CN115845810B - Preparation method and application of cellulose-based porous material for carbon capture - Google Patents
Preparation method and application of cellulose-based porous material for carbon capture Download PDFInfo
- Publication number
- CN115845810B CN115845810B CN202211476492.2A CN202211476492A CN115845810B CN 115845810 B CN115845810 B CN 115845810B CN 202211476492 A CN202211476492 A CN 202211476492A CN 115845810 B CN115845810 B CN 115845810B
- Authority
- CN
- China
- Prior art keywords
- cellulose
- solution
- porous material
- based porous
- distilled water
- 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
- 229920002678 cellulose Polymers 0.000 title claims abstract description 75
- 239000001913 cellulose Substances 0.000 title claims abstract description 75
- 239000011148 porous material Substances 0.000 title claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 38
- 239000004593 Epoxy Substances 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 87
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 81
- 239000000243 solution Substances 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000012153 distilled water Substances 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 28
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 23
- 229960002218 sodium chlorite Drugs 0.000 claims description 23
- 238000010257 thawing Methods 0.000 claims description 22
- 238000007710 freezing Methods 0.000 claims description 21
- 230000008014 freezing Effects 0.000 claims description 21
- 239000000835 fiber Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 13
- 238000004108 freeze drying Methods 0.000 claims description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 11
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 claims description 10
- 239000002028 Biomass Substances 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 229920000875 Dissolving pulp Polymers 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241001330002 Bambuseae Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 48
- 238000001179 sorption measurement Methods 0.000 abstract description 28
- 239000001569 carbon dioxide Substances 0.000 abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 24
- 238000004064 recycling Methods 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 230000036541 health Effects 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 239000004964 aerogel Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 125000003277 amino group Chemical group 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000036619 pore blockages Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A preparation method and application of a cellulose-based porous material for carbon capture relate to a preparation method and application of a cellulose-based porous material. The invention aims to solve the problems of pore canal blockage, low adsorption quantity, low recycling rate, instability and environmental pollution in the preparation process and threat to human health of the existing porous solid for capturing carbon dioxide. The method comprises the following steps: 1. preparing a cellulose aqueous solution; 2. preparing epoxy functional polyethyleneimine; 3. preparing a cellulose-based porous material. A cellulose-based porous material for carbon capture is used to capture carbon. The cellulose-based porous material for carbon capture, which is prepared by the invention, has a porous structure and a large specific surface area of 149.5m 2/g, has good carbon dioxide adsorption capacity, and can reach 6.45mmol/g under 298k and 1bar conditions. The invention can obtain a cellulose-based porous material for carbon capture.
Description
Technical Field
The invention relates to a preparation method and application of a cellulose-based porous material.
Background
At present, in the carbon dioxide capturing process, the application of liquid absorption and physical adsorption is limited because of the low utilization rate, environmental pollution and other problems, and the introduction of aminosilane, organic amine and the like into a large-surface-area porous solid is a very promising preparation method of the CO 2 adsorbent, but the preparation method still has the defects:
1. cell channel blockage: after the porous material is modified, active materials such as amino groups and the like can be gathered in a large amount in the pore canal to cause the pore canal to be blocked, the specific surface area is reduced, the accessibility of carbon dioxide molecules is reduced, and the carbon dioxide adsorption capacity is reduced.
2. The adsorption quantity is low: because of the blockage of the amino aggregation pore canal, the contact area with carbon dioxide molecules is reduced, and a large number of aggregated reactive sites are reduced, so that the adsorption quantity is low.
3. The repeated utilization rate is low: the adsorbent needs to be used for multiple times, but the porous material modified by the amino group can lose active amino groups after being adsorbed and desorbed again, so that the capacity of capturing carbon dioxide is reduced and the porous material cannot be used for multiple times.
4. Instability: the traditional impregnated or grafted modified porous material has the advantages that amino groups can be attached to the surface, the amino groups are unstable and easy to fall off, reactive active points are few, carbon dioxide molecules can be accumulated on the surface to block the entry of the carbon dioxide molecules, and the adsorption quantity is reduced.
5. The preparation process uses partial solvent to volatilize or degrade toxic substances, pollute the environment and threaten the health of human bodies.
Disclosure of Invention
The invention aims to solve the problems of pore canal blockage, low adsorption quantity, low recycling rate, instability, environmental pollution in the preparation process and threat to human health of the existing porous solid carbon dioxide trapping, and provides a preparation method and application of a cellulose-based porous material for carbon trapping.
The preparation method of the cellulose-based porous material for carbon capture is completed according to the following steps:
1. Preparation of an aqueous cellulose solution:
dissolving cellulose powder in sodium hydroxide/urea aqueous solution, freezing again, taking out, and thawing to obtain cellulose aqueous solution;
2. Preparing epoxy functional polyethyleneimine:
dissolving polyethyleneimine in distilled water to obtain polyethyleneimine solution; adding 1, 2-epoxybutane into the polyethyleneimine solution, and stirring at room temperature to obtain an epoxy functional polyethyleneimine solution;
3. Preparing a cellulose-based porous material:
① . Respectively dripping epichlorohydrin and epoxy functional polyethyleneimine solution into cellulose water solution under the stirring condition, and uniformly stirring; obtaining a mixed solution;
② . Freezing the mixed solution, taking out and thawing;
③ . Circulating the third ② times to 6 times to obtain cellulose gel;
④ . Neutralizing the cellulose gel to be neutral by using acetic acid solution with the mass fraction of 1% -2%, and freeze-drying to obtain the cellulose-based porous material for carbon capture.
A cellulose-based porous material for carbon capture is used to capture carbon.
The invention has the advantages that:
1. Improving the aperture: according to the invention, through modifying the organic amine and adding the cross-linking agent, amino groups are uniformly distributed on the cellulose matrix, so that the problem of pore channel blockage caused by massive aggregation of the amino groups after loading is solved, a micro-nano composite structure is formed, the specific surface area is increased, the accessibility of carbon dioxide molecules is increased, and the adsorption capacity is increased;
2. The adsorption quantity is high: the invention maintains a large specific surface area and a porous structure, and simultaneously increases more reactive sites for effective amino loading, and the physical adsorption and chemical adsorption act together, thereby greatly improving the adsorption capacity of the sample;
3. the repeated utilization rate is high: the invention can be desorbed and regenerated for continuous use after absorbing carbon dioxide, realizes the multiple use of the adsorbent and has high recycling rate;
4. stable amino loading: the amino groups and cellulose are tightly combined together through the cross-linking agent, so that the condition of agglomeration and blocking of pore channels is improved, more effective amino reaction sites are provided, carbon dioxide molecules can enter the inside as much as possible, and the adsorption quantity is increased.
5. The preparation process is simple, the operability is good, and the preparation process is environment-friendly;
6. The cellulose-based porous material for carbon capture, which is prepared by the invention, solves the problems of pore blockage and great reduction of specific surface area of the existing amino modified porous material, has a porous structure and a large specific surface area of 149.5m 2/g, has good carbon dioxide adsorption capacity, and can achieve carbon dioxide adsorption capacity of 6.45mmol/g under 298k and 1bar conditions;
7. The cellulose-based porous material for carbon capture prepared by the method has high recycling rate, can be reused after desorption, and can still reach 6.28mmol/g after five regeneration cycles.
The invention can obtain a cellulose-based porous material for carbon capture.
Drawings
FIG. 1 is a macroscopic photograph of a cellulose-based porous material for carbon capture prepared in example 1;
FIG. 2 is a SEM image showing a pure cellulose aerogel of comparative example 1, b a plugged aerogel prepared in comparative example 2, c a cellulose-based porous material for carbon capture prepared in example 1;
FIG. 3 is a graph of nitrogen adsorption and desorption, wherein the left graph of the graph shows the pore blocking aerogel prepared in comparative example 2, and the right graph shows the cellulose-based porous material for carbon capture prepared in example 1;
FIG. 4 is a graph of the adsorption capacity test of a sample;
fig. 5 is a graph of adsorption amount of carbon dioxide by repeating adsorption of carbon dioxide using the cellulose-based porous material for carbon capture prepared in example 1.
Detailed Description
The first embodiment is as follows: the preparation method of the cellulose-based porous material for carbon capture in the embodiment is completed according to the following steps:
1. Preparation of an aqueous cellulose solution:
dissolving cellulose powder in sodium hydroxide/urea aqueous solution, freezing again, taking out, and thawing to obtain cellulose aqueous solution;
2. Preparing epoxy functional polyethyleneimine:
dissolving polyethyleneimine in distilled water to obtain polyethyleneimine solution; adding 1, 2-epoxybutane into the polyethyleneimine solution, and stirring at room temperature to obtain an epoxy functional polyethyleneimine solution;
3. Preparing a cellulose-based porous material:
① . Respectively dripping epichlorohydrin and epoxy functional polyethyleneimine solution into cellulose water solution under the stirring condition, and uniformly stirring; obtaining a mixed solution;
② . Freezing the mixed solution, taking out and thawing;
③ . Circulating the third ② times to 6 times to obtain cellulose gel;
④ . Neutralizing the cellulose gel to be neutral by using acetic acid solution with the mass fraction of 1% -2%, and freeze-drying to obtain the cellulose-based porous material for carbon capture.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the cellulose powder in the first step is self-made cellulose powder or commercial cellulose powder. The other steps are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the preparation method of the self-made cellulose powder is specifically completed by the following steps:
① . Adding biomass powder into a mixed solution of distilled water, acetic acid and sodium chlorite, and reacting in water bath at 80-90 ℃;
② . Repeating the first ① times to 5 times, and then carrying out suction filtration and cleaning to obtain a fiber A;
③ . Adding the fiber A into NaOH solution, heating to 80-90 ℃, treating at 80-90 ℃, carrying out suction filtration, and finally repeatedly washing with distilled water to obtain fiber B;
④ . Adding the fiber B into a mixed solution of distilled water, acetic acid and sodium chlorite, then reacting in a water bath at 80-90 ℃, then adding into a NaOH solution, heating to 80-90 ℃, treating at 80-90 ℃, finally carrying out suction filtration, and washing to be neutral to obtain the self-made cellulose powder. The other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: the volume ratio of the mass of the biomass powder in the step ① to the mixed solution of distilled water, acetic acid and sodium chlorite is (4 g-8 g) (180 mL-210 mL); the biomass powder in step ① is wood powder or bamboo powder; the reaction time in the water bath at 80-90 ℃ in the step ① is 1-3 h; the volume ratio of the mass of the fiber A to the NaOH solution in the step ③ is (4 g-8 g) (90 mL-120 mL); in the step ③, the treatment time is 1 to 2 hours at the temperature of between 80 and 90 ℃; in the step ③, distilled water is used for repeatedly washing for 3 to 5 times; the volume ratio of the mass of the fiber B to the mixed solution of distilled water, acetic acid and sodium chlorite in the step ④ is (4 g-8 g) (180 mL-210 mL); adding the fiber B in the step ④ into a mixed solution of distilled water, acetic acid and sodium chlorite, then reacting for 1-2 h in a water bath at 80-90 ℃, then adding into a NaOH solution, heating to 80-90 ℃, and treating for 0.5-1 h at 80-90 ℃; the concentration of acetic acid in the mixed solution of distilled water, acetic acid and sodium chlorite in the steps ① and ④ is 1.1 mol/L-1.4 mol/L; the concentration of sodium chlorite in the mixed solution of distilled water, acetic acid and sodium chlorite in the steps ① and ④ is 0.12 mol/L-0.15 mol/L; the concentration of the NaOH solution in the steps ③ and ④ is 0.3mol/L to 0.4mol/L. The other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: the volume ratio of the mass of the cellulose powder to the sodium hydroxide/urea aqueous solution in the first step is (4 g-6 g) (80 mL-150 mL); the mass fraction of sodium hydroxide in the sodium hydroxide/urea aqueous solution in the first step is 6-12%, and the mass fraction of urea is 8-15%. Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: the freezing temperature in the first step is-30-40 ℃, and the freezing time is 6-8 hours; the thawing temperature in the first step is 20-25 ℃, and the thawing time is 3-6 h. Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: the mass ratio of the polyethyleneimine to the distilled water in the second step is (33-44) (50-70); the mass ratio of the polyethyleneimine to the 1, 2-epoxybutane in the second step is (33-44) (10-15); and step two, stirring at room temperature for 10-12 hours. Other steps are the same as those of embodiments one to six.
Eighth embodiment: one difference between the present embodiment and the first to seventh embodiments is that: the volume ratio of the epichlorohydrin to the epoxy functional polyethyleneimine solution in the step III ① is (1-3) (1-5); the volume ratio of the epichlorohydrin to the cellulose water solution in the step III ① is (1-3) (20-25). The other steps are the same as those of embodiments one to seven.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: the freezing temperature in the step III ② is-30 ℃ to-40 ℃ and the freezing time is 6h to 8h; the thawing temperature in the step III ② is 20-25 ℃, and the thawing time is 4-6 h; the freeze-drying temperature in the step III ④ is-35 ℃ to-45 ℃ and the freeze-drying time is 48h to 60h. Other steps are the same as those of embodiments one to eight.
Detailed description ten: the present embodiment is a cellulose-based porous material for carbon capture for capturing carbon.
The following examples are used to verify the benefits of the present invention:
example 1: the preparation method of the cellulose-based porous material for carbon capture is completed according to the following steps:
1. Preparation of an aqueous cellulose solution:
① . Adding biomass powder into a mixed solution of distilled water, acetic acid and sodium chlorite, and reacting for 1.5 hours in a water bath at 85 ℃;
The volume ratio of the mass of the biomass powder in the step one ① to the mixed solution of distilled water, acetic acid and sodium chlorite is 5 g/200 mL;
the biomass powder in the first ① step is wood powder;
② . Repeating the first ① times, and filtering and cleaning to obtain fiber A;
③ . Adding the fiber A into NaOH solution, heating to 85 ℃, treating for 1h at 85 ℃, carrying out suction filtration, and finally washing 3 times by using distilled water to obtain fiber B;
The volume ratio of the mass of the fiber A to the NaOH solution in the step one ③ is 5g to 120mL;
④ . Adding the fiber B into a mixed solution of distilled water, acetic acid and sodium chlorite, then reacting for 1h in a water bath at 85 ℃, then adding into a NaOH solution, heating to 85 ℃, treating for 1h at 85 ℃, finally performing suction filtration, and washing with water to be neutral to obtain cellulose powder;
in the first ④ step, the volume ratio of the mass of the fiber B to the mixed solution of distilled water, acetic acid and sodium chlorite is 5 g/200 mL;
the concentration of acetic acid in the mixed solution of distilled water, acetic acid and sodium chlorite in the step one ① and the step one ④ is 1.2mol/L;
The concentration of sodium chlorite in the mixed solution of distilled water, acetic acid and sodium chlorite in the step one ① and the step one ④ is 0.12mol/L;
The concentration of the NaOH solution in the step one ③ and the step one ④ is 0.3mol/L;
⑤ . Dissolving cellulose powder in sodium hydroxide/urea aqueous solution, freezing again, taking out, and thawing to obtain cellulose aqueous solution;
The volume ratio of the mass of the cellulose powder to the sodium hydroxide/urea aqueous solution in the first ⑤ is 5g to 120mL;
The mass fraction of sodium hydroxide in the sodium hydroxide/urea aqueous solution in the first ⑤ is 7%, and the mass fraction of urea is 12%;
the freezing temperature in the first ⑤ step is-38 ℃, and the freezing time is 7 hours;
the thawing temperature in the first ⑤ step is 23 ℃ and the thawing time is 5h;
2. Preparing epoxy functional polyethyleneimine:
dissolving polyethyleneimine in distilled water to obtain polyethyleneimine solution; adding 1, 2-epoxybutane into the polyethyleneimine solution, and stirring at room temperature to obtain an epoxy functional polyethyleneimine solution;
the mass ratio of the polyethyleneimine to distilled water in the second step is 40 g/60 g;
The mass ratio of the polyethyleneimine to the 1, 2-epoxybutane in the second step is 40g to 11g;
Stirring at room temperature for 12 hours;
3. Preparing a cellulose-based porous material:
① . Respectively dripping epichlorohydrin and epoxy functional polyethyleneimine solution into cellulose water solution under stirring condition, and uniformly stirring; obtaining a mixed solution;
The volume ratio of the epichlorohydrin to the epoxy functionalized polyethyleneimine solution in the step III ① is 1mL to 2mL;
The volume ratio of the epichlorohydrin to the cellulose water solution in the step III ① is 1mL to 20mL;
② . Freezing the mixed solution, taking out and thawing;
The freezing temperature in the step III ② is-38 ℃, and the freezing time is 7 hours;
the thawing temperature in the step III ② is 23 ℃, and the thawing time is 5 hours;
③ . The third ② times of circulation step is carried out to obtain cellulose gel;
④ . Neutralizing the cellulose gel to be neutral by using acetic acid solution with the mass fraction of 1%, and freeze-drying to obtain a cellulose-based porous material for carbon capture;
The freeze-drying temperature in step three ④ was-40℃and the freeze-drying time was 50h.
Comparative example 1: the preparation method of the pure cellulose aerogel comprises the following steps:
And (3) putting 20mL of cellulose solution into a refrigerator at the temperature of minus 38 ℃ to freeze for 7 hours, taking out, thawing for 5 hours, repeating the steps 5 times, neutralizing the obtained cellulose gel with 1% acetic acid solution to be neutral, and then performing freeze drying by a one-step method to obtain the pure cellulose aerogel.
Comparative example 2: the preparation method of the pore canal blocking aerogel comprises the following steps:
① . 40g of polyethyleneimine is dissolved in 60g of distilled water to obtain polyethyleneimine solution;
② . Adding 1mL of epichlorohydrin and 2mL of polyethyleneimine dropwise into 20mL of cellulose solution under the action of magnetic stirring, putting into a refrigerator at the temperature of minus 38 ℃ for freezing for 7h, taking out, thawing for 5h at the temperature of 23 ℃, repeating the steps for 5 times, neutralizing the obtained cellulose gel with 1% acetic acid solution to be neutral, and then performing freeze drying by a one-step method to obtain the pore channel blocking aerogel. .
FIG. 1 is a macroscopic photograph of a cellulose-based porous material for carbon capture prepared in example 1;
the cellulose-based porous material for carbon capture prepared in example 1 can be used to prepare samples of various sizes and specifications by adjusting the reaction vessel, and the density of the samples is calculated to be as low as 0.037g/cm 3.
FIG. 2 is a SEM image showing a pure cellulose aerogel of comparative example 1, b a plugged aerogel prepared in comparative example 2, c a cellulose-based porous material for carbon capture prepared in example 1;
As can be seen from fig. 2: the cellulose of the pure cellulose aerogel is agglomerated in large pieces, has a rough surface, irregular bulges and a compact pore structure; the pore blocking aerogel prepared in comparative example 2 had partially irregular macropores; the cellulose-based porous material for carbon capture prepared in the embodiment 1 has a layered porous structure, the epoxy functional polyethyleneimine is uniformly distributed, and a micro-nano composite structure is formed, so that the problem that a large amount of agglomeration blocks the pore canal after amino loading is solved, carbon dioxide diffusion is facilitated, and the adsorption capacity of a sample is improved.
The nitrogen adsorption and desorption test was performed on the pore blocking aerogel prepared in comparative example 2 and the cellulose-based porous material for carbon capture prepared in example 1 under the same conditions, and the specific surface area was calculated by the Brunauer (Brunauer), emmet (Emmet) and taylor (Teller) equations (BET equations) as shown in fig. 3. The specific surface area of the cellulose-based porous material for carbon capture prepared in the embodiment 1 is as high as 149.5m 2/g, the specific surface area is greatly improved, and the accessibility of carbon dioxide molecules is increased.
The adsorptivity of the samples was tested: the carbon dioxide adsorption capacity of the pore blocking aerogel prepared in comparative example 2 and the cellulose-based porous material for carbon capture prepared in example 1 was tested at 298k at 1bar, as shown in fig. 4;
FIG. 4 is a graph of the adsorption capacity test of a sample;
as can be seen from fig. 4: the cellulose-based porous material for carbon capture prepared in example 1 has a carbon dioxide adsorption capacity of 6.45mmol/g, which is 2.46 times that of the pore blocking aerogel prepared in comparative example 2, and is superior to most cellulose-based adsorbents.
The cellulose-based porous material for carbon capture prepared in example 1 was tested for recycling rate, as shown in fig. 5;
FIG. 5 is a graph of the adsorption amount of carbon dioxide by repeating the adsorption of carbon dioxide using the cellulose-based porous material for carbon capture prepared in example 1;
as can be seen from fig. 5: after five adsorption-desorption cycles, the carbon dioxide adsorption capacity of the cellulose-based porous material for carbon capture prepared in the example 1 still can reach 6.28mmol/g, which indicates that the cellulose-based porous material for carbon capture prepared in the example 1 can be desorbed and regenerated for use, and the recycling rate is high.
Claims (6)
1. A method for preparing a cellulose-based porous material for carbon capture, characterized by the steps of:
1. Preparation of an aqueous cellulose solution:
dissolving cellulose powder in sodium hydroxide/urea aqueous solution, freezing again, taking out, and thawing to obtain cellulose aqueous solution;
the volume ratio of the mass of the cellulose powder to the sodium hydroxide/urea aqueous solution in the first step is (4 g-6 g) (80 mL-150 mL);
The mass fraction of sodium hydroxide in the sodium hydroxide/urea aqueous solution in the first step is 6-12%, and the mass fraction of urea is 8-15%; the freezing temperature in the first step is-30-40 ℃, and the freezing time is 6-8 hours;
The thawing temperature in the first step is 20-25 ℃, and the thawing time is 3-6 h;
2. Preparing epoxy functional polyethyleneimine:
dissolving polyethyleneimine in distilled water to obtain polyethyleneimine solution; adding 1, 2-epoxybutane into the polyethyleneimine solution, and stirring at room temperature to obtain an epoxy functional polyethyleneimine solution;
the mass ratio of the polyethyleneimine to the distilled water in the second step is (33-44) (50-70);
The mass ratio of the polyethyleneimine to the 1, 2-epoxybutane in the second step is (33-44) (10-15);
Stirring at room temperature for 10-12 h;
3. Preparing a cellulose-based porous material:
① . Respectively dripping epichlorohydrin and epoxy functional polyethyleneimine solution into cellulose water solution under the stirring condition, and uniformly stirring; obtaining a mixed solution;
The volume ratio of the epichlorohydrin to the epoxy functional polyethyleneimine solution in the step III ① is (1-3) (1-5);
The volume ratio of the epichlorohydrin to the cellulose water solution in the step III ① is (1-3) (20-25);
② . Freezing the mixed solution, taking out and thawing;
③ . Circulating the third ② times to 6 times to obtain cellulose gel;
④ . Neutralizing the cellulose gel to be neutral by using acetic acid solution with the mass fraction of 1% -2%, and freeze-drying to obtain the cellulose-based porous material for carbon capture.
2. The method of claim 1, wherein the cellulose powder in the first step is a self-made cellulose powder or a commercially available cellulose powder.
3. The method for preparing the cellulose-based porous material for carbon capture according to claim 2, wherein the preparation method of the self-made cellulose powder is specifically completed by the following steps:
① . Adding biomass powder into a mixed solution of distilled water, acetic acid and sodium chlorite, and reacting in water bath at 80-90 ℃;
② . Repeating the first ① times to 5 times, and then carrying out suction filtration and cleaning to obtain a fiber A;
③ . Adding the fiber A into NaOH solution, heating to 80-90 ℃, treating at 80-90 ℃, carrying out suction filtration, and finally repeatedly washing with distilled water to obtain fiber B;
④ . Adding the fiber B into a mixed solution of distilled water, acetic acid and sodium chlorite, then reacting in a water bath at 80-90 ℃, then adding into a NaOH solution, heating to 80-90 ℃, treating at 80-90 ℃, finally carrying out suction filtration, and washing to be neutral to obtain the self-made cellulose powder.
4. The method for preparing a cellulose-based porous material for carbon capture according to claim 3, wherein the volume ratio of the mass of the biomass powder to the mixed solution of distilled water, acetic acid and sodium chlorite in step ① is (4 g-8 g): 180 mL-210 mL); the biomass powder in step ① is wood powder or bamboo powder; the reaction time in the water bath at 80-90 ℃ in the step ① is 1-3 h; the volume ratio of the mass of the fiber A to the NaOH solution in the step ③ is (4 g-8 g) (90 mL-120 mL); in the step ③, the treatment time is 1 to 2 hours at the temperature of between 80 and 90 ℃; in the step ③, distilled water is used for repeatedly washing for 3 to 5 times; the volume ratio of the mass of the fiber B to the mixed solution of distilled water, acetic acid and sodium chlorite in the step ④ is (4 g-8 g) (180 mL-210 mL); adding the fiber B in the step ④ into a mixed solution of distilled water, acetic acid and sodium chlorite, then reacting for 1-2 h in a water bath at 80-90 ℃, then adding into a NaOH solution, heating to 80-90 ℃, and treating for 0.5-1 h at 80-90 ℃; the concentration of acetic acid in the mixed solution of distilled water, acetic acid and sodium chlorite in the steps ① and ④ is 1.1 mol/L-1.4 mol/L; the concentration of sodium chlorite in the mixed solution of distilled water, acetic acid and sodium chlorite in the steps ① and ④ is 0.12 mol/L-0.15 mol/L; the concentration of the NaOH solution in the steps ③ and ④ is 0.3mol/L to 0.4mol/L.
5. The method for preparing a cellulose-based porous material for carbon capture according to claim 1, wherein the freezing temperature in step three ② is-30 ℃ to-40 ℃ and the freezing time is 6h to 8h; the thawing temperature in the step III ② is 20-25 ℃, and the thawing time is 4-6 h; the freeze-drying temperature in the step III ④ is-35 ℃ to-45 ℃ and the freeze-drying time is 48h to 60h.
6. Use of a cellulose-based porous material for carbon capture prepared by the preparation method according to claim 1, characterized in that a cellulose-based porous material for carbon capture is used for capturing carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211476492.2A CN115845810B (en) | 2022-11-23 | 2022-11-23 | Preparation method and application of cellulose-based porous material for carbon capture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211476492.2A CN115845810B (en) | 2022-11-23 | 2022-11-23 | Preparation method and application of cellulose-based porous material for carbon capture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115845810A CN115845810A (en) | 2023-03-28 |
| CN115845810B true CN115845810B (en) | 2024-05-03 |
Family
ID=85665499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211476492.2A Active CN115845810B (en) | 2022-11-23 | 2022-11-23 | Preparation method and application of cellulose-based porous material for carbon capture |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115845810B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106975465A (en) * | 2017-04-01 | 2017-07-25 | 东华大学 | Functionalized polyethy-lene imines grafted porous nanofiber sorbing material and its preparation |
| CN108339536A (en) * | 2018-03-15 | 2018-07-31 | 南京大学 | An a kind of one-step preparation method of the CMC/PEI double-network hydrogels for efficiently removing Cr (VI) |
| CN109289805A (en) * | 2018-10-12 | 2019-02-01 | 南京林业大学 | A kind of method nano-cellulose composite aerogel adsorbent preparation and its adsorb heavy metal ion |
| CN111250062A (en) * | 2020-02-28 | 2020-06-09 | 西南交通大学 | Cellulose foam capable of visually identifying and removing chromium, preparation method thereof and chromium removal method |
| CN111389381A (en) * | 2020-04-14 | 2020-07-10 | 广西大学 | Near-infrared low-temperature desorption type intelligent adsorption material and preparation method and application thereof |
| CN114632479A (en) * | 2022-03-13 | 2022-06-17 | 东北林业大学 | Preparation method of graphene/nano-cellulose/polyethyleneimine aerogel |
-
2022
- 2022-11-23 CN CN202211476492.2A patent/CN115845810B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106975465A (en) * | 2017-04-01 | 2017-07-25 | 东华大学 | Functionalized polyethy-lene imines grafted porous nanofiber sorbing material and its preparation |
| CN108339536A (en) * | 2018-03-15 | 2018-07-31 | 南京大学 | An a kind of one-step preparation method of the CMC/PEI double-network hydrogels for efficiently removing Cr (VI) |
| CN109289805A (en) * | 2018-10-12 | 2019-02-01 | 南京林业大学 | A kind of method nano-cellulose composite aerogel adsorbent preparation and its adsorb heavy metal ion |
| CN111250062A (en) * | 2020-02-28 | 2020-06-09 | 西南交通大学 | Cellulose foam capable of visually identifying and removing chromium, preparation method thereof and chromium removal method |
| CN111389381A (en) * | 2020-04-14 | 2020-07-10 | 广西大学 | Near-infrared low-temperature desorption type intelligent adsorption material and preparation method and application thereof |
| CN114632479A (en) * | 2022-03-13 | 2022-06-17 | 东北林业大学 | Preparation method of graphene/nano-cellulose/polyethyleneimine aerogel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115845810A (en) | 2023-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Su et al. | High efficiency extraction of U (VI) from seawater by incorporation of polyethyleneimine, polyacrylic acid hydrogel and Luffa cylindrical fibers | |
| Su et al. | Polyethyleneimine-functionalized Luffa cylindrica for efficient uranium extraction | |
| CN109174034A (en) | A kind of copper ion blotting chitosan/sodium carboxymethylcellulose compound adsorbent and preparation method thereof | |
| CN111167402B (en) | Zinc-cobalt Prussian blue analogue adsorbent with hollow structure and preparation method and application thereof | |
| CN112456491A (en) | Production process of environment-friendly regenerated activated carbon | |
| CN111558350A (en) | Preparation method of HTO/cellulose aerogel microspheres for extracting lithium from seawater | |
| CN103193228A (en) | Preparation method of melon seed shell based activated carbon capable of adsorbing CO2 in high efficiency | |
| CN102367182A (en) | Method for treating waste water with organic modified bentonite | |
| CN115845810B (en) | Preparation method and application of cellulose-based porous material for carbon capture | |
| CN115722214B (en) | Ammonia-removal resin material and preparation method thereof | |
| CN112774630A (en) | Preparation method of activated carbon adsorbent for regenerating and adsorbing methyl orange | |
| CN116850956A (en) | Modified ZIF-8-based nitrogen-doped carbon CO 2 Method for preparing adsorbent | |
| CN102068960B (en) | Regeneration method of honeycomb activated carbon absorbent for absorbing nitric oxide | |
| CN114672064B (en) | Preparation method and application of MIL-100 (Fe)/cellulose porous composite pellet | |
| CN113797897B (en) | For capturing CO 2 Preparation method of modified chitosan-based carbon aerogel | |
| CN113477231B (en) | Preparation and application of amidoxime functionalized konjac glucomannan sponge for uranium extraction from seawater | |
| Song et al. | Assembly of a core–shell MOF with stability into Polyacrylamide hydrogel for boosting extraction of uranium from seawater | |
| CN113304734B (en) | Preparation method, product and application of modified lignite | |
| CN112237905B (en) | Lithium extraction adsorbent for raw halogen and preparation method thereof | |
| CN113559829A (en) | Preparation method and application of uranium/lithium synchronous adsorption material | |
| CN108714414B (en) | Foam-like magnetic chitosan adsorbent and preparation method thereof | |
| CN113351187A (en) | Heavy metal ion imprinted hydrogel ball and preparation method and application thereof | |
| CN107511139B (en) | A kind of porous adsorbent for heavy metal and preparation method thereof | |
| CN109865504A (en) | Rubidium ion adsorption microspheres and its application | |
| CN110743512A (en) | Preparation and regeneration method and application of carbon dioxide molecular imprinting adsorbent |
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 | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Yingying Inventor after: Zhu Wenjie Inventor after: Wang Hanwei Inventor after: Yang Yushan Inventor after: Chen Xinjie Inventor after: Lin Jian Inventor after: Sun Qingfeng Inventor after: Wang Youqing Inventor after: Wang Huinan Inventor after: Feng Yingxuan Inventor after: Tian Linping Inventor after: Chai Hao Inventor before: Li Yingying Inventor before: Wang Hanwei Inventor before: Yang Yushan Inventor before: Chen Xinjie Inventor before: Lin Jian Inventor before: Sun Qingfeng Inventor before: Wang Youqing Inventor before: Feng Yingxuan Inventor before: Tian Linping Inventor before: Chai Hao Inventor before: Zhu Wenjie |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |