CN103450494A - Preparation method of nanocellulose film precipitated by applying water solution - Google Patents
Preparation method of nanocellulose film precipitated by applying water solution Download PDFInfo
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Abstract
The invention discloses a preparation method of a nanocellulose film precipitated by applying a water solution. The preparation method comprises the following steps: dissolving cellulose with concentration of 10-40g/L into a mixed solution of sodium hydroxide, urea and water at minus 15-minus 8 DEG C; after heating the cellulose solution to the room temperature, dropwise adding water to the cellulose solution to precipitate cellulose to obtain nanocellulose colloid dispersion liquid; filter-pressing the nanocellulose colloid dispersion liquid to obtain the nanocellulose film, wherein the mixed solution contains 5-10% of sodium hydroxide, 10-15% of urea and the balance of water by mass percent, and the volume ratio of water to the cellulose solution is (1-3):1. The method overcomes the defects of difficulty in acid waste liquor recovery, high preparation cost, high preparation energy consumption, heavy environmental pollution and the like in the existing preparation method of nanocellulose and the film thereof, and has the advantages of simplicity and high efficiency in operation, solvent reusability, environment friendliness and low energy consumption.
Description
Technical field
The present invention relates to Mierocrystalline cellulose, particularly relate to a kind of nano-cellulose, specifically relate to a kind of preparation method who applies the nano-cellulose film that the aqueous solution separates out, belong to material processing field.
Background technology
Along with the fast-developing of human society and to the irrational utilization of fossil energy, the problem of energy scarcity and environmental pollution is day by day serious, and people are the research of this inexhaustible, nexhaustible renewable resources of growing interest Mierocrystalline cellulose also.With common Mierocrystalline cellulose, compare, the singularity of nano-cellulose on aggregated structure and physical property makes it have broad application prospects in fields such as nanometer fine chemistry industry, nanometer medicine, nanometer food, nano composite material and new forms of energy.
The preparation method of nano-cellulose comprises at present: (1) acid system prepares nano-cellulose, utilize mineral acid or organic acid for catalyzer, provide the high concentration of hydrogen ion to enter cellulosic pars amorpha and destroy hydrogen bond, make its hydrolysis generate the carbohydrates such as glucose, cracking to a certain degree occurs in cellulose chain simultaneously, cause the decline of cellulosic degree of polymerization, thereby obtain nano-cellulose, nineteen forty-seven prepares the nano-cellulose colloidal dispersion by Nickerson and Habrle with hydrochloric acid and sulphuric acid hydrolysis timber and cotton-wool, but the method need to be used strong acid, to conversion unit, require high, can produce acid waste liquid, reclaim and the processing reaction difficulty, (2) enzymolysis process prepares nano-cellulose, utilize cellulase optionally enzymolysis fall unbodied Mierocrystalline cellulose and remaining part cellulose crystals, the method can improve quality and the purity of nano-cellulose, does not need to use chemical, but has the defect that productive rate is low, cost is high, (3) the TEMPO oxidation style prepares nano-cellulose, utilize the TEMPO catalyzed oxidation to prepare nano-cellulose, TEMPO is the selective oxidation to the upper primary hydroxyl of Mierocrystalline cellulose C6 as the agent of catalyzer accelerating oxidation, it is oxidized to polyglucuronic acid, make the fibril surface with negative charge, thereby produce electrostatic repulsion between fibril and obtain stable nano-cellulose colloidal dispersion, in the method, TEMPO is expensive.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned prior art, the preparation method of the nano-cellulose film of provide that a kind of method is simple, the application aqueous solution of less energy consumption, environmental protection being separated out, the method contains the nano-cellulose colloidal dispersion by preparation, finally prepares the cellulosefilm that intensity can reach 64.72MPa.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method who applies the nano-cellulose film that the aqueous solution separates out comprises the following steps:
At-15 ℃～-8 ℃, cellulose dissolution, in the mixing solutions of sodium hydroxide, urea and water, is obtained to cellulose solution; In described cellulose solution, cellulosic concentration is 10～40g/L, and in described mixing solutions, sodium hydroxide quality percentage composition is 5～10%, and the quality percentage composition of urea is 10～15%;
Described cellulose solution is warming up to room temperature naturally, drips water Mierocrystalline cellulose is separated out, obtain the nano-cellulose colloidal dispersion; The volume of described dropping water and the volume ratio of cellulose solution are (1～3): 1;
Described nano-cellulose colloidal dispersion is carried out to press filtration and obtain the nano-cellulose film.
The preparation method of the nano-cellulose film that the application aqueous solution provided by the invention is separated out is under the temperature condition of-15 ℃～-8 ℃, by cellulose dissolution in sodium hydroxide, in the mixing solutions of urea and water, destroy the Hyarogen-bonding between cellulosic molecule, Mierocrystalline cellulose is dissolved, form homogeneous cellulose solution, add again water and change cellulosic solution environmental, make Mierocrystalline cellulose separate out the formation nano-cellulose, the control of realization to Mierocrystalline cellulose size and precipitation process, obtain the nano-grade cellulosic colloidal dispersion that aggregation extent is little, obtain through press filtration the nano-cellulose film that intensity significantly improves again.
Described cellulosic dissolution process does not have particular requirement, dispersed in order to make Mierocrystalline cellulose, preferably in dissolution process, is stirred.May contain the impurity that raw material is brought in described cellulose solution, preferably remove by centrifugation, obtain the cellulose solution of clarification, this solution is the viscous solution of clarification.Described centrifugal process wants seeking time short, avoids solution to change.
Preferably, the volume ratio of the volume of described dropping water and cellulose solution is 1.5: 1.
Preferably, in described mixing solutions, the weight ratio of sodium hydroxide and urea is (6～8): (11～14).
Preferably, in described cellulose solution, the weight ratio of Mierocrystalline cellulose and sodium hydroxide is 1: (2.25～10).In the conversion process of this weight ratio, according to the density of described cellulose solution, be the 1g/ml meter.
Preferably, the volume ratio of the volume of described dropping water and cellulose solution is 1.5: 1.
More preferably, in the water of described dropping and cellulose solution, cellulosic amount ratio is (75～100) ml: 1g, and under this condition, Mierocrystalline cellulose is evenly separated out, and the nano-cellulose length-to-diameter ratio is large, and aggregation extent is low.In the conversion process of this amount ratio, the density of water and cellulose solution is all in 1g/ml.
Described dropping water can be tap water or distilled water, less on cellulosic precipitation process impact.The process of described dropping water preferably drips while stirring, and stirring and drop rate are so that water mixes as purpose with Mierocrystalline cellulose, and concrete operations are not particularly limited.
Preferably, described press filtration is to adopt polyvinylidene difluoride (PVDF) (PVDF) filtering membrane that aperture is 0.22 μ m to carry out press filtration.
The Mierocrystalline cellulose that the present invention uses is from conventional cellulosic material, comprises one or more the mixture in hardwood pulp, softwood pulp, bamboo pulp, Straw Pulp, reed pulp, bagasse pulp, Herba Poae Sphondylodis slurry, Microcrystalline Cellulose and linters.
The present invention is by changing the solution environmental of cellulose solution, and Mierocrystalline cellulose is separated out becomes nano-cellulose, then prepares the nano-cellulose film.In prior art, with organic phase toluene and tensio-active agent, make the fiber dispersion of dissolving in organic phase and water, the toluene molecule is combined dispersion with the cellulose amides skeleton, part toluene molecule enters in the Mierocrystalline cellulose space simultaneously, destroy the hydrogen bond between cellulosic molecule, Mierocrystalline cellulose is disperseed, then, by adding hydrochloric acid that amide group is reduced into to hydroxyl, obtain nano-cellulose, the method is used organic solvent toluene, and environment is caused to very big pollution.And method environmental protection of the present invention, change cellulosic solution environmental by the method that drips water, make cellulosic molecule separate out gradually the formation nano-cellulose, in solvent system of the present invention, sodium hydroxide and Mierocrystalline cellulose generate soda cellulose, there is strong interaction of hydrogen bond between urea and Mierocrystalline cellulose, can play destruction to hydrogen bond between cellulosic molecule, and sodium hydroxide, Absorption for Urea is on cellulosic molecule, cellulose dissolution, when amount of water very few, the concentration of sodium hydroxide and urea is still in higher level, still exist a large amount of sodium hydroxide and urea to destroy hydrogen bond action between cellulosic molecule, Mierocrystalline cellulose is not separated out, and amount of water is too much, sodium hydroxide and urea concentration descend, sodium hydroxide on cellulosic molecule and urea are not enough to destroy the hydrogen bond action between cellulosic molecule, strong segregation occurs in Mierocrystalline cellulose, can not form nano-cellulose, thereby the volume ratio of restriction water and cellulose solution is 1～3:1.Now, hydrogen bond between cellulosic molecule is damaged and slight gathering has occurred, form nano-cellulose, but surface still exists part sodium hydroxide and urea to maintain it stablizes, further gathering does not occur in Mierocrystalline cellulose, obtain the low nano-grade cellulosic of aggregation extent, further prepared film, can effectively improve the intensity of film.
The present invention compared with prior art has the following advantages and effect:
1. in preparation method of the present invention, the nano-cellulose length-to-diameter ratio of separating out is large, easy film forming, and after film forming, tensile strength is high; And that acid system prepares the nano-cellulose length-to-diameter ratio is little, film forming separately;
2. the preparation method of the nano-cellulose film that the application aqueous solution of the present invention is separated out significantly reduces with mechanical process phase specific energy consumption, and the large-scale application cost is low;
3. the inventive method is simple to operate efficient, uses that reagent is cheap to be easy to get; And enzymolysis process, TEMPO oxidation style etc. all exist complex operation complicated or use the expensive problem of reagent;
4. method of the present invention is used the equal green non-pollution of reagent, and all operations is to complete under aqueous solvent, and solvent is reusable; And other solvent liberation method use solvent is organic solvent, environmental pollution is serious.
The accompanying drawing explanation
Fig. 1 is the size distribution figure of nano-cellulose in the nano-cellulose colloidal dispersion of embodiment 1.
Fig. 2 is the transmission electron microscope figure of nano-cellulose in the nano-cellulose colloidal dispersion of embodiment 1.
Fig. 3 is the tensile stress-tension strain figure of the nano-cellulose film of embodiment 1 preparation.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described, it should be noted that, embodiment does not form the restriction to the claimed scope of the present invention.
Take 1g bamboo dissolved pulp oven dry stock, under the condition of-8 ℃, the bamboo dissolved pulp oven dry stock is dissolved in the mixing solutions of 100ml sodium hydroxide, urea and water, in mixing solutions, the mass ratio of sodium hydroxide, urea and water is 7: 12: 81.Within centrifugal 10 minutes, remove impurity with the centrifugal speed of 10000r/min maintaining under the condition of-8 ℃ after stirring 3 minutes, obtain the cellulose solution of 100ml clarification thickness.Naturally drip while stirring 100ml water after being warming up to room temperature in the 100ml cellulose solution, cellulosic molecule is separated out gradually and is obtained the nano-cellulose colloidal dispersion.Use PVDF filtering membrane (the Polyvinylidene Fluoride GVWP14250 that aperture is 0.22 μ m, 0.22 μ m pore size, Millipore, Ireland), two overlapping placements, with pressure filter (142-mm Millipore Hazardous Waste Filtration System, Millipore, Ireland) the nano-cellulose colloidal dispersion made is carried out to press filtration and obtain wet nano-cellulose film, first respectively place a PVDF filtering membrane in wet nano-cellulose film upper and lower surface, respectively place again three water suction filter paper, on sample after pressurization 25kg weight, be placed in thermostat container in 60 ℃ of dry 24h, then remove weight, filtering membrane and filter paper, obtain the nano-cellulose film.
Fig. 1 is used dynamic light scattering (manufacturer: U.S. Brookhaven company, model: the size distribution figure that ZetaPlus) gained nano-cellulose colloidal dispersion is tested the wherein nano-cellulose obtained, as shown in Figure 1: under the colloidal dispersion state, the nano-cellulose particle diameter is in 15～25nm interval, the dynamic light scattering analytical results shows that the median size of nano-cellulose is 17.4nm, shows that preparation method of the present invention can make the Mierocrystalline cellulose of Nano grade.
Fig. 2 is the transmission electron microscope figure of nano-cellulose in the prepared nano-cellulose colloidal dispersion of the present embodiment, testing method is that the nano-cellulose colloidal dispersion is dripped on copper sheet, use deionized water rinsing after standing 30 minutes, functional quality concentration 0.5% acetic acid uranium negative staining was used transmission electron microscope observing after 3 minutes, voltage is 80kV, and magnification is 25000 times.As shown in Figure 2, the cellulosic width that the present invention makes by aqueous solution liberation method is about 20 nanometers, shows that Mierocrystalline cellulose that preparation method of the present invention obtains is in Nano grade.
The tensile stress that Fig. 3 is the prepared nano-cellulose film of the present embodiment-tension strain figure, testing method is for to be placed in relative temperature 50% by the nano-cellulose film, in the constant-temperature constant-humidity environment that temperature is 23 ℃ equilibrium water content after 24 hours according to TAPPI T519 standard testing tensile strength, the test result demonstration, its tensile strength is 64.72MPa.Document shows (king's money money; The research of lignocellulose substrate to cellulase Adsorption law and the standby nano-cellulose of pre-treatment interlock system; The tensile strength of the nano-cellulose film that Guangzhou: South China Science & Engineering University, 2012), mechanical process makes is also in 60-70MPa.
The nano-cellulose film that adopts ultraviolet-visible pectrophotometer test the present embodiment to prepare, testing method is placed in the ultraviolet-visible pectrophotometer sample cell for getting prepared nano-cellulose film, the wavelength region of measuring is that 200nm is to 1000nm, sweep velocity 300nm/min, sampling interval 1nm, spectral bandwidth 4nm, change lamp wavelength 340nm, measures 25 ℃ of temperature.Visible ray (400nm-700nm) transmitance of nano-cellulose film prepared by the present embodiment is 91.7%, and common nano-cellulose film visible ray (400nm-700nm) transmitance the highest can only reach 86.9% rank (Hu Yue, Lee is large, Xu Li etc.; The preparation and property research of high-strength transparence nano-cellulose film; Cellulose Science and technology; 2012,20(3): 51-26).
Embodiment 2
Take 1g leaf wood bleached pulp oven dry stock, under the condition of-8 ℃, leaf wood bleached pulp oven dry stock is dissolved in the mixing solutions of 100ml sodium hydroxide, urea and water, in mixing solutions, the mass ratio of sodium hydroxide, urea and water is 5:15:80.Within centrifugal 10 minutes, remove impurity with the centrifugal speed of 10000r/min maintaining under the condition of-8 ℃ after stirring 3 minutes, obtain the cellulose solution of 100ml clarification thickness.Naturally be warming up to after room temperature and drip while stirring 150ml water in the 100ml cellulose solution, cellulosic molecule is separated out gradually and is obtained the nano-cellulose colloidal dispersion.Use PVDF filtering membrane (the Polyvinylidene Fluoride GVWP14250 that aperture is 0.22 μ m, 0.22 μ m pore size, Millipore, Ireland), two overlapping placements, with pressure filter (142-mm Millipore Hazardous Waste Filtration System, Millipore, Ireland) the nano-cellulose colloidal dispersion made is carried out to press filtration and obtain wet nano-cellulose film, first respectively place a PVDF filtering membrane in wet nano-cellulose film upper and lower surface, respectively place again three water suction filter paper, on sample after pressurization 25kg weight, be placed in thermostat container in 60 ℃ of dry 24h, then remove weight, filtering membrane and filter paper, obtain the nano-cellulose film.
Embodiment 3
Take the 1g Microcrystalline Cellulose, under the condition of-15 ℃, Microcrystalline Cellulose is dissolved in the mixing solutions of 100ml sodium hydroxide, urea and water, in mixing solutions, the mass ratio of sodium hydroxide, urea and water is 10:10:80.Within centrifugal 10 minutes, remove impurity with the centrifugal speed of 10000r/min maintaining under the condition of-15 ℃ after stirring 3 minutes, obtain the cellulose solution of 100ml clarification thickness.Naturally at room temperature in the 100ml cellulose solution, drip while stirring 200ml water after being warming up to room temperature, cellulosic molecule is separated out gradually and is obtained the dispersion of nano-cellulose colloid.Use PVDF filtering membrane (the Polyvinylidene Fluoride GVWP14250 that aperture is 0.22 μ m, 0.22 μ m pore size, Millipore, Ireland), two overlapping placements, with pressure filter (142-mm Millipore Hazardous Waste Filtration System, Millipore, Ireland) the nano-cellulose colloidal dispersion made is carried out to press filtration and obtain wet nano-cellulose film, first respectively place a PVDF filtering membrane in wet nano-cellulose film upper and lower surface, respectively place again three water suction filter paper, on sample after pressurization 25kg weight, be placed in thermostat container in 60 ℃ of dry 24h, then remove weight, filtering membrane and filter paper, obtain the nano-cellulose film.
Embodiment 4
Take 4g bamboo dissolved pulp oven dry stock, under the condition of-15 ℃, the bamboo dissolved pulp oven dry stock is dissolved in the mixing solutions of 100ml sodium hydroxide, urea and water, in mixing solutions, the mass ratio of sodium hydroxide, urea and water is 9:15:76.Within centrifugal 10 minutes, remove impurity with the centrifugal speed of 10000r/min maintaining under the condition of-15 ℃ after stirring 5 minutes, obtain the cellulose solution of 100ml clarification thickness.Naturally at room temperature in the 100ml cellulose solution, drip while stirring 300ml water after being warming up to room temperature, cellulosic molecule is separated out gradually and is obtained the nano-cellulose colloidal dispersion.Use PVDF filtering membrane (the Polyvinylidene Fluoride GVWP14250 that aperture is 0.22 μ m, 0.22 μ m pore size, Millipore, Ireland), two overlapping placements, with pressure filter (142-mm Millipore Hazardous Waste Filtration System, Millipore, Ireland) the nano-cellulose colloidal dispersion made is carried out to press filtration and obtain wet nano-cellulose film, first respectively place a PVDF filtering membrane in wet nano-cellulose film upper and lower surface, respectively place again three water suction filter paper, on sample after pressurization 25kg weight, be placed in thermostat container in 60 ℃ of dry 24h, then remove weight, filtering membrane and filter paper, obtain the nano-cellulose film.
Embodiment 5
Take 1g bamboo dissolved pulp oven dry stock, under the condition of-12 ℃, the bamboo dissolved pulp oven dry stock is dissolved in the mixing solutions of 100ml sodium hydroxide, urea and water, in mixing solutions, the mass ratio of sodium hydroxide, urea and water is 6:14:80.Within centrifugal 20 minutes, remove impurity with the centrifugal speed of 10000r/min maintaining under the condition of-12 ℃ after stirring 3 minutes, obtain the cellulose solution of 100ml clarification thickness.Naturally at room temperature in the 100ml cellulose solution, drip while stirring 150ml water after being warming up to room temperature, cellulosic molecule is separated out gradually and is obtained the nano-cellulose colloidal dispersion.Use PVDF filtering membrane (the Polyvinylidene Fluoride GVWP14250 that aperture is 0.22 μ m, 0.22 μ m pore size, Millipore, Ireland), two overlapping placements, with pressure filter (142-mm Millipore Hazardous Waste Filtration System, Millipore, Ireland) the nano-cellulose colloidal dispersion made is carried out to press filtration and obtain wet nano-cellulose film, first respectively place a PVDF filtering membrane in wet nano-cellulose film upper and lower surface, respectively place again three water suction filter paper, on sample after pressurization 25kg weight, be placed in thermostat container in 60 ℃ of dry 24h, then remove weight, filtering membrane and filter paper, obtain the nano-cellulose film.
Embodiment 6
Take the 2g linters, under the condition of-15 ℃, linters is dissolved in the mixing solutions of 100ml sodium hydroxide, urea and water, in mixing solutions, the mass ratio of sodium hydroxide, urea and water is 8:11:81.Within centrifugal 5 minutes, remove impurity with the centrifugal speed of 10000r/min maintaining under the condition of-15 ℃ after stirring 3 minutes, obtain the cellulose solution of 100ml clarification thickness.Naturally at room temperature in the 100ml cellulose solution, drip while stirring 100ml water after being warming up to room temperature, cellulosic molecule is separated out gradually and is obtained the nano-cellulose colloidal dispersion.Use PVDF filtering membrane (the Polyvinylidene Fluoride GVWP14250 that aperture is 0.22 μ m, 0.22 μ m pore size, Millipore, Ireland), two overlapping placements, with pressure filter (142-mm Millipore Hazardous Waste Filtration System, Millipore, Ireland) the nano-cellulose colloidal dispersion made is carried out to press filtration and obtain wet nano-cellulose film, first respectively place a PVDF filtering membrane in wet nano-cellulose film upper and lower surface, respectively place again three water suction filter paper, on sample after pressurization 25kg weight, be placed in thermostat container in 60 ℃ of dry 24h, then remove weight, filtering membrane and filter paper, obtain the nano-cellulose film.
Use dynamic light scattering to test to the nano-cellulose colloidal dispersion of embodiment 2-6 the size distribution figure that obtains nano-cellulose similar to Fig. 1, in the nano-cellulose colloidal dispersion, the transmission electron microscope figure of nano-cellulose is also basically identical with Fig. 2; The tensile stress of nano-cellulose film-tension strain figure and Fig. 3 are basic identical, at this, do not enumerate.
Claims (6)
1. a preparation method who applies the nano-cellulose film that the aqueous solution separates out is characterized in that comprising the following steps:
At-15 ℃～-8 ℃, cellulose dissolution, in the mixing solutions of sodium hydroxide, urea and water, is obtained to cellulose solution; In described cellulose solution, cellulosic concentration is 10～40g/L, and in described mixing solutions, sodium hydroxide quality percentage composition is 5～10%, and the quality percentage composition of urea is 10～15%;
Described cellulose solution is warming up to room temperature naturally, drips water Mierocrystalline cellulose is separated out, obtain the nano-cellulose colloidal dispersion; The volume of described dropping water and the volume ratio of cellulose solution are (1～3): 1;
Described nano-cellulose colloidal dispersion is carried out to press filtration, obtain the nano-cellulose film.
2. the preparation method of the nano-cellulose film that the application aqueous solution according to claim 1 is separated out is characterized in that: the volume of described dropping water and the volume ratio of cellulose solution are 1.5: 1.
3. the preparation method of the nano-cellulose film that the application aqueous solution according to claim 2 is separated out, it is characterized in that: in the water of described dropping and cellulose solution, cellulosic amount ratio is (75～100) ml: 1g.
4. the preparation method of the nano-cellulose film of separating out according to the described application aqueous solution of claim 1～3 any one is characterized in that: in described mixing solutions, the weight ratio of sodium hydroxide and urea is (6～8): (11～14).
5. the preparation method of the nano-cellulose film of separating out according to the described application aqueous solution of claim 1～3 any one is characterized in that: in described cellulose solution, the weight ratio of Mierocrystalline cellulose and sodium hydroxide is 1: (2.25～10).
6. the preparation method of the nano-cellulose film that the application aqueous solution according to claim 1 is separated out is characterized in that: described press filtration is to adopt the polyvinylidene difluoride (PVDF) filtering membrane that aperture is 0.22 μ m to carry out press filtration.
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| CN105536567A (en) * | 2015-12-25 | 2016-05-04 | 武汉大学 | Sea squirt nano cellulose ultrafiltration membrane as well as preparation method and application of sea squirt nano cellulose ultrafiltration membrane |
| CN106633126A (en) * | 2016-10-15 | 2017-05-10 | 浙江理工大学 | Method for reinforcing hemi-cellulose membrane by utilizing CNCC (Cationic Nanocrystalline Cellulose) |
| CN108755212A (en) * | 2018-05-15 | 2018-11-06 | 昆明理工大学 | A method of repairing secondary stock or reclaimed fibre keratinization |
| CN110585934A (en) * | 2019-08-01 | 2019-12-20 | 华南农业大学 | Composite filter membrane of nano-pore surface layer/micron-pore supporting layer and preparation method and application thereof |
| CN110841610A (en) * | 2019-12-11 | 2020-02-28 | 广西科技大学 | Preparation method of immobilized macromolecule heavy metal adsorbent |
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| CN1112396A (en) * | 1993-11-15 | 1995-11-29 | 郑奎 | Fresh bean gluten (dried soy bean slices) (soy bean) |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105536567A (en) * | 2015-12-25 | 2016-05-04 | 武汉大学 | Sea squirt nano cellulose ultrafiltration membrane as well as preparation method and application of sea squirt nano cellulose ultrafiltration membrane |
| CN105536567B (en) * | 2015-12-25 | 2018-11-13 | 武汉大学 | A kind of ascidian nano-cellulose ultrafiltration membrane and its preparation method and application |
| CN106633126A (en) * | 2016-10-15 | 2017-05-10 | 浙江理工大学 | Method for reinforcing hemi-cellulose membrane by utilizing CNCC (Cationic Nanocrystalline Cellulose) |
| CN106633126B (en) * | 2016-10-15 | 2019-06-18 | 浙江金龙纸业有限公司 | Utilize the method for cation nanometer microcrystalline cellulose enhancing hemicellulose membrane |
| CN108755212A (en) * | 2018-05-15 | 2018-11-06 | 昆明理工大学 | A method of repairing secondary stock or reclaimed fibre keratinization |
| CN110585934A (en) * | 2019-08-01 | 2019-12-20 | 华南农业大学 | Composite filter membrane of nano-pore surface layer/micron-pore supporting layer and preparation method and application thereof |
| CN110841610A (en) * | 2019-12-11 | 2020-02-28 | 广西科技大学 | Preparation method of immobilized macromolecule heavy metal adsorbent |
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