CN110105615B - Preparation method of amino modified cellulose aerogel - Google Patents

Preparation method of amino modified cellulose aerogel Download PDF

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CN110105615B
CN110105615B CN201910306586.7A CN201910306586A CN110105615B CN 110105615 B CN110105615 B CN 110105615B CN 201910306586 A CN201910306586 A CN 201910306586A CN 110105615 B CN110105615 B CN 110105615B
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孔勇
张嘉月
沈晓冬
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Nanjing Tech University
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    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • B01D2257/50—Carbon oxides
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    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
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    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention relates to a preparation method of amino modified cellulose aerogel. The method comprises the steps of dissolving cellulose in a sodium hydroxide-urea-water solvent system to obtain a clear and transparent cellulose solution, forming cellulose gel by a phase inversion method, washing the gel with an acetic acid aqueous solution, soaking the gel in an amino modifier for amino modification, and then performing solvent replacement and drying to obtain the amino modified cellulose aerogel. The preparation method of the amino modified cellulose aerogel provided by the invention is simple, is suitable for large-scale production, can be used for high-efficiency selective adsorption of formaldehyde, carbon dioxide and other gases, and has the carbon dioxide adsorption amount of 2.9mmol/g and the formaldehyde adsorption amount of 3.2 mmol/g.

Description

Preparation method of amino modified cellulose aerogel
Technical Field
The invention belongs to the field of preparation of new materials, and relates to a preparation method of amino modified cellulose aerogel.
Background
The cellulose aerogel has the characteristics of ultralow density, high specific surface area, large porosity and the like. In order to meet the application of different requirements, the functional modification of the cellulose aerogel draws wide attention of researchers, and particularly, the amino modified cellulose aerogel can be used in the fields of carbon dioxide and metal ion adsorption and the like. Patent CN106750384A provides a method for modifying cellulose aerogel by gas phase method, which comprises the steps of preparing cellulose aerogel, and then modifying in gaseous aminosilane, wherein the modification process has many steps, needs special equipment, and is not suitable for large-scale industrial production. The document (journal of southwest university of forestry, 2018,38(3): 181-.
Disclosure of Invention
The invention aims to make up the defects of the prior art, and provides a preparation method of amino modified cellulose aerogel.
The technical scheme of the invention is as follows: a preparation method of amino modified cellulose aerogel comprises the following specific steps:
(1) dissolving cellulose in a sodium hydroxide-urea-water solvent system at the temperature of-20 to-10 ℃ to obtain a clear and transparent cellulose solution, and forming cellulose gel from the cellulose solution by a phase inversion method;
(2) washing the cellulose gel obtained in the step (1) with an acetic acid aqueous solution, and soaking the cellulose gel in an amino modifier treated by carbon dioxide at 0-60 ℃ to modify amino;
(3) and (3) carrying out solvent replacement and drying on the amino modified cellulose gel obtained in the step (2) to obtain the amino modified cellulose aerogel.
Preferably, the mass ratio of the sodium hydroxide to the urea to the water in the sodium hydroxide-urea-water solvent system in the step (1) is 1 (1.5-2.5) to (10-15).
Preferably, the phase inversion method in step (1) is as follows: and (3) placing the mould filled with the cellulose solution into a container filled with a coagulating bath, and volatilizing and diffusing the coagulating bath into the cellulose solution to enable the cellulose solution to generate phase-inversion gel.
Preferably, the solvent in the coagulation bath is water or ethanol; the temperature of the coagulation bath is generally 20 to 50 ℃.
Preferably, the volume concentration of the acetic acid aqueous solution in the step (2) is 1-10%.
Preferably, the volume concentration of the carbon dioxide gas in the step (2) is 10-100%; the gas flow rate is 0.1-1L/min; the treatment time is 10-60 min.
Preferably, the amino modifier in step (2) is a solution of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, polyethyleneimine or tetraethylenepentamine.
The method for treating the carbon dioxide gas as the amino modifier in the step (2) comprises the following steps: and introducing carbon dioxide gas into the amino modifier until the pH value of the solution is stable.
Preferably, the solvent replacement in the step (3) adopts water, ethanol or n-hexane as a solvent.
Preferably, the drying in step (3) is vacuum drying, freeze drying or supercritical drying.
Has the advantages that:
the preparation method of the amino modified cellulose aerogel provided by the invention is simple and suitable for large-scale production, and the prepared amino modified cellulose aerogel can be used for efficient and selective adsorption of formaldehyde, carbon dioxide and other gases, wherein the adsorption capacity of the carbon dioxide is 2.0-2.9 mmol/g, and the adsorption capacity of the formaldehyde is 2.1-3.2 mmol/g.
Drawings
FIG. 1 is an XRD pattern of the cellulose powder and cellulose aerogel of example 1.
Detailed Description
Example 1
Dissolving 2g of cellulose in a sodium hydroxide/urea/water solvent system at the temperature of-20 ℃ to obtain a clear and transparent cellulose solution, wherein the mass ratio of sodium hydroxide to urea to water is 1:1.5:10, placing a mould filled with the cellulose solution into a container filled with a 25 ℃ water coagulation bath, volatilizing and diffusing the coagulation bath into the cellulose solution to enable the cellulose solution to generate phase inversion gel, washing the gel with 1% acetic acid aqueous solution by volume concentration, and soaking the gel in carbon dioxide-treated 3-aminopropyl at the temperature of 0 DEG CPerforming amino modification in the solution of the trimethoxy silane until the pH of the solution is stable, wherein the volume concentration of carbon dioxide gas for treatment is 100%, the gas flow rate is 0.1/min, the treatment time is 30min, and then performing water replacement and freeze drying to obtain the amino modified cellulose aerogel, wherein the carbon dioxide adsorption capacity of the amino modified cellulose aerogel is 2.9mmol/g, and the formaldehyde adsorption capacity is 3.2 mmol/g. FIG. 1 is an XRD pattern of cellulose powder and the cellulose aerogel of this example. As can be seen from the phase analysis of the cellulose powder, the diffraction angles of the starting material 2 θ of the cellulose powder, 14.79 °, 16.53 °, 20.59 °, 22.82 ° and 34.46 °, match the diffraction angles of the characteristic peaks of cellulose I, and the corresponding plane indices (101), (la), (lb), and (lb), respectively,
Figure BDA0002030005140000032
(021) (002) and (040) show that the cellulose powder (raw material) shows a typical natural cellulose type I structure. Whereas, in contrast to the cellulose aerogels, a distinct precipitate is produced, the presence of which is related to the addition of sodium hydroxide. Meanwhile, the diffraction angles of 12.09 degrees, 20.18 degrees and 21.64 degrees at 2 theta are matched with the diffraction angle of the cellulose II, and the corresponding plane indexes are respectively (101),
Figure BDA0002030005140000031
And (002), which shows the conversion of the cellulose crystal structure from the typical type I structure to the type II structure, and at the same time, generates a relatively obvious crystallization phase.
Example 2
Dissolving 6g of cellulose in a sodium hydroxide/urea/water solvent system at the temperature of-15 ℃ to obtain a clear and transparent cellulose solution, wherein the mass ratio of sodium hydroxide to urea to water is 1:2:11, placing a mould filled with the cellulose solution into a container filled with a 25 ℃ ethanol coagulation bath, volatilizing and diffusing the coagulation bath into the cellulose solution to enable the cellulose solution to generate phase-inversion gel, washing the gel with a 5% acetic acid aqueous solution by volume concentration, soaking the gel in a carbon dioxide treated solution of 3-aminopropyltriethoxysilane at 20 ℃ for amino modification until the pH of the solution is stable, treating the gel with carbon dioxide gas at the volume concentration of 50%, the gas flow rate is 0.5L/min, the treatment time is 10min, then performing ethanol displacement and supercritical drying to obtain an amino-modified cellulose aerogel, wherein the carbon dioxide adsorption capacity of the amino-modified cellulose aerogel is 2.5mmol/g, the formaldehyde adsorption capacity was 2.8 mmol/g.
Example 3
Dissolving 8g of cellulose in a sodium hydroxide/urea/water solvent system at the temperature of-10 ℃ to obtain a clear and transparent cellulose solution, wherein the mass ratio of sodium hydroxide to urea to water is 1:2.5:13, placing a mould filled with the cellulose solution into a container filled with a 45 ℃ water coagulation bath, volatilizing and diffusing the coagulation bath into the cellulose solution to enable the cellulose solution to generate phase conversion gel, washing the gel with 8% of acetic acid aqueous solution with volume concentration, soaking the gel in a 40 ℃ polyethyleneimine solution treated by carbon dioxide to perform amino modification until the pH of the solution is stable, performing treatment with carbon dioxide gas with volume concentration of 70%, gas flow rate of 1L/min and treatment time of 45min, performing ethanol displacement and supercritical drying to obtain amino-modified cellulose aerogel, wherein the carbon dioxide adsorption amount of the amino-modified cellulose aerogel is 2.0mmol/g, the formaldehyde adsorption amount was 2.1 mmol/g.
Example 4
Dissolving 10g of cellulose in a sodium hydroxide/urea/water solvent system at the temperature of-10 ℃ to obtain a clear and transparent cellulose solution, wherein the mass ratio of sodium hydroxide to urea to water is 1:1.8:15, placing a mould filled with the cellulose solution into a container filled with a 50 ℃ water coagulation bath, volatilizing and diffusing the coagulation bath into the cellulose solution to enable the cellulose solution to generate phase transformation gel, washing the gel with 10% of acetic acid aqueous solution with volume concentration, soaking the gel in 60 ℃ tetraethylenepentamine solution treated by carbon dioxide to perform amino modification until the pH of the solution is stable, performing treatment with carbon dioxide gas with volume concentration of 10%, gas flow rate of 0.7L/min and treatment time of 60min, then performing n-hexane replacement and vacuum drying to obtain amino-modified cellulose aerogel, wherein the carbon dioxide adsorption capacity of the amino-modified cellulose aerogel is 2.6mmol/g, the formaldehyde adsorption amount was 2.7 mmol/g.

Claims (6)

1. A preparation method of amino modified cellulose aerogel comprises the following specific steps:
(1) dissolving cellulose in a sodium hydroxide-urea-water solvent system at the temperature of minus 20 to minus 10 ℃ to obtain a clear and transparent cellulose solution, and forming cellulose gel from the cellulose solution by a phase inversion method;
(2) washing the cellulose gel obtained in the step (1) with an acetic acid aqueous solution, and soaking the cellulose gel in an amino modifier treated by carbon dioxide at 0-60 ℃ to modify amino; wherein the volume concentration of the acetic acid aqueous solution is 1-10%; the volume concentration of the carbon dioxide gas is 10-100%; the gas flow rate is 0.1-1L/min; the treatment time is 10-60 min; the amino modifier is a solution of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, polyethyleneimine or tetraethylenepentamine;
(3) and (3) carrying out solvent replacement and drying on the amino modified cellulose gel obtained in the step (2) to obtain the amino modified cellulose aerogel.
2. The method according to claim 1, wherein the mass ratio of sodium hydroxide to urea to water in the sodium hydroxide-urea-water solvent system in step (1) is 1 (1.5-2.5) to (10-15).
3. The production method according to claim 1, characterized in that the phase inversion method in the step (1) is: and (3) placing the mould filled with the cellulose solution into a container filled with a coagulating bath, and volatilizing and diffusing the coagulating bath into the cellulose solution to enable the cellulose solution to generate phase-inversion gel.
4. The production method according to claim 3, characterized in that the solvent in the coagulation bath is water or ethanol.
5. The method according to claim 1, wherein the solvent in the step (3) is replaced with water, ethanol or n-hexane.
6. The method according to claim 1, wherein the drying in the step (3) is vacuum drying, freeze drying or supercritical drying.
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CN111715189A (en) * 2020-06-23 2020-09-29 天津科技大学 Preparation of amino acid modified cellulose composite membrane with efficient formaldehyde adsorption characteristic
CN113083243A (en) * 2021-04-06 2021-07-09 南京林业大学 Wood-based CO2Preparation method of adsorbing material
CN115124757A (en) * 2022-07-29 2022-09-30 江南大学 Cellulose-based aerogel small ball capable of efficiently removing chromium, and preparation method and application thereof

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氨基改性纳米纤维素气凝胶的制备及吸附性能研究;张天蒙等;《西南林业大学学报(自然科学)》;20180515;第38卷(第03期);第231页第1栏第21-30行，第232页第1栏表2以及第2栏图2 *
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