 | 2017-11-24 | 武汉大学 | A kind of hydrophobically modified method of nano-cellulose |
| CN107602711A (en) * | 2017-09-14 | 2018-01-19 | 北京理工大学 | A kind of modified cellulose nano whisker, fiber and preparation method thereof |
| CN109438580A (en) * | 2018-11-27 | 2019-03-08 | 陕西科技大学 | Method for preparing nano cellulose crystal from ultralow acid hydrolysis fiber |
Non-Patent Citations (6)
| Title |
|---|
| B.DEEPA 等: ""Utilization of various lignocellulosic biomass for the production of nanocellulose: a comparative study"", 《CELLULOSE》 * |
| LI HENGCHEN 等: ""Highly thermal-stable and functional cellulose nanocrystals and nanofibrils produced using fully recyclable organic acids"", 《GREEN CHEMISTRY》 * |
| 刘志明 等编: "《生物质纳米纤维素及其功能材料的制备和表征》", 31 December 2016, 东北林业大学出版社 * |
| 张浩 等编: "《基于纳米结晶纤维素复合材料的性能机制研究》", 31 May 2018, 黄河水利出版社 * |
| 范子千 等: ""纳米纤维素研究及应用进展Ⅱ"", 《高分子通报》 * |
| 邹竹帆 等: ""酸水解法制备纤维素纳米晶体的研究进展"", 《中国造纸》 * |
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