CN115845810A - 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
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 81
- 239000001913 cellulose Substances 0.000 title claims abstract description 81
- 239000011148 porous material Substances 0.000 title claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 39
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- 239000004593 Epoxy Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 42
- 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
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- 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 16
- 239000000843 powder Substances 0.000 claims description 14
- 238000010257 thawing Methods 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 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
- 238000000967 suction filtration Methods 0.000 claims description 9
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- 238000010438 heat treatment Methods 0.000 claims description 8
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 7
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 230000009919 sequestration Effects 0.000 claims 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 46
- 238000001179 sorption measurement Methods 0.000 abstract description 28
- 239000001569 carbon dioxide Substances 0.000 abstract description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 23
- 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
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 238000002336 sorption--desorption measurement Methods 0.000 description 3
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- 150000001412 amines Chemical class 0.000 description 2
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- 230000001788 irregular Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
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- 238000003760 magnetic stirring Methods 0.000 description 1
- 231100000614 poison Toxicity 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
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- 239000000758 substrate Substances 0.000 description 1
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- 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
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- 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 channel blockage, low adsorption capacity, low repeated utilization rate and instability in the existing porous solid carbon dioxide capture process, environmental pollution in the preparation process and threat to human health. The method comprises the following steps: 1. preparing a cellulose aqueous solution; 2. preparing epoxy functionalized polyethyleneimine; 3. preparing a cellulose-based porous material. A cellulose-based porous material for carbon capture is used to capture carbon. Book (I)The cellulose-based porous material for carbon capture prepared by the invention has a porous structure and 149.5m 2 The specific surface area is large per gram, the carbon dioxide adsorption capacity is good, and the carbon dioxide adsorption capacity can reach 6.45mmol/g under the conditions of 298k and 1 bar. The present invention makes it possible to 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 process of capturing carbon dioxide, the application of liquid absorption and physical adsorption is limited due to the problems of low utilization rate, environmental pollution and the like, and aminosilane, organic amine and the like are introduced into a porous solid with large surface area, so that the method is a very promising CO 2 Adsorbent preparation methods, however, still suffer from the following disadvantages:
1. and (3) pore channel blocking: after the porous material is modified, active materials such as amino and the like can be greatly gathered in the pore channels to cause the blockage of the pore channels, the specific surface area is reduced, the accessibility of carbon dioxide molecules is reduced, and further the carbon dioxide adsorption capacity is reduced.
2. The adsorption capacity is low: due to the blockage of the amino aggregation pore channel, the contact area with carbon dioxide molecules is reduced, and a large number of reaction active sites are reduced after aggregation, so that the adsorption quantity is low.
3. The repeated utilization rate is low: the adsorbent needs to be used for many times, but active amino groups are lost when the porous material modified by the amino groups is desorbed after adsorption, so that the capability of capturing carbon dioxide is reduced, and the porous material cannot be used for many times.
4. Instability: in the traditional impregnated or grafted modified porous material, amino groups can be attached to the surface, the material is unstable and easy to fall off, reactive active points are few, and the material can be gathered on the surface to block carbon dioxide molecules from entering, so that the adsorption quantity is reduced.
5. In the preparation process, part of the solvent is used and can volatilize or degrade toxic substances, so that the environment is polluted and the human health is threatened.
Disclosure of Invention
The invention aims to solve the problems of pore channel blockage, low adsorption capacity, low repeated utilization rate, instability, environmental pollution in the preparation process and threat to human health in the existing porous solid carbon dioxide capture, and provides a preparation method and application of a cellulose-based porous material for carbon capture.
A preparation method of a cellulose-based porous material for carbon capture comprises the following steps:
1. preparing a cellulose aqueous solution:
dissolving cellulose powder in a sodium hydroxide/urea aqueous solution, freezing, taking out, and thawing to obtain a cellulose aqueous solution;
2. preparing epoxy functionalized polyethyleneimine:
dissolving polyethyleneimine in distilled water to obtain a polyethyleneimine solution; adding 1, 2-butylene oxide into the polyethyleneimine solution, and stirring at room temperature to obtain an epoxy functionalized polyethyleneimine solution;
3. preparing a cellulose-based porous material:
(1) respectively dripping epoxy chloropropane and epoxy functionalized polyethyleneimine solution into a cellulose aqueous solution under the condition of stirring, and uniformly stirring; obtaining a mixed solution;
(2) freezing the mixed solution, taking out and unfreezing;
(3) and circulating the step three (2) for 5 to 6 times to obtain cellulose gel;
(4) and neutralizing the cellulose gel to be neutral by using an 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 organic amine and adding a cross-linking agent, amino groups are uniformly distributed on a cellulose substrate, so that the problem of pore channel blockage caused by the aggregation of a large number of 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 capacity is high: the invention keeps large specific surface area and porous structure, effectively increases more reactive active sites by amino load, and greatly improves the adsorption capacity of the sample under the combined action of physical adsorption and chemical adsorption;
3. the repeated utilization rate is high: the carbon dioxide adsorbent can be desorbed and regenerated for continuous use after adsorbing carbon dioxide, so that the adsorbent is repeatedly utilized, and the repeated utilization rate is high;
4. stable amino loading: amino and cellulose are tightly combined together through a cross-linking agent, the stable and uniform loading improves the condition of agglomerated blocked pore channels, more effective amino reaction sites are provided, carbon dioxide molecules can enter the interior as far as possible, and the adsorption capacity is increased.
5. The preparation process is simple, the operability is good, and the preparation process is green and environment-friendly;
6. the cellulose-based porous material for carbon capture prepared by the invention solves the problems of pore channel blockage and great reduction of specific surface area after the existing amino modified porous material is prepared, and has a porous structure and 149.5m 2 The specific surface area is large per gram, the carbon dioxide adsorption capacity is good, and the carbon dioxide adsorption capacity can reach 6.45mmol/g under the conditions of 298k and 1 bar;
7. the cellulose-based porous material for carbon capture prepared by the invention has high reuse rate, can be repeatedly used after desorption, and has adsorption capacity of 6.28mmol/g after five regeneration cycles.
The present invention makes it possible to obtain a cellulose-based porous material for carbon capture.
Drawings
Fig. 1 is a macro photograph of a cellulose-based porous material for carbon capture prepared in example 1;
FIG. 2 is an SEM photograph in which a is a pure cellulose aerogel of comparative example 1, b is a cell-plugging aerogel prepared by comparative example 2, and c is a cellulose-based porous material for carbon capture prepared by example 1;
fig. 3 is a nitrogen adsorption-desorption curve, in which the left graph is the cell-plugged aerogel prepared in comparative example 2 and the right graph is the cellulose-based porous material for carbon capture prepared in example 1;
FIG. 4 is a graph showing the adsorption capacity test of a sample;
fig. 5 is a graph showing the adsorption amount of carbon dioxide adsorbed by recycling 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. preparing a cellulose aqueous solution:
dissolving cellulose powder in a sodium hydroxide/urea aqueous solution, freezing, taking out, and thawing to obtain a cellulose aqueous solution;
2. preparing epoxy functionalized polyethyleneimine:
dissolving polyethyleneimine in distilled water to obtain a polyethyleneimine solution; adding 1, 2-butylene oxide into the polyethyleneimine solution, and stirring at room temperature to obtain an epoxy functionalized polyethyleneimine solution;
3. preparing a cellulose-based porous material:
(1) respectively dripping epoxy chloropropane and epoxy functionalized polyethyleneimine solution into a cellulose aqueous solution under the condition of stirring, and uniformly stirring; obtaining a mixed solution;
(2) freezing the mixed solution, taking out and unfreezing;
(3) and circulating the step three (2) for 5 to 6 times to obtain cellulose gel;
(4) and neutralizing the cellulose gel to be neutral by using an 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 present embodiment in that: the cellulose powder in the step one is self-made cellulose powder or commercially available cellulose powder. The other steps are the same as those in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the preparation method of the self-made cellulose powder is specifically completed according to the following steps:
(1) adding the biomass powder into a mixed solution of distilled water, acetic acid and sodium chlorite, and reacting in a water bath at the temperature of 80-90 ℃;
(2) repeating the step one (1) for 3 to 5 times, and then performing suction filtration and cleaning to obtain fiber A;
(3) adding the fiber A into NaOH solution, heating to 80-90 ℃, treating at 80-90 ℃, then 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, reacting in a water bath at the temperature of 80-90 ℃, adding into a NaOH solution, heating to the temperature of 80-90 ℃, treating at the temperature of 80-90 ℃, finally performing suction filtration, and washing to be neutral to obtain the self-made cellulose powder. The other steps are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: 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 (4-8 g) to (180-210 mL); the biomass powder in the step (1) is wood powder or bamboo powder; the reaction time in the water bath at the temperature of 80-90 ℃ in the step (1) is 1-3 h; the ratio of the mass of the fiber A in the step (3) to the volume of the NaOH solution is (4 g-8 g) to (90 mL-120 mL); the treatment time at 80-90 ℃ in the step (3) is 1-2 h; in the step (3), the washing times of the washing with distilled water are 3-5 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, reacting for 1-2 h in a water bath at the temperature of 80-90 ℃, then adding into a NaOH solution, heating to the temperature of 80-90 ℃, and treating for 0.5-1 h at the temperature of 80-90 ℃; the concentration of the acetic acid in the mixed solution of the distilled water, the acetic acid and the sodium chlorite in the step (1) and the step (4) is 1.1-1.4 mol/L; the concentration of sodium chlorite in the mixed solution of distilled water, acetic acid and sodium chlorite in the step (1) and the step (4) is 0.12-0.15 mol/L; the concentration of the NaOH solution in the step (3) and the step (4) is 0.3 mol/L-0.4 mol/L. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the ratio of the mass of the cellulose powder to the volume of the sodium hydroxide/urea aqueous solution in the first step is (4-6 g): 80-150 mL; in the first step, the mass fraction of the sodium hydroxide in the sodium hydroxide/urea aqueous solution is 6-12%, and the mass fraction of the urea is 8-15%. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode is as follows: the difference between this embodiment and one of the first to fifth embodiments is as follows: the freezing temperature in the step one is-30 ℃ to 40 ℃, and the freezing time is 6h to 8h; the thawing temperature in the step one is 20-25 ℃, and the thawing time is 3-6 h. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the mass ratio of the polyethyleneimine to the distilled water in the second step is (33-44) to (50-70); the mass ratio of the polyethyleneimine to the 1, 2-butylene oxide in the second step is (33-44) to (10-15); and the stirring time at room temperature in the step two is 10-12 h. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the volume ratio of the epoxy chloropropane to the epoxy functionalized polyethyleneimine solution in the step three (1) is (1-3) to (1-5); the volume ratio of the epoxy chloropropane to the cellulose aqueous solution in the step three (1) is (1-3) to (20-25). The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the freezing temperature in the step three (2) is-30 ℃ to-40 ℃, and the freezing time is 6h to 8h; the thawing temperature in the step three (2) is 20-25 ℃, and the thawing time is 4-6 h; the temperature of the freeze drying in the step three (4) is-35 ℃ to-45 ℃, and the time of the freeze drying is 48h to 60h. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment is a cellulose-based porous material for carbon capture for capturing carbon.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: a preparation method of a cellulose-based porous material for carbon capture comprises the following steps:
1. preparing a cellulose aqueous solution:
(1) adding the biomass powder into a mixed solution of distilled water, acetic acid and sodium chlorite, and reacting for 1.5h in a water bath at the temperature of 85 ℃;
the volume ratio of the mass of the biomass powder in the first step (1) to the mixed solution of distilled water, acetic acid and sodium chlorite is 5g;
the biomass powder in the step one (1) is wood powder;
(2) repeating the step one (1) for 5 times, and then performing suction filtration and cleaning to obtain fiber A;
(3) adding the fiber A into a NaOH solution, heating to 85 ℃, treating at 85 ℃ for 1h, then carrying out suction filtration, and finally washing with distilled water for 3 times to obtain a fiber B;
the volume ratio of the mass of the fiber A to the NaOH solution in the first step (3) is 5 g;
(4) adding the fiber B into a mixed solution of distilled water, acetic acid and sodium chlorite, 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 to be neutral to obtain cellulose powder;
in the step one (4), the volume ratio of the mass of the fiber B to the mixed solution of distilled water, acetic acid and sodium chlorite is 5g;
the concentration of the acetic acid in the mixed solution of the distilled water, the acetic acid and the 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 first step (3) and the first step (4) is 0.3mol/L;
(5) dissolving cellulose powder in a sodium hydroxide/urea aqueous solution, freezing, taking out, and thawing to obtain a cellulose aqueous solution;
the volume ratio of the mass of the cellulose powder in the first step (5) to the sodium hydroxide/urea aqueous solution is 5g;
the mass fraction of sodium hydroxide in the sodium hydroxide/urea aqueous solution in the step one (5) is 7 percent, and the mass fraction of urea is 12 percent;
the freezing temperature in the step one (5) is-38 ℃, and the freezing time is 7h;
the unfreezing temperature in the step one (5) is 23 ℃, and the unfreezing time is 5 hours;
2. preparing epoxy functionalized polyethyleneimine:
dissolving polyethyleneimine in distilled water to obtain a polyethyleneimine solution; adding 1, 2-butylene oxide into the polyethyleneimine solution, and stirring at room temperature to obtain an epoxy functionalized polyethyleneimine solution;
the mass ratio of the polyethyleneimine to the distilled water in the second step is 40g;
the mass ratio of the polyethyleneimine to the 1, 2-butylene oxide in the second step is 40g;
stirring at room temperature for 12h in the step two;
3. preparing a cellulose-based porous material:
(1) respectively dripping epoxy chloropropane and epoxy functionalized polyethyleneimine solution into the cellulose aqueous solution under the condition of stirring, and uniformly stirring; obtaining a mixed solution;
the volume ratio of the epichlorohydrin to the epoxy functionalized polyethyleneimine solution in the step three (1) is 1mL;
the volume ratio of the epichlorohydrin to the cellulose aqueous solution in the step three (1) is 1mL;
(2) freezing the mixed solution, taking out and unfreezing;
the freezing temperature in the step three (2) is-38 ℃, and the freezing time is 7h;
the thawing temperature in the step three (2) is 23 ℃, and the thawing time is 5 hours;
(3) and 5 times of circulating the step three (2) to obtain cellulose gel;
(4) neutralizing the cellulose gel to be neutral by using an acetic acid solution with the mass fraction of 1%, and freeze-drying to obtain a cellulose-based porous material for carbon capture;
and (5) performing freeze drying at the temperature of minus 40 ℃ for 50h in the step three (4).
Comparative example 1: the preparation method of the pure cellulose aerogel comprises the following steps:
and (2) putting 20mL of cellulose solution into a refrigerator at the temperature of-38 ℃ for freezing for 7h, taking out and then unfreezing for 5h, 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 one-step method to obtain the pure cellulose aerogel.
Comparative example 2: the preparation method of the aerogel with the blocked pore channels comprises the following steps:
(1) dissolving 40g of polyethyleneimine in 60g of distilled water to obtain a polyethyleneimine solution;
(2) dropwise adding 1mL of epichlorohydrin and 2mL of polyethyleneimine into 20mL of cellulose solution under the action of magnetic stirring, uniformly stirring, putting into a refrigerator at-38 ℃ for freezing for 7h, taking out, unfreezing for 5h at 23 ℃, repeating the steps for 5 times, neutralizing the obtained cellulose gel to be neutral by using 1% acetic acid solution, and then carrying out freeze drying by one-step method to obtain the aerogel with blocked pores. .
Fig. 1 is a photomicrograph 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 prepared into samples of different 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 photograph in which a is a pure cellulose aerogel of comparative example 1, b is a cell-clogging aerogel prepared by comparative example 2, and c is a cellulose-based porous material for carbon capture prepared by example 1;
as can be seen from fig. 2: the cellulose of the pure cellulose aerogel is agglomerated in a large scale, the surface is rough, and the pure cellulose aerogel has an irregular, convex and compact pore structure; the pore channel plugging aerogel prepared in comparative example 2 had partially irregular large pores; the cellulose-based porous material for carbon capture prepared in the embodiment 1 has a layered porous structure, epoxy functionalized polyethyleneimine is uniformly distributed, a micro-nano composite structure is formed, the problem that a large amount of amino-loaded polyethyleneimine is agglomerated to block a pore channel is solved, carbon dioxide can be diffused and enter the porous material, and the adsorption capacity of a sample is improved.
The nitrogen adsorption desorption test was performed on the cell-plugged 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 Brunauer (Brunauer), emmet (Emmet), and Teller (Teller) equation (BET equation) as shown in fig. 3. The specific surface area of the cellulose-based porous material for carbon capture prepared in example 1 was up to 149.5m 2 The specific surface area is greatly improved, and the accessibility of carbon dioxide molecules is increased.
The adsorption performance of the samples was tested: the channel-plugged aerogel prepared in comparative example 2 and the cellulose-based porous material for carbon capture prepared in example 1 were tested for carbon dioxide adsorption capacity under the conditions of 298k, 1bar, as shown in fig. 4;
FIG. 4 is a graph showing the adsorption capacity test of a sample;
as can be seen from fig. 4: the adsorption amount of carbon dioxide of the cellulose-based porous material for carbon capture prepared in example 1 was 6.45mmol/g, which is 2.46 times that of the cell-blocked 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 efficiency, as shown in fig. 5;
fig. 5 is a graph showing the adsorption amount of carbon dioxide adsorbed by recycling the cellulose-based porous material for carbon capture prepared in example 1;
as can be seen from fig. 5: after five times of adsorption-desorption cycles, the carbon dioxide adsorption capacity of the cellulose-based porous material for carbon capture prepared in example 1 can still reach 6.28mmol/g, which shows that the cellulose-based porous material for carbon capture prepared in example 1 can be desorbed, regenerated and used, and has high recycling rate.
Claims (10)
1. A method for preparing a cellulose-based porous material for carbon capture, characterized in that it is completed according to the following steps:
1. preparing a cellulose aqueous solution:
dissolving cellulose powder in a sodium hydroxide/urea aqueous solution, freezing, taking out, and thawing to obtain a cellulose aqueous solution;
2. preparing epoxy functionalized polyethyleneimine:
dissolving polyethyleneimine in distilled water to obtain a polyethyleneimine solution; adding 1, 2-butylene oxide into the polyethyleneimine solution, and stirring at room temperature to obtain an epoxy functionalized polyethyleneimine solution;
3. preparing a cellulose-based porous material:
(1) respectively dripping epoxy chloropropane and epoxy functionalized polyethyleneimine solution into a cellulose aqueous solution under the condition of stirring, and uniformly stirring; obtaining a mixed solution;
(2) freezing the mixed solution, taking out and unfreezing;
(3) and circulating the step three (2) for 5 to 6 times to obtain cellulose gel;
(4) and neutralizing the cellulose gel to be neutral by using an 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 for preparing a cellulose-based porous material for carbon sequestration according to 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 a cellulose-based porous material for carbon sequestration according to claim 2, wherein the method for preparing the self-made cellulose powder is specifically completed according to the following steps:
(1) adding the biomass powder into a mixed solution of distilled water, acetic acid and sodium chlorite, and reacting in a water bath at the temperature of 80-90 ℃;
(2) repeating the step one (1) for 3 to 5 times, and then performing suction filtration and cleaning to obtain fiber A;
(3) adding the fiber A into NaOH solution, heating to 80-90 ℃, treating at 80-90 ℃, then 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, reacting in a water bath at the temperature of 80-90 ℃, adding into a NaOH solution, heating to the temperature of 80-90 ℃, treating at the temperature of 80-90 ℃, finally performing 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 sequestration according to claim 3, wherein the ratio of the mass of the biomass powder to the volume of the mixed solution of distilled water, acetic acid and sodium chlorite in step (1) is (4-8 g): (180-210 mL); the biomass powder in the step (1) is wood powder or bamboo powder; the reaction time in the water bath at the temperature of 80-90 ℃ in the step (1) is 1-3 h; the ratio of the mass of the fiber A in the step (3) to the volume of the NaOH solution is (4 g-8 g) to (90 mL-120 mL); the treatment time at 80-90 ℃ in the step (3) is 1-2 h; the number of times of repeatedly washing with distilled water in the step (3) is 3-5 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, reacting for 1-2 h in a water bath at the temperature of 80-90 ℃, then putting into a NaOH solution, heating to the temperature of 80-90 ℃, and treating for 0.5-1 h at the temperature of 80-90 ℃; the concentration of the acetic acid in the mixed solution of the distilled water, the acetic acid and the sodium chlorite in the step (1) and the step (4) is 1.1-1.4 mol/L; the concentration of sodium chlorite in the mixed solution of distilled water, acetic acid and sodium chlorite in the step (1) and the step (4) is 0.12-0.15 mol/L; the concentration of the NaOH solution in the step (3) and the step (4) is 0.3 mol/L-0.4 mol/L.
5. The method of preparing a cellulose-based porous material for carbon capture according to claim 1, wherein the ratio of the mass of the cellulose powder to the volume of the sodium hydroxide/urea aqueous solution in the first step is (4 g-6 g) to (80 mL-150 mL); in the first step, the mass fraction of the sodium hydroxide in the sodium hydroxide/urea aqueous solution is 6-12%, and the mass fraction of the urea is 8-15%.
6. The method for preparing a cellulose-based porous material for carbon sequestration according to claim 1, wherein the freezing temperature in the first step is-30 ℃ to 40 ℃ and the freezing time is 6h to 8h; the thawing temperature in the step one is 20-25 ℃, and the thawing time is 3-6 h.
7. The method for preparing a cellulose-based porous material for carbon capture according to claim 1, wherein the mass ratio of polyethyleneimine to distilled water in the second step is (33-44): (50-70); the mass ratio of the polyethyleneimine to the 1, 2-butylene oxide in the second step is (33-44) to (10-15); and the stirring time at room temperature in the step two is 10-12 h.
8. The method for preparing a cellulose-based porous material for carbon capture according to claim 1, wherein the volume ratio of the epichlorohydrin to the epoxy functionalized polyethyleneimine solution in the step three (1) is (1-3) to (1-5); the volume ratio of the epichlorohydrin to the cellulose aqueous solution in the step three (1) is (1-3) to (20-25).
9. The method for preparing a cellulose-based porous material for carbon sequestration according to claim 1, wherein the freezing temperature in the step three (2) is-30 ℃ to-40 ℃, and the freezing time is 6h to 8h; the thawing temperature in the step three (2) is 20-25 ℃, and the thawing time is 4-6 h; the temperature of the freeze drying in the step three (4) is-35 ℃ to-45 ℃, and the time of the freeze drying is 48h to 60h.
10. Use of a cellulose-based porous material for carbon capture prepared by the preparation method as set forth in claim 1, characterized in that a cellulose-based porous material for carbon capture is used for capturing carbon.
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