CN110105615A - Preparation method of amino modified cellulose aerogel - Google Patents
Preparation method of amino modified cellulose aerogel Download PDFInfo
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- CN110105615A CN110105615A CN201910306586.7A CN201910306586A CN110105615A CN 110105615 A CN110105615 A CN 110105615A CN 201910306586 A CN201910306586 A CN 201910306586A CN 110105615 A CN110105615 A CN 110105615A
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- cellulose
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- amino modified
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- gel
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 66
- 239000001913 cellulose Substances 0.000 title claims abstract description 66
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 37
- 239000004964 aerogel Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 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 abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 230000001112 coagulating effect Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 239000003125 aqueous solvent Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 238000000352 supercritical drying Methods 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- -1 amino modified cellulose gel Chemical class 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 22
- 239000007789 gas Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 229920000875 Dissolving pulp Polymers 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 238000000614 phase inversion technique Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- MGMBFZBQKZNAHF-UHFFFAOYSA-M sodium urea hydroxide hydrate Chemical compound O.NC(=O)N.[OH-].[Na+] MGMBFZBQKZNAHF-UHFFFAOYSA-M 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 11
- 239000000499 gel Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- 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
- B01J20/28047—Gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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
Technical field
The invention belongs to the preparation fields of new material, are related to a kind of preparation method of amino modified cellulose aerogels.
Background technique
Cellulose aerogels have the characteristics such as extremely-low density, high-specific surface area, macroporosity.In order to meet different demands
Cause researcher's extensive concern using, the functional modification of cellulose aerogels, especially amino modified cellulose aerogels,
It can be used for the numerous areas such as carbon dioxide and adsorption of metal ions.It is modified fine that patent CN106750384A provides a kind of vapor phase method
The method for tieing up plain aeroge, this method prepare cellulose aerogels first, then modified in gaseous state amino silane, modified technique
Step is more, needs special equipment, is not suitable for large-scale industrial production.Document (Southwest Forestry University's journal, 2018,38
(3): 181-187 a kind of method for) also reporting amino modified cellulose aerogels, this method prepare fiber by raw material of paper pulp
Element, titration obtains hydrogel after cellulose is configured to cellulose sol, and this method cumbersome, titration technique are not suitable for extensive
Production.
Summary of the invention
The purpose of the invention is to make up the deficiencies in the prior art, and provide a kind of amino modified cellulose aerogels
Preparation method, prepared amino modified cellulose aerogels can carry out efficient selective with PARA FORMALDEHYDE PRILLS(91,95) and carbon dioxide gas
Absorption.
The technical solution of the present invention is as follows: a kind of preparation method of amino modified cellulose aerogels, the specific steps of which are as follows:
Cellulose dissolution is obtained into clear in sodium hydroxide-urea-aqueous solvent at (1) -20~-10 DEG C
Cellulose solution, cellulose solution form cellulose gel by phase inversion；
(2) it after the cellulose gel that step (1) obtains is washed with aqueous acetic acid, is immersed in and is handled through carbon dioxide gas
It is carried out in amino modified dose of 0~60 DEG C crossed amino modified；
(3) the amino modified cellulose gel that step (2) obtains replaces and is dried to obtain amino modified cellulose through solvent
Aeroge.
Sodium hydroxide in sodium hydroxide-urea-aqueous solvent described in preferred steps (1): urea: the quality of water
Than for 1:(1.5~2.5): (10~15).
Phase inversion described in preferred steps (1) are as follows: the mold equipped with cellulose solution is placed in equipped with coagulating bath
In container, coagulating bath volatilization, which diffuses in cellulose solution, makes cellulose solution that inversion of phases gel occur.
It is preferred that the solvent in the coagulating bath is water or ethyl alcohol；The temperature of coagulating bath is generally 20~50 DEG C.
The volumetric concentration of aqueous acetic acid described in preferred steps (2) is 1~10%.
Carbon dioxide gas volumetric concentration described in preferred steps (2) is 10%~100%；Gas flow rate be 0.1~
1L/min；The processing time is 10~60min.
Amino modified dose is 3- aminopropyl triethoxysilane, 3- aminopropyl trimethoxy described in preferred steps (2)
The solution of silane, polyethyleneimine or tetraethylenepentamine.
Amino modified dose of carbon dioxide gas processing method described in step (2) are as follows: carbon dioxide gas is passed through ammonia
Stablize in base modifying agent to pH value of solution.
The displacement of solvent described in preferred steps (3) uses water, ethyl alcohol or n-hexane for solvent.
Drying described in preferred steps (3) is vacuum drying, freeze-drying or supercritical drying.
The utility model has the advantages that
Amino modified cellulose aerogels preparation method provided by the present invention is simple, is suitble to large-scale production, prepared
Amino modified cellulose aerogels can be used for the gases such as formaldehyde and carbon dioxide efficient selective absorption, carbon dioxide adsorption
Amount is 2.0~2.9mmol/g, and formaldehyde absorbing amount is 2.1~3.2mmol/g.
Detailed description of the invention
Fig. 1 is the XRD spectrum of embodiment 1 cellulose powder and cellulose aerogels.
Specific embodiment
Example 1
2g cellulose dissolution is obtained into the cellulose of clear in sodium hydroxide/urea/aqueous solvent at -20 DEG C
Solution, sodium hydroxide: urea: water quality ratio is 1:1.5:10, and the mold equipped with cellulose solution is placed in equipped with 25 DEG C of water-settings
Admittedly in the container bathed, coagulating bath volatilization, which diffuses in cellulose solution, makes cellulose solution that inversion of phases gel, gel body occur
Product concentration is that 0 DEG C of the 3- aminopropyl trimethoxysilane that carbon dioxide treatment is crossed is immersed in after 1% aqueous acetic acid washs
Carried out in solution it is amino modified stablize to pH value of solution, processing carbon dioxide gas volumetric concentration is 100%, and gas flow rate is
0.1/min, processing time are 30min, then obtain amino modified cellulose aerogels through water displacement and freeze-drying, amino changes
Property cellulose aerogels carbon dioxide adsorption be 2.9mmol/g, formaldehyde absorbing amount be 3.2mmol/g.Fig. 1 is cellulose powder
With the XRD spectrum of the present embodiment cellulose aerogels.It can be seen that 2 θ of raw material of cellulose powder from the material phase analysis of cellulose powder
=14.79 °, 16.53 °, 20.59 °, 22.82 ° and 34.46 ° of the angle of diffraction matches with the angle of diffraction of the characteristic peak of cellulose I,
The indices of crystallographic plane corresponding simultaneously be respectively (101),(021), (002), (040) illustrate that cellulose powder (raw material) is aobvious
Typical native cellulose I type structure is shown.And relative to cellulose aerogels, apparent precipitated phase is produced, precipitated phase
Presence it is related with the sodium hydroxide of addition.Simultaneously in 2 θ=12.09 °, the angle of diffraction and the cellulose Ⅱ of 20.18 ° and 21.64 °
The angle of diffraction match, the corresponding indices of crystallographic plane be respectively (101),(002), illustrate to show cellulose crystalline structure
Transformation from from typical I type structure to II type structure, while producing obvious crystallization phase.
Example 2
6g cellulose dissolution is obtained into the cellulose of clear in sodium hydroxide/urea/aqueous solvent at -15 DEG C
Solution, sodium hydroxide: urea: water quality ratio is 1:2:11, and the mold equipped with cellulose solution is placed in and is coagulated equipped with 25 DEG C of ethyl alcohol
Admittedly in the container bathed, coagulating bath volatilization, which diffuses in cellulose solution, makes cellulose solution that inversion of phases gel, gel body occur
Product concentration is that 20 DEG C of the 3- aminopropyl triethoxysilane that carbon dioxide treatment is crossed is immersed in after 5% aqueous acetic acid washs
Carried out in solution it is amino modified stablize to pH value of solution, processing carbon dioxide gas volumetric concentration is 50%, and gas flow rate is
0.5L/min, processing time are 10min, then obtain amino modified cellulose aerogels through ethanol replacement and supercritical drying,
The carbon dioxide adsorption of amino modified cellulose aerogels is 2.5mmol/g, and formaldehyde absorbing amount is 2.8mmol/g.
Example 3
8g cellulose dissolution is obtained into the cellulose of clear in sodium hydroxide/urea/aqueous solvent at -10 DEG C
Solution, sodium hydroxide: urea: water quality ratio is 1:2.5:13, and the mold equipped with cellulose solution is placed in equipped with 45 DEG C of water-settings
Admittedly in the container bathed, coagulating bath volatilization, which diffuses in cellulose solution, makes cellulose solution that inversion of phases gel, gel body occur
Product concentration is to be immersed in the solution for 40 DEG C of the polyethyleneimine that carbon dioxide treatment is crossed to carry out after 8% aqueous acetic acid washs
Amino modified to stablize to pH value of solution, processing is 70%, gas flow rate 1L/min with carbon dioxide gas volumetric concentration, when processing
Between be 45min, then obtain amino modified cellulose aerogels, amino modified cellulose gas through ethanol replacement and supercritical drying
The carbon dioxide adsorption of gel is 2.0mmol/g, and formaldehyde absorbing amount is 2.1mmol/g.
Example 4
10g cellulose dissolution is obtained into the fiber of clear in sodium hydroxide/urea/aqueous solvent at -10 DEG C
Plain solution, sodium hydroxide: urea: water quality ratio is 1:1.8:15, and the mold equipped with cellulose solution is placed in equipped with 50 DEG C of water
In the container of coagulating bath, coagulating bath volatilization, which diffuses in cellulose solution, makes cellulose solution that inversion of phases gel occur, and gel is used
Volumetric concentration is to be immersed in the solution for 60 DEG C of the tetraethylenepentamine that carbon dioxide treatment is crossed after 10% aqueous acetic acid washs
Carry out it is amino modified to pH value of solution stablize, processing with carbon dioxide gas volumetric concentration be 10%, gas flow rate 0.7L/min,
The processing time is 60min, then obtains amino modified cellulose aerogels, amino modified fibre through n-hexane displacement and vacuum drying
The carbon dioxide adsorption for tieing up plain aeroge is 2.6mmol/g, and formaldehyde absorbing amount is 2.7mmol/g.
Claims (9)
1. a kind of preparation method of amino modified cellulose aerogels, the specific steps of which are as follows:
Cellulose dissolution is obtained into the fiber of clear in sodium hydroxide-urea-aqueous solvent at (1) -20~-10 DEG C
Plain solution, cellulose solution form cellulose gel by phase inversion；
(2) it after the cellulose gel that step (1) obtains is washed with aqueous acetic acid, is immersed in processed through carbon dioxide gas
It is carried out in amino modified dose of 0~60 DEG C amino modified；
(3) the amino modified cellulose gel that step (2) obtains replaces and is dried to obtain amino modified cellulose airsetting through solvent
Glue.
2. preparation method according to claim 1, it is characterised in that sodium hydroxide-urea-described in step (1) is water-soluble
Sodium hydroxide in agent system: urea: the mass ratio of water is 1:(1.5~2.5): (10~15).
3. preparation method according to claim 1, it is characterised in that phase inversion described in step (1) are as follows: will be equipped with
The mold of cellulose solution is placed in the container equipped with coagulating bath, and coagulating bath volatilization, which diffuses in cellulose solution, keeps cellulose molten
Inversion of phases gel occurs for liquid.
4. preparation method according to claim 1, it is characterised in that the solvent in the coagulating bath is water or ethyl alcohol.
5. preparation method according to claim 1, it is characterised in that the volume of aqueous acetic acid described in step (2) is dense
Degree is 1~10%.
6. preparation method according to claim 1, it is characterised in that carbon dioxide gas volume described in step (2) is dense
Degree is 10%~100%；Gas flow rate is 0.1~1 L/min；The processing time is 10~60min.
7. preparation method according to claim 1, it is characterised in that amino modified dose is 3- ammonia third described in step (2)
The solution of ethyl triethoxy silicane alkane, 3- aminopropyl trimethoxysilane, polyethyleneimine or tetraethylenepentamine.
8. preparation method according to claim 1, it is characterised in that the displacement of solvent described in step (3) uses water, second
Alcohol or n-hexane are solvent.
9. preparation method according to claim 1, it is characterised in that drying described in step (3) is to be dried in vacuo, is cold
Dry or supercritical drying is lyophilized.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| 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 |
| CN115920859A (en) * | 2022-12-08 | 2023-04-07 | 深圳市真味生物科技有限公司 | Preparation method of composite aerogel for reducing phenols and carbonyl substances in smoke and product thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN115920859A (en) * | 2022-12-08 | 2023-04-07 | 深圳市真味生物科技有限公司 | Preparation method of composite aerogel for reducing phenols and carbonyl substances in smoke and product thereof |
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