CN114011345B - Nanocellulose aerogel and preparation method and application thereof - Google Patents
Nanocellulose aerogel and preparation method and application thereof Download PDFInfo
- Publication number
- CN114011345B CN114011345B CN202111337884.6A CN202111337884A CN114011345B CN 114011345 B CN114011345 B CN 114011345B CN 202111337884 A CN202111337884 A CN 202111337884A CN 114011345 B CN114011345 B CN 114011345B
- Authority
- CN
- China
- Prior art keywords
- nanocellulose
- nano cellulose
- aerogel
- preparation
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 285
- 239000004964 aerogel Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 71
- 238000001914 filtration Methods 0.000 claims abstract description 26
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims description 79
- 239000000017 hydrogel Substances 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- 229920002678 cellulose Polymers 0.000 claims description 46
- 239000001913 cellulose Substances 0.000 claims description 46
- 239000000499 gel Substances 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 238000004108 freeze drying Methods 0.000 claims description 32
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 16
- 125000000524 functional group Chemical group 0.000 claims description 15
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 15
- 238000007873 sieving Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- 238000003786 synthesis reaction Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000002002 slurry Substances 0.000 description 26
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 26
- 238000003756 stirring Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 16
- 239000005708 Sodium hypochlorite Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000007710 freezing Methods 0.000 description 13
- 230000008014 freezing Effects 0.000 description 13
- 239000011521 glass Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000002791 soaking Methods 0.000 description 13
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 229920002749 Bacterial cellulose Polymers 0.000 description 2
- 239000005016 bacterial cellulose Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000008104 plant cellulose Substances 0.000 description 2
- 241000700605 Viruses Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/02—Loose filtering material, e.g. loose fibres
- B01D39/04—Organic material, e.g. cellulose, cotton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a nano cellulose aerogel and a preparation method and application thereof, belonging to the technical field of material synthesis; the nano cellulose aerogel provided by the technical scheme of the invention has the characteristics of porous net structure in the interior, high porosity, high mechanical strength and the like, can be effectively applied to the field of air filtration, and has the efficiency of removing particles with the particle size of 0.01-2 mu m in air up to more than 99.9%; meanwhile, as the nano cellulose aerogel has high specific surface area and porosity, besides effectively intercepting particulate matters in the air, the filtering resistance is small, namely, the product provided by the technical scheme of the invention can give consideration to resistance pressure drop and filtering efficiency; meanwhile, the nano cellulose aerogel provided by the technical scheme of the invention takes nano cellulose as a raw material, wherein the nano cellulose also has a pore structure, has a certain interception effect on particulate matters, and is simple and easy to obtain by taking the nano cellulose as the raw material, and the acquisition path is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a nano cellulose aerogel and a preparation method and application thereof.
Background
At present, the haze problem has become a very serious environmental problem facing people, and the preparation of materials for effectively filtering small particles in air has become a problem to be solved urgently. However, the existing air filtering materials generally have the defects of low filtering efficiency, large resistance pressure drop and the like. HEPA (High-EFFICIENCY PARTICULATE AIR) filter materials are currently very efficient air filter materials, and the filtration efficiency of typical HEPA materials can reach 99.99%, but this technology is still under exploration in China. The most commonly used air filter materials are fiber materials such as polytetrafluoroethylene films, nonwoven materials of polymer fibers and glass fiber materials. Although the materials have better filtration efficiency, the materials have the defects of environmental protection, low functionality, large resistance pressure drop and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the nano cellulose aerogel which can not only meet the filtration of particulate matters, viruses and the like in the air, but also meet the green environment-friendly requirement, and the preparation method and the application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the nano cellulose aerogel has a porous network structure inside, the average pore diameter of the nano cellulose aerogel is 100-240nm, and the porosity of the nano cellulose aerogel is 69% -88%; the nano cellulose aerogel is prepared from nano cellulose, the length of the nano cellulose is 200-800nm, the diameter of the nano cellulose is 5-80nm, and the content of carboxyl functional groups on the surface is 0.3-1.0mmol/g.
The nano cellulose aerogel provided by the technical scheme of the invention has the characteristics of porous net structure in the interior, high porosity, high mechanical strength and the like, can be effectively applied to the field of air filtration, and has the efficiency of removing particles with the particle size of 0.01-2um in the air of more than 99.9%; meanwhile, the nano cellulose for preparing the nano cellulose aerogel also has a pore structure, has a certain interception effect on particulate matters, and is simple and easy to obtain by taking the nano cellulose as a raw material, and the obtained path is environment-friendly.
In addition, the invention also provides a preparation method of the nano cellulose aerogel, which comprises the following steps:
(1) Preparing a nano cellulose aqueous solution: treating cellulose by using a TEMPO oxidation system to obtain cellulose pulp, crushing, sieving and adding water to the cellulose pulp to obtain a nano cellulose aqueous solution;
(2) Preparation of nanocellulose hydrogel: the nano cellulose aqueous solution in the step (1) is added into a solution containing chloride ions in a rotary dropwise manner, so as to obtain nano cellulose hydrogel;
(3) Preparation of nanocellulose alcohol gel: continuously replacing the nanocellulose hydrogel obtained in the step (2) with a replacement solvent to obtain nanocellulose alcohol gel;
(4) Preparation of nanocellulose aerogel: and (3) freeze-drying the nanocellulose alcohol gel in the step (3) to obtain nanocellulose aerogel.
As a preferred embodiment of the production method of the present invention, in the step (1), the cellulose includes bacterial cellulose or natural plant cellulose.
Bacterial cellulose and natural plant cellulose are wide in sources, simple in acquisition path and environment-friendly.
As a preferred embodiment of the preparation method of the present invention, in the step (1), the mass percentage concentration of the nanocellulose in the nanocellulose aqueous solution is 0.2-1.0%.
When the mass percentage concentration of the nano cellulose in the nano cellulose aqueous solution is in the range, the average pore diameter of the prepared nano cellulose aerogel is proper, the porosity is moderate, and when the nano cellulose aerogel is applied to air filtration, the filtration efficiency of the nano cellulose aerogel on particles with the particle size of 0.01-2um in the air is as high as more than 99.9%.
As a preferred embodiment of the production method of the present invention, in the step (2), the solution containing chloride ions includes a zinc chloride solution, a calcium chloride solution or a sodium chloride solution.
As a preferred embodiment of the production method of the present invention, in the step (2), the concentration of chloride ions in the solution containing chloride ions is 0.8 to 1.6mol/L.
As a preferred embodiment of the preparation method of the present invention, in the step (2), the volume ratio of the solution containing chloride ions to the nanocellulose aqueous solution is 1: (1-5).
As a preferred embodiment of the production method of the present invention, in the step (3), the displacement solvent includes t-butanol or ethanol.
As a preferred embodiment of the preparation method of the present invention, in the step (3), the specific process of continuous substitution is as follows: the nanocellulose hydrogel is respectively and continuously soaked in 25%, 50%, 75% and 100% of replacement solvents for 12-24 hours in sequence.
As a preferred embodiment of the preparation method of the present invention, in the step (4), the time of freeze-drying is 12-24 hours, and the temperature of freeze-drying is (-24) - (-20) deg.C.
In addition, the invention also provides application of the nano cellulose aerogel in the field of air filtration.
Compared with the prior art, the invention has the beneficial effects that:
first: the nano cellulose aerogel provided by the technical scheme of the invention has the characteristics of porous net structure in the interior, high porosity, high mechanical strength and the like, can be effectively applied to the field of air filtration, and has the efficiency of removing particles with the particle size of 0.01-2um in the air of more than 99.9%; meanwhile, as the nano cellulose aerogel has high specific surface area and porosity, besides effectively intercepting particulate matters in the air, the filtering resistance is small, namely, the product provided by the technical scheme of the invention can give consideration to resistance pressure drop and filtering efficiency;
Second,: according to the technical scheme provided by the invention, the nano cellulose aerogel takes the nano cellulose as a raw material, wherein the nano cellulose also has a pore structure, a certain interception effect on particulate matters is achieved, and the nano cellulose is taken as the raw material, so that the method is simple and easy to obtain, and the obtained path is environment-friendly.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Example 1
The specific synthesis steps of the nanocellulose aerogel provided in this embodiment are as follows:
(1) Preparation of nanocellulose slurry: adding 0.032g TEMPO and 0.2g NaBr into 200mL of water, adding 2g cellulose, then adding 3.2g sodium hypochlorite solution with the mass percent of 12%, stirring for 10 minutes at room temperature, then dropwise adding 1% NaOH aqueous solution into a reaction system under the stirring condition until the pH value of the system is 10, and stopping the reaction to obtain cellulose slurry;
(2) Preparing a nano cellulose aqueous solution: crushing the cellulose pulp prepared in the step (1) for 10 minutes by using a homogenizer, sieving the crushed substance with a 100-mesh sieve, and adding the filtered product into 400g of water to obtain a nano cellulose aqueous solution; the diameter of the obtained nanocellulose is about 6nm, the length is about 420nm, and the content of carboxyl functional groups on the surface is 0.9mmol/g;
(3) Preparation of nanocellulose hydrogel: the nano cellulose aqueous solution in the step (2) is added into a ZnCl 2 solution with the concentration of 0.4mol/L and 200mL in a rotating manner, so as to obtain nano cellulose hydrogel, and the nano cellulose hydrogel is washed by deionized water;
(4) Preparation of nanocellulose alcohol gel: soaking the nanocellulose hydrogel obtained in the step (3) in 25%, 50%, 75% and 100% of tertiary butanol aqueous solution for 20 hours at a time to obtain nanocellulose alcohol gel;
(5) Preparation of nanocellulose aerogel: pouring the nanocellulose alcohol gel obtained in the step (4) into a glass bottle, unscrewing a bottle cap, putting into liquid nitrogen for 5 minutes, freezing, putting into a cold dryer for 24 hours, freeze-drying at (-20) DEG C, and freeze-drying to obtain the nanocellulose aerogel.
Example 2
The specific synthesis steps of the nanocellulose aerogel provided in this embodiment are as follows:
(1) Preparation of nanocellulose slurry: adding 0.016g of TEMPO and 0.2g of NaBr into 200mL of water, adding 2g of cellulose, then adding 1.6g of sodium hypochlorite solution with the mass percent of 12%, stirring for 10 minutes at room temperature, then dropwise adding 1% of NaOH aqueous solution into a reaction system under the stirring condition until the pH value of the system is 10, and stopping the reaction to obtain cellulose slurry;
(2) Preparing a nano cellulose aqueous solution: crushing the cellulose pulp prepared in the step (1) for 5 minutes by using a homogenizer, sieving the crushed substance with a 100-mesh sieve, and adding the filtered product into 400g of water to obtain a nano cellulose aqueous solution; the diameter of the obtained nanocellulose is about 13nm, the length is about 320nm, and the content of carboxyl functional groups on the surface is 0.5mmol/g;
(3) Preparation of nanocellulose hydrogel: the nano cellulose aqueous solution in the step (2) is added into a ZnCl 2 solution with the concentration of 0.4mol/L and 200mL in a rotating manner, so as to obtain nano cellulose hydrogel, and the nano cellulose hydrogel is washed by deionized water;
(4) Preparation of nanocellulose alcohol gel: soaking the nanocellulose hydrogel obtained in the step (3) in 25%, 50%, 75% and 100% of tertiary butanol aqueous solution for 20 hours at a time to obtain nanocellulose alcohol gel;
(5) Preparation of nanocellulose aerogel: pouring the nanocellulose alcohol gel obtained in the step (4) into a glass bottle, unscrewing a bottle cap, putting into liquid nitrogen for 5 minutes, freezing, putting into a cold dryer for 24 hours, freeze-drying at (-20) DEG C, and freeze-drying to obtain the nanocellulose aerogel.
Example 3
The specific synthesis steps of the nanocellulose aerogel provided in this embodiment are as follows:
(1) Preparation of nanocellulose slurry: adding 0.032g TEMPO and 0.2g NaBr into 200mL of water, adding 2g cellulose, then adding 3.2g sodium hypochlorite solution with the mass percent of 12%, stirring for 10 minutes at room temperature, then dropwise adding 1% NaOH aqueous solution into a reaction system under the stirring condition until the pH value of the system is 10, and stopping the reaction to obtain cellulose slurry;
(2) Preparing a nano cellulose aqueous solution: crushing the cellulose pulp prepared in the step (1) for 10 minutes by using a homogenizer, sieving the crushed substance with a 100-mesh sieve, and adding the filtered product into 400g of water to obtain a nano cellulose aqueous solution; the diameter of the obtained nanocellulose is about 6nm, the length is about 420nm, and the content of carboxyl functional groups on the surface is 0.9mmol/g;
(3) Preparation of nanocellulose hydrogel: the nano cellulose aqueous solution in the step (2) is added into 200mL CaCl 2 solution with the concentration of 0.4mol/L in a rotating and dripping manner, so as to obtain nano cellulose hydrogel, and the nano cellulose hydrogel is washed by deionized water;
(4) Preparation of nanocellulose alcohol gel: soaking the nanocellulose hydrogel obtained in the step (3) in 25%, 50%, 75% and 100% of tertiary butanol aqueous solution for 20 hours at a time to obtain nanocellulose alcohol gel;
(5) Preparation of nanocellulose aerogel: pouring the nanocellulose alcohol gel obtained in the step (4) into a glass bottle, unscrewing a bottle cap, putting into liquid nitrogen for 5 minutes, freezing, putting into a cold dryer for 24 hours, freeze-drying at (-20) DEG C, and freeze-drying to obtain the nanocellulose aerogel.
Example 4
The specific synthesis steps of the nanocellulose aerogel provided in this embodiment are as follows:
(1) Preparation of nanocellulose slurry: adding 0.032g TEMPO and 0.2g NaBr into 200mL of water, adding 2g cellulose, then adding 3.2g sodium hypochlorite solution with the mass percent of 12%, stirring for 10 minutes at room temperature, then dropwise adding 1% NaOH aqueous solution into a reaction system under the stirring condition until the pH value of the system is 10, and stopping the reaction to obtain cellulose slurry;
(2) Preparing a nano cellulose aqueous solution: crushing the cellulose pulp prepared in the step (1) for 10 minutes by using a homogenizer, sieving the crushed substance with a 100-mesh sieve, and adding the filtered product into 400g of water to obtain a nano cellulose aqueous solution; the diameter of the obtained nanocellulose is about 6nm, the length is about 420nm, and the content of carboxyl functional groups on the surface is 0.9mmol/g;
(3) Preparation of nanocellulose hydrogel: the nano cellulose aqueous solution in the step (2) is added into a ZnCl 2 solution with the concentration of 0.8mol/L and 200mL in a rotating manner, so as to obtain nano cellulose hydrogel, and the nano cellulose hydrogel is washed by deionized water;
(4) Preparation of nanocellulose alcohol gel: soaking the nanocellulose hydrogel obtained in the step (3) in 25%, 50%, 75% and 100% of tertiary butanol aqueous solution for 20 hours at a time to obtain nanocellulose alcohol gel;
(5) Preparation of nanocellulose aerogel: pouring the nanocellulose alcohol gel obtained in the step (4) into a glass bottle, unscrewing a bottle cap, putting into liquid nitrogen for 5 minutes, freezing, putting into a cold dryer for 24 hours, freeze-drying at (-20) DEG C, and freeze-drying to obtain the nanocellulose aerogel.
Example 5
The specific synthesis steps of the nanocellulose aerogel provided in this embodiment are as follows:
(1) Preparation of nanocellulose slurry: adding 0.032g TEMPO and 0.2g NaBr into 200mL of water, adding 2g cellulose, then adding 3.2g sodium hypochlorite solution with the mass percent of 12%, stirring for 10 minutes at room temperature, then dropwise adding 1% NaOH aqueous solution into a reaction system under the stirring condition until the pH value of the system is 10, and stopping the reaction to obtain cellulose slurry;
(2) Preparing a nano cellulose aqueous solution: crushing the cellulose pulp prepared in the step (1) for 10 minutes by using a homogenizer, sieving the crushed substance with a 100-mesh sieve, and adding the filtered product into 1000g of water to obtain a nano cellulose aqueous solution; the diameter of the obtained nanocellulose is about 6nm, the length is about 420nm, and the content of carboxyl functional groups on the surface is 0.9mmol/g;
(3) Preparation of nanocellulose hydrogel: the nano cellulose aqueous solution in the step (2) is added into a ZnCl 2 solution with the concentration of 0.4mol/L and 200mL in a rotating manner, so as to obtain nano cellulose hydrogel, and the nano cellulose hydrogel is washed by deionized water;
(4) Preparation of nanocellulose alcohol gel: soaking the nanocellulose hydrogel obtained in the step (3) in 25%, 50%, 75% and 100% of tertiary butanol aqueous solution for 20 hours at a time to obtain nanocellulose alcohol gel;
(5) Preparation of nanocellulose aerogel: pouring the nanocellulose alcohol gel obtained in the step (4) into a glass bottle, unscrewing a bottle cap, putting into liquid nitrogen for 5 minutes, freezing, putting into a cold dryer for 24 hours, freeze-drying at (-20) DEG C, and freeze-drying to obtain the nanocellulose aerogel.
Example 6
The specific synthesis steps of the nanocellulose aerogel provided in this embodiment are as follows:
(1) Preparation of nanocellulose slurry: adding 0.032g TEMPO and 0.2g NaBr into 200mL of water, adding 4g cellulose, then adding 3.2g sodium hypochlorite solution with the mass percent of 12%, stirring for 10 minutes at room temperature, then dropwise adding 1% NaOH aqueous solution into a reaction system under the stirring condition until the pH value of the system is 10, and stopping the reaction to obtain cellulose slurry;
(2) Preparing a nano cellulose aqueous solution: crushing the cellulose pulp prepared in the step (1) for 10 minutes by using a homogenizer, sieving the crushed substance with a 100-mesh sieve, and adding the filtered product into 400g of water to obtain a nano cellulose aqueous solution; the diameter of the obtained nanocellulose is about 6nm, the length is about 420nm, and the content of carboxyl functional groups on the surface is 0.6mmol/g;
(3) Preparation of nanocellulose hydrogel: the nano cellulose aqueous solution in the step (2) is added into a ZnCl 2 solution with the concentration of 0.4mol/L and 200mL in a rotating manner, so as to obtain nano cellulose hydrogel, and the nano cellulose hydrogel is washed by deionized water;
(4) Preparation of nanocellulose alcohol gel: soaking the nanocellulose hydrogel obtained in the step (3) in 25%, 50%, 75% and 100% of tertiary butanol aqueous solution for 20 hours at a time to obtain nanocellulose alcohol gel;
(5) Preparation of nanocellulose aerogel: pouring the nanocellulose alcohol gel obtained in the step (4) into a glass bottle, unscrewing a bottle cap, putting into liquid nitrogen for 5 minutes, freezing, putting into a cold dryer for 24 hours, freeze-drying at (-20) DEG C, and freeze-drying to obtain the nanocellulose aerogel.
Example 7
The specific synthesis steps of the nanocellulose aerogel provided in this embodiment are as follows:
(1) Preparation of nanocellulose slurry: adding 0.032g TEMPO and 0.2g NaBr into 200mL of water, adding 2g cellulose, then adding 3.2g sodium hypochlorite solution with the mass percent of 12%, stirring for 10 minutes at room temperature, then dropwise adding 1% NaOH aqueous solution into a reaction system under the stirring condition until the pH value of the system is 10, and stopping the reaction to obtain cellulose slurry;
(2) Preparing a nano cellulose aqueous solution: crushing the cellulose pulp prepared in the step (1) for 5 minutes by using a homogenizer, sieving the crushed substance with a 100-mesh sieve, and adding the filtered product into 400g of water to obtain a nano cellulose aqueous solution; the diameter of the obtained nanocellulose is about 45nm, the length is about 560nm, and the content of carboxyl functional groups on the surface is 0.9mmol/g;
(3) Preparation of nanocellulose hydrogel: the nano cellulose aqueous solution in the step (2) is added into a ZnCl 2 solution with the concentration of 0.4mol/L and 200mL in a rotating manner, so as to obtain nano cellulose hydrogel, and the nano cellulose hydrogel is washed by deionized water;
(4) Preparation of nanocellulose alcohol gel: soaking the nanocellulose hydrogel obtained in the step (3) in 25%, 50%, 75% and 100% of tertiary butanol aqueous solution for 20 hours at a time to obtain nanocellulose alcohol gel;
(5) Preparation of nanocellulose aerogel: pouring the nanocellulose alcohol gel obtained in the step (4) into a glass bottle, unscrewing a bottle cap, putting into liquid nitrogen for 5 minutes, freezing, putting into a cold dryer for 24 hours, freeze-drying at (-20) DEG C, and freeze-drying to obtain the nanocellulose aerogel.
Example 8
The specific synthesis steps of the nanocellulose aerogel provided in this embodiment are as follows:
(1) Preparation of nanocellulose slurry: adding 0.032g TEMPO and 0.2g NaBr into 200mL of water, adding 2g cellulose, then adding 3.2g sodium hypochlorite solution with the mass percent of 12%, stirring for 10 minutes at room temperature, then dropwise adding 1% NaOH aqueous solution into a reaction system under the stirring condition until the pH value of the system is 10, and stopping the reaction to obtain cellulose slurry;
(2) Preparing a nano cellulose aqueous solution: crushing the cellulose pulp prepared in the step (1) for 10 minutes by using a homogenizer, sieving the crushed substance with a 100-mesh sieve, and adding the filtered product into 400g of water to obtain a nano cellulose aqueous solution; the diameter of the obtained nanocellulose is about 80nm, the length is about 740nm, and the content of carboxyl functional groups on the surface is 0.9mmol/g;
(3) Preparation of nanocellulose hydrogel: the nano cellulose aqueous solution in the step (2) is added into a ZnCl 2 solution with the concentration of 0.4mol/L and 200mL in a rotating manner, so as to obtain nano cellulose hydrogel, and the nano cellulose hydrogel is washed by deionized water;
(4) Preparation of nanocellulose alcohol gel: soaking the nanocellulose hydrogel obtained in the step (3) in 25%, 50%, 75% and 100% of tertiary butanol aqueous solution for 20 hours at a time to obtain nanocellulose alcohol gel;
(5) Preparation of nanocellulose aerogel: pouring the nanocellulose alcohol gel obtained in the step (4) into a glass bottle, unscrewing a bottle cap, putting into liquid nitrogen for 5 minutes, freezing, putting into a cold dryer for 24 hours, freeze-drying at (-20) DEG C, and freeze-drying to obtain the nanocellulose aerogel.
Comparative example 1
The specific synthesis steps of the nanocellulose aerogel provided in this comparative example are as follows:
(1) Preparation of nanocellulose slurry: adding 0.032g TEMPO and 0.2g NaBr into 200mL of water, adding 2g cellulose, then adding 3.2g sodium hypochlorite solution with the mass percent of 12%, stirring for 10 minutes at room temperature, then dropwise adding 1% NaOH aqueous solution into a reaction system under the stirring condition until the pH value of the system is 10, and stopping the reaction to obtain cellulose slurry;
(2) Preparing a nano cellulose aqueous solution: crushing the cellulose pulp prepared in the step (1) for 1 minute by using a homogenizer, sieving the crushed substance with a 100-mesh sieve, and adding the filtered product into 400g of water to obtain a nano cellulose aqueous solution; the diameter of the obtained nanocellulose is about 160nm, the length is about 940nm, and the content of carboxyl functional groups on the surface is 0.9mmol/g;
(3) Preparation of nanocellulose hydrogel: the nano cellulose aqueous solution in the step (2) is added into a ZnCl 2 solution with the concentration of 0.4mol/L and 200mL in a rotating manner, so as to obtain nano cellulose hydrogel, and the nano cellulose hydrogel is washed by deionized water;
(4) Preparation of nanocellulose alcohol gel: soaking the nanocellulose hydrogel obtained in the step (3) in 25%, 50%, 75% and 100% of tertiary butanol aqueous solution for 20 hours at a time to obtain nanocellulose alcohol gel;
(5) Preparation of nanocellulose aerogel: pouring the nanocellulose alcohol gel obtained in the step (4) into a glass bottle, unscrewing a bottle cap, putting into liquid nitrogen for 5 minutes, freezing, putting into a cold dryer for 24 hours, freeze-drying at (-20) DEG C, and freeze-drying to obtain the nanocellulose aerogel.
Comparative example 2
The specific synthesis steps of the nanocellulose aerogel provided in this comparative example are as follows:
(1) Preparation of nanocellulose slurry: adding 0.032g TEMPO and 0.2g NaBr into 200mL of water, adding 2g cellulose, then adding 3.2g sodium hypochlorite solution with the mass percent of 12%, stirring for 10 minutes at room temperature, then dropwise adding 1% NaOH aqueous solution into a reaction system under the stirring condition until the pH value of the system is 10, and stopping the reaction to obtain cellulose slurry;
(2) Preparing a nano cellulose aqueous solution: crushing the cellulose pulp prepared in the step (1) for 10 minutes by using a homogenizer, sieving the crushed substance with a 100-mesh sieve, and adding the filtered product into 400g of water to obtain a nano cellulose aqueous solution; the diameter of the obtained nanocellulose is about 6nm, the length is about 420nm, and the content of carboxyl functional groups on the surface is 0.9mmol/g;
(3) Preparation of nanocellulose hydrogel: the nano cellulose aqueous solution in the step (2) is added into a ZnCl 2 solution with the concentration of 2.0mol/L and 200mL in a rotating manner, so as to obtain nano cellulose hydrogel, and the nano cellulose hydrogel is washed by deionized water;
(4) Preparation of nanocellulose alcohol gel: soaking the nanocellulose hydrogel obtained in the step (3) in 25%, 50%, 75% and 100% of tertiary butanol aqueous solution for 20 hours at a time to obtain nanocellulose alcohol gel;
(5) Preparation of nanocellulose aerogel: pouring the nanocellulose alcohol gel obtained in the step (4) into a glass bottle, unscrewing a bottle cap, putting into liquid nitrogen for 5 minutes, freezing, putting into a cold dryer for 24 hours, freeze-drying at (-20) DEG C, and freeze-drying to obtain the nanocellulose aerogel.
Comparative example 3
The specific synthesis steps of the nanocellulose aerogel provided in this comparative example are as follows:
(1) Preparation of nanocellulose slurry: adding 0.032g TEMPO and 0.2g NaBr into 200mL of water, adding 2g cellulose, then adding 3.2g sodium hypochlorite solution with the mass percent of 12%, stirring for 10 minutes at room temperature, then dropwise adding 1% NaOH aqueous solution into a reaction system under the stirring condition until the pH value of the system is 10, and stopping the reaction to obtain cellulose slurry;
(2) Preparing a nano cellulose aqueous solution: crushing the cellulose pulp prepared in the step (1) for 10 minutes by using a homogenizer, sieving the crushed substance with a 100-mesh sieve, and adding the filtered product into 1500g of water to obtain a nano cellulose aqueous solution; the diameter of the obtained nanocellulose is about 6nm, the length is about 420nm, and the content of carboxyl functional groups on the surface is 0.9mmol/g;
(3) Preparation of nanocellulose hydrogel: the nano cellulose aqueous solution in the step (2) is added into a ZnCl 2 solution with the concentration of 0.4mol/L and 200mL in a rotating manner, so as to obtain nano cellulose hydrogel, and the nano cellulose hydrogel is washed by deionized water;
(4) Preparation of nanocellulose alcohol gel: soaking the nanocellulose hydrogel obtained in the step (3) in 25%, 50%, 75% and 100% of tertiary butanol aqueous solution for 20 hours at a time to obtain nanocellulose alcohol gel;
(5) Preparation of nanocellulose aerogel: pouring the nanocellulose alcohol gel obtained in the step (4) into a glass bottle, unscrewing a bottle cap, putting into liquid nitrogen for 5 minutes, freezing, putting into a cold dryer for 24 hours, freeze-drying at (-20) DEG C, and freeze-drying to obtain the nanocellulose aerogel.
Comparative example 4
The specific synthesis steps of the nanocellulose aerogel provided in this comparative example are as follows:
(1) Preparation of nanocellulose slurry: adding 0.032g TEMPO and 0.2g NaBr into 200mL of water, adding 10g cellulose, then adding 3.2g sodium hypochlorite solution with the mass percent of 12%, stirring for 10 minutes at room temperature, then dropwise adding 1% NaOH aqueous solution into a reaction system under the stirring condition until the pH value of the system is 10, and stopping the reaction to obtain cellulose slurry;
(2) Preparing a nano cellulose aqueous solution: crushing the cellulose pulp prepared in the step (1) for 10 minutes by using a homogenizer, sieving the crushed substance with a 100-mesh sieve, and adding the filtered product into 400g of water to obtain a nano cellulose aqueous solution; the diameter of the obtained nanocellulose is about 6nm, the length is about 420nm, and the content of carboxyl functional groups on the surface is 0.2mmol/g;
(3) Preparation of nanocellulose hydrogel: the nano cellulose aqueous solution in the step (2) is added into a ZnCl 2 solution with the concentration of 0.4mol/L and 200mL in a rotating manner, so as to obtain nano cellulose hydrogel, and the nano cellulose hydrogel is washed by deionized water;
(4) Preparation of nanocellulose alcohol gel: soaking the nanocellulose hydrogel obtained in the step (3) in 25%, 50%, 75% and 100% of tertiary butanol aqueous solution for 20 hours at a time to obtain nanocellulose alcohol gel;
(5) Preparation of nanocellulose aerogel: pouring the nanocellulose alcohol gel obtained in the step (4) into a glass bottle, unscrewing a bottle cap, putting into liquid nitrogen for 5 minutes, freezing, putting into a cold dryer for 24 hours, freeze-drying at (-20) DEG C, and freeze-drying to obtain the nanocellulose aerogel.
Comparative example 5
The specific synthesis steps of the nanocellulose aerogel provided in this comparative example are as follows:
(1) Preparation of nanocellulose slurry: adding 0.096g TEMPO and 0.6g NaBr into 200mL of water, adding 2g cellulose, adding 3.2g sodium hypochlorite solution with the mass percent of 12%, stirring for 10 minutes at room temperature, then dropwise adding NaOH aqueous solution with the mass percent of 1% into a reaction system under the stirring condition until the pH value of the system is 10, and stopping the reaction to obtain cellulose slurry;
(2) Preparing a nano cellulose aqueous solution: crushing the cellulose pulp prepared in the step (1) for 10 minutes by using a homogenizer, sieving the crushed substance with a 100-mesh sieve, and adding the filtered product into 400g of water to obtain a nano cellulose aqueous solution; the diameter of the obtained nanocellulose is about 6nm, the length is about 420nm, and the content of carboxyl functional groups on the surface is 1.5mmol/g;
(3) Preparation of nanocellulose hydrogel: the nano cellulose aqueous solution in the step (2) is added into a ZnCl 2 solution with the concentration of 0.4mol/L and 200mL in a rotating manner, so as to obtain nano cellulose hydrogel, and the nano cellulose hydrogel is washed by deionized water;
(4) Preparation of nanocellulose alcohol gel: soaking the nanocellulose hydrogel obtained in the step (3) in 25%, 50%, 75% and 100% of tertiary butanol aqueous solution for 20 hours at a time to obtain nanocellulose alcohol gel;
(5) Preparation of nanocellulose aerogel: pouring the nanocellulose alcohol gel obtained in the step (4) into a glass bottle, unscrewing a bottle cap, putting into liquid nitrogen for 5 minutes, freezing, putting into a cold dryer for 24 hours, freeze-drying at (-20) DEG C, and freeze-drying to obtain the nanocellulose aerogel.
Effect example
The nanocellulose aerogels prepared in examples 1-8 and comparative examples 1-5 were subjected to measurement of average pore diameter and porosity, and the average filtration efficiency and resistance pressure drop when the nanocellulose aerogel prepared by application was subjected to air filtration were detected, wherein the statistics when the nanocellulose aerogel was applied to air filtration are the filtration efficiency of particles with the particle size of 0.01-2um, and the results are shown in table 1;
Table 1: characterization and application data for nanocellulose aerogel
As can be seen from table 1, when the technical scheme provided by the invention is adopted, the average filtration efficiency of the prepared nano cellulose aerogel is more than 99.9%, and the average resistance pressure drop is smaller and is less than 81%; it can be seen from examples 1-8 that the larger the porosity is, the higher the filtration efficiency is, but the resistance pressure drop is also increased, and in the preparation process, the parameters such as the mass percent of the nanocellulose in the nanocellulose aqueous solution, the volume ratio of the nanocellulose to the chloridion-containing solution, the mass percent of the chloridion in the chloridion-containing solution and the like all have influence on the average pore diameter and the porosity of the product; it can be seen from examples 1 and comparative example 1 that when the diameter of the prepared nanocellulose is too large, the filtration efficiency is significantly reduced, and from examples 1 and comparative example 2, when the mass percentage of chloride ions in the chloride ion-containing solution is too high, the pore size of the obtained nanocellulose aerogel is too small, while good filtration efficiency can be ensured, but resistance pressure drop is caused to be too high, and from examples 1 and comparative example 3, when the mass percentage of nanocellulose in the nanocellulose aqueous solution is too low, the nanocellulose pore size is too low, and thus the filtration efficiency is significantly reduced, and from examples 1 and comparative example 4, resistance pressure drop is caused to be too high, and from examples 1 and comparative example 5, when the surface carboxyl content in the nanocellulose aqueous solution is too high.
Finally, it should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, and that those skilled in the art will understand that changes can be made to the technical solutions of the invention or equivalents thereof without departing from the spirit and scope of the technical solutions of the invention.
Claims (5)
1. The nano cellulose aerogel is characterized in that the inside of the nano cellulose aerogel is in a porous network structure, the average pore diameter is 100-240nm, and the porosity is 69% -88%; the nano cellulose aerogel is prepared from nano cellulose, the length of the nano cellulose is 200-800nm, the diameter of the nano cellulose is 5-80nm, and the content of carboxyl functional groups on the surface is 0.5-1.0mmol/g; the preparation method of the nano cellulose aerogel comprises the following steps:
(1) Preparing a nano cellulose aqueous solution: treating cellulose by using a TEMPO oxidation system to obtain cellulose pulp, crushing, sieving and adding water to the cellulose pulp to obtain a nano cellulose aqueous solution;
(2) Preparation of nanocellulose hydrogel: the nano cellulose aqueous solution in the step (1) is added into a solution containing chloride ions in a rotary dropwise manner, so as to obtain nano cellulose hydrogel;
(3) Preparation of nanocellulose alcohol gel: continuously replacing the nanocellulose hydrogel obtained in the step (2) with a replacement solvent to obtain nanocellulose alcohol gel;
(4) Preparation of nanocellulose aerogel: freeze-drying the nanocellulose alcohol gel obtained in the step (3) to obtain nanocellulose aerogel;
In the step (1), the mass percentage concentration of the nanocellulose in the nanocellulose aqueous solution is 0.2-1.0%;
in the step (2), the concentration of chloride ions in the solution containing the chloride ions is 0.8-1.6mol/L;
in the step (2), the volume ratio of the solution containing chloride ions to the nano cellulose aqueous solution is 1: (1-5);
in the step (3), the specific process of continuous replacement is as follows: the nanocellulose hydrogel is respectively and continuously soaked in 25%, 50%, 75% and 100% of replacement solvents for 12-24 hours in sequence.
2. The nanocellulose aerogel of claim 1 wherein in step (2) the solution containing chloride ions comprises a zinc chloride solution, a calcium chloride solution, or a sodium chloride solution.
3. The nanocellulose aerogel of claim 1 wherein in step (3), the displacement solvent comprises t-butanol or ethanol.
4. The nanocellulose aerogel as claimed in claim 1 wherein in step (4) the time of freeze drying is 12-24 hours and the temperature of freeze drying is (-24) - (-20) deg.c.
5. Use of the nanocellulose aerogel of claim 1 in the field of air filtration.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111337884.6A CN114011345B (en) | 2021-11-12 | 2021-11-12 | Nanocellulose aerogel and preparation method and application thereof |
| PCT/CN2022/078328 WO2023082498A1 (en) | 2021-11-12 | 2022-02-28 | Nanocellulose aerogel, preparation method therefor and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111337884.6A CN114011345B (en) | 2021-11-12 | 2021-11-12 | Nanocellulose aerogel and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114011345A CN114011345A (en) | 2022-02-08 |
| CN114011345B true CN114011345B (en) | 2024-05-28 |
Family
ID=80063668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111337884.6A Active CN114011345B (en) | 2021-11-12 | 2021-11-12 | Nanocellulose aerogel and preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114011345B (en) |
| WO (1) | WO2023082498A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114011345B (en) * | 2021-11-12 | 2024-05-28 | 清远高新华园科技协同创新研究院有限公司 | Nanocellulose aerogel and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103562284A (en) * | 2011-03-25 | 2014-02-05 | 丝路技术公司 | Cellulose-based materials comprising nanofibrillated cellulose from native cellulose |
| CN106750384A (en) * | 2016-12-29 | 2017-05-31 | 南京林业大学 | A kind of method of amino silane modified nano-cellulose aerogel |
| CN106893116A (en) * | 2017-02-24 | 2017-06-27 | 浙江和也健康科技有限公司 | A kind of preparation method of cellulose nano-fibrous biomass gel and aeroge |
| CN107722338A (en) * | 2017-10-31 | 2018-02-23 | 天津科技大学 | The preparation method and nano-cellulose aerogel of a kind of nano-cellulose aerogel |
| CN110172185A (en) * | 2019-05-08 | 2019-08-27 | 南京林业大学 | A kind of anisotropy nano-cellulose aerogel and preparation method thereof and device |
| CN111793241A (en) * | 2020-07-23 | 2020-10-20 | 武汉纺织大学 | Ramie bone nanocrystalline cellulose aerogel and preparation method thereof |
| JP2020189947A (en) * | 2019-05-23 | 2020-11-26 | 本田技研工業株式会社 | Manufacturing method of cellulose porous body |
| CN112876713A (en) * | 2021-03-02 | 2021-06-01 | 内蒙古科技大学 | Preparation method of cellulose aerogel-based efficient air filtering membrane |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0916031D0 (en) * | 2009-09-14 | 2009-10-28 | Univ Nottingham | Cellulose nanoparticle aerogels,hydrogels and organogels |
| CN105017555B (en) * | 2014-04-29 | 2018-10-02 | 中国科学院化学研究所 | A kind of preparation method of cellulose aerogels and its hybrid aerogel |
| CN106076283B (en) * | 2016-06-11 | 2018-09-14 | 华南理工大学 | A kind of nano-cellulose/poly-dopamine hydrogel adsorbent and the preparation method and application thereof |
| US11180627B2 (en) * | 2017-01-11 | 2021-11-23 | The Regents Of The University Of Colorado, A Body Corporate | Cellulose enabled orientationally ordered flexible gels |
| CN110483830B (en) * | 2019-07-31 | 2021-08-17 | 武汉纺织大学 | Ultra-light high-elasticity fibroin micro-nano fiber aerogel and preparation method and application thereof |
| CN114011345B (en) * | 2021-11-12 | 2024-05-28 | 清远高新华园科技协同创新研究院有限公司 | Nanocellulose aerogel and preparation method and application thereof |
-
2021
- 2021-11-12 CN CN202111337884.6A patent/CN114011345B/en active Active
-
2022
- 2022-02-28 WO PCT/CN2022/078328 patent/WO2023082498A1/en unknown
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103562284A (en) * | 2011-03-25 | 2014-02-05 | 丝路技术公司 | Cellulose-based materials comprising nanofibrillated cellulose from native cellulose |
| CN106750384A (en) * | 2016-12-29 | 2017-05-31 | 南京林业大学 | A kind of method of amino silane modified nano-cellulose aerogel |
| CN106893116A (en) * | 2017-02-24 | 2017-06-27 | 浙江和也健康科技有限公司 | A kind of preparation method of cellulose nano-fibrous biomass gel and aeroge |
| CN107722338A (en) * | 2017-10-31 | 2018-02-23 | 天津科技大学 | The preparation method and nano-cellulose aerogel of a kind of nano-cellulose aerogel |
| CN110172185A (en) * | 2019-05-08 | 2019-08-27 | 南京林业大学 | A kind of anisotropy nano-cellulose aerogel and preparation method thereof and device |
| JP2020189947A (en) * | 2019-05-23 | 2020-11-26 | 本田技研工業株式会社 | Manufacturing method of cellulose porous body |
| CN111793241A (en) * | 2020-07-23 | 2020-10-20 | 武汉纺织大学 | Ramie bone nanocrystalline cellulose aerogel and preparation method thereof |
| CN112876713A (en) * | 2021-03-02 | 2021-06-01 | 内蒙古科技大学 | Preparation method of cellulose aerogel-based efficient air filtering membrane |
Non-Patent Citations (1)
| Title |
|---|
| 叔丁醇冷冻干燥法制备纳米纤维素气凝胶;王晓宇等;《林业工程学报》;第第2卷卷(第第1期期);第103-107页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023082498A1 (en) | 2023-05-19 |
| CN114011345A (en) | 2022-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2815026B1 (en) | Method and apparatus for processing fibril cellulose and fibril cellulose product | |
| CN107556495B (en) | A kind of preparation method of functional nano cellulose composite aerogel | |
| CN103993380B (en) | A kind of preparation method of Chitosan Fiber With High Tenacity | |
| CN109513404B (en) | Loaded TiO (titanium dioxide)2Preparation method of functional cellulose aerogel composite material of nano particles | |
| CN103172989B (en) | Environment-friendly antibacterial polyester material and preparation method thereof | |
| CN114011345B (en) | Nanocellulose aerogel and preparation method and application thereof | |
| CN102417606A (en) | Preparation method of chitin aerogel | |
| CN107441848B (en) | Silk fibroin nanofiltration membrane with micro-nano structure on surface, preparation method and application thereof | |
| CN110240723B (en) | Ultraviolet high-shielding cellulose membrane and preparation method and application thereof | |
| CN1282777C (en) | Konjaku high hygroscopicity fibre and its preparation method | |
| CN112812343B (en) | Method for preparing regenerated cellulose membrane by using lithium bromide, product and application thereof | |
| KR101551850B1 (en) | Manufacturing method porous paper filter and porous paper filter manufactured by the method | |
| CN111001314A (en) | Preparation method and application of nanocrystalline cellulose/dopamine composite membrane | |
| CN110975833A (en) | Preparation method and application of silicon dioxide/cellulose composite porous material | |
| CN109908876A (en) | A kind of preparation method and application of the chitosan-based bionical attractive gel of polysaccharide nano microcrystalline doping | |
| CN111944178A (en) | Preparation method of nano holocellulose reinforced composite membrane and prepared composite membrane | |
| CN113145080A (en) | Preparation method of TEMPO oxidized holocellulose-chitosan adsorption material, prepared adsorption material and application | |
| CN107792872B (en) | A kind of preparation process of spindle nanometer calcium carbonate | |
| Liu et al. | Reinforced chitosan beads by chitin nanofibers for the immobilization of β-glucosidase | |
| CN106343429A (en) | Preparation method of purified konjak refined flour capable of being quickly dissolved | |
| CN110508260A (en) | A kind of preparation method of lead ion trace composite hollow microballoon | |
| CN109569330A (en) | The preparation method of the cross-linking modified nanofiltration membrane of regenerated cellulose base | |
| CN110229384B (en) | Silver-loaded diamidoxime cellulose/chitosan/fibroin composite aerogel and preparation method thereof | |
| CN112495435A (en) | Chitosan-based graphene/TiO2Composite microsphere and preparation method thereof | |
| CN109046190B (en) | Pectin composite silicon dioxide aerogel and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |