CN106111195B - A kind of preparation method of continuous cellulose-nano metal composite aerogel fiber - Google Patents
A kind of preparation method of continuous cellulose-nano metal composite aerogel fiber Download PDFInfo
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- CN106111195B CN106111195B CN201610472038.8A CN201610472038A CN106111195B CN 106111195 B CN106111195 B CN 106111195B CN 201610472038 A CN201610472038 A CN 201610472038A CN 106111195 B CN106111195 B CN 106111195B
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- 239000000835 fiber Substances 0.000 title claims abstract description 119
- 239000004964 aerogel Substances 0.000 title claims abstract description 86
- 239000002905 metal composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 32
- 229920002678 cellulose Polymers 0.000 claims abstract description 119
- 239000001913 cellulose Substances 0.000 claims abstract description 119
- 238000009987 spinning Methods 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 230000001112 coagulating effect Effects 0.000 claims abstract description 46
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003292 glue Substances 0.000 claims abstract description 27
- 235000019441 ethanol Nutrition 0.000 claims abstract description 22
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003863 metallic catalyst Substances 0.000 claims abstract description 18
- 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 17
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 238000002166 wet spinning Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000006073 displacement reaction Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 238000004804 winding Methods 0.000 claims description 19
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- 229920000742 Cotton Polymers 0.000 claims description 17
- 239000002105 nanoparticle Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 12
- 241000894006 Bacteria Species 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 238000000352 supercritical drying Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 239000008104 plant cellulose Substances 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 27
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000011943 nanocatalyst Substances 0.000 abstract description 2
- 235000010980 cellulose Nutrition 0.000 description 107
- 239000000243 solution Substances 0.000 description 73
- 239000002131 composite material Substances 0.000 description 52
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 24
- 229940106681 chloroacetic acid Drugs 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 14
- 239000010931 gold Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 230000008859 change Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- 238000001879 gelation Methods 0.000 description 8
- 238000004255 ion exchange chromatography Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B01J35/615—
-
- B01J35/647—
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
Abstract
The present invention provides a kind of manufacturing method of continuous cellulose-nano metal composite aerogel fiber, comprising the following steps: prepares cellulose dispersion liquid as spinning solution, metallic catalyst is then added；Acid solution, ethanol solution or acetone soln are added in coagulating basin as coagulating bath；Spinning solution after addition nanocatalyst is added in coagulating bath, wet spinning is carried out, obtains the cellulose gel glue fiber containing metallic catalyst；By the cellulose gel fiber roll containing metallic catalyst around, it immerses room temperature in aged solution and is aged 15min~1h, it is washed with deionized to neutrality, then solvent displacement is carried out with deionized water, ethyl alcohol or the tert-butyl alcohol, it is dry, obtain the continuous cellulose with catalytic performance-nano metal composite aerogel fiber.Continuous cellulose provided by the invention-nano metal composite aerogel fiber manufacturing method has the characteristics that raw material sources are extensive, at low cost, preparation process is simple and green non-pollution, good spinnability.
Description
Technical field
The invention belongs to the preparation field of aeroge, in particular to a kind of continuous cellulose-nano metal composite aerogel
The preparation method of fiber, the continuous cellulose-nano metal composite aerogel fiber have catalysis.
Background technique
Catalyst is a kind of substance that can change chemical reaction velocity and not enter in final product molecular composition itself.
In practical applications, the often more expensive and utilization rate such as catalytic active component such as Au Ag Pt Pd is not high, to improve catalysis
Agent catalytic efficiency reduces catalytic active component dosage, catalytic active component is supported on carrier, carrier can make manufactured catalysis
Agent has certain shape, size and mechanical strength, can make active component dispersion on the surface of the carrier, obtain higher specific surface
Product improves the catalytic efficiency of unit mass active component.Aeroge (aerogel) is a kind of highly porous solid, in solid
Gassy (usually air) in the hole and network structure of matrix has high porosity and high-specific surface area etc. a series of excellent
Different characteristic.The aerogel material of Present Attitude aperture can with high specific surface area, biggish hole appearance and aperture size because of it
The characteristics of tune, becomes the research hotspot in catalyst carrier field.
Aeroge is divided into inorganic aerogels and organic aerogel, compared to frangible inorganic aerogels, organic aerogel tool
There are mechanics better performances, the good advantage of flexibility.The present invention is urged using a kind of organic cellulose airsetting glue fiber as nano metal
The carrier of agent, the carrier not only have good mechanical performance and flexibility, but also the most wide renewable, reserves of its raw material sources
It is abundant, nontoxic and can biodegrade.
The current research in relation to cellulose aerogels supported nano-gold metal catalyst has focused largely on two dimension, three-dimensional fiber element
On aerogel material, if Zhang Xinxing seminar, Sichuan University is microcrystalline cellulose and Fe3O4Nano particle mixes in ionic liquid
Uniformly, Fe is made after solidification regeneration3O4Nanofiber fiber hydrogel is coated, hydrogel obtained is immersed AgNO3Solution
In, Fe is obtained by the hydroxyl in-situ reducing on cellulose3O4The nanofiber fiber hydrogel coated jointly with Ag, passes through
Freeze-drying and air dried method respectively obtain nano metal composite aerogel block and nano metal composite membrane, by right
NaBH is catalyzed than them4The reaction for restoring 4- nitrophenol is obtained because aeroge has the feature of high-specific surface area, is increased
The accessibility of reactant and catalytic active center Ag nano particle, substantially increases reaction speed, make reaction rate constant by
0.0106min-1Increase to 0.2min-1；Zhang Lina seminar, Wuhan University cellulose dissolution in alkalinuria element low temperature system,
Cellulose aquagel film is obtained after regeneration, is dipped in metal salt solution, is prepared in situ using its three-dimensional porous network structure
Controlled dimensions, Ag, Au and Pt nano particle of shape and stable dispersion, then obtained by supercritical drying with high-ratio surface
Long-pending cellulose nano metal composite aerogel film can be applied to the fields such as catalysis load.But current one dimension fibre element gas
Gelatinous fibre supported nano-gold metal catalyst but has not been reported.This is because compared to the aerogel material of other dimensions, fiber
Shape aerogel material requires raw material and preparation condition harsher.However, fibrous aerogel material is compared to two dimension, three-dimensional
Aerogel material has unique advantage.With the aerogel material of carried metal palladium to Disinfection Byproducts in Drinking Water chloroacetic acid
For catalytic hydrogenating reduction, contact complexity of the chloroacetic acid with palladium catalyst determines the catalytic efficiency of material.With bulk
And film-like material is compared, fibrous material further improves the contact area with chloroacetic acid, while chloroacetic acid is in material
Diffusional resistance in material is substantially reduced with transmission range, makes it easier for contacting with catalytic active center palladium, improves catalysis effect
Rate, and zero dimension catalysis material may cause reunion in use, and be not easy to be kept completely separate, and be easy to cause secondary pollution.
There is about addition nano metal preparation in situ the compound airsetting of continuous cellulose-nano metal of catalytic performance at present
The method of glue fiber has not been reported.
Summary of the invention
The purpose of the present invention is in order to solve the above problem, the present invention provides a kind of compound gas of continuous cellulose-nano metal
The manufacturing method of gelatinous fibre, this manufacturing method is extensive, at low cost with raw material sources, preparation process is simple and green is without dirt
The characteristics of dye, good spinnability.By the technology in situ for adding nano metal, make obtained cellulose-nano metal composite gas
Gelatinous fibre has good flexibility, and has hole abundant and high specific surface area, while pulp freeness, fiber
The advantage that middle nano metal content is adjustable.
A kind of manufacturing method of continuous cellulose-nano metal composite aerogel fiber, comprising the following steps:
(1) cellulose dispersion liquid is prepared as spinning solution, and metallic catalyst is then added；
(2) acid solution, ethanol solution or acetone soln are added in coagulating basin as coagulating bath；
(3) spinning solution after addition nanocatalyst in step (1) is expressed into the coagulating bath in step (2), into
Row wet spinning obtains the cellulose gel glue fiber containing metallic catalyst；
(4) the cellulose gel glue fiber in step (3) containing metallic catalyst is wound in coagulating bath, is immersed old
Change room temperature in solution and be aged 15min~1h, be washed with deionized to neutrality, then with deionized water, ethyl alcohol or the tert-butyl alcohol into
The displacement of row solvent, it is dry, obtain the continuous cellulose with catalytic performance-nano metal composite aerogel fiber.
Preferably, step (1) includes: that dispersing agent is added in plant cellulose or bacteria cellulose, is made into cellulose point
Dispersion liquid, the mass fraction of cellulose dispersion liquid are 2%~7%.
Preferably, step (1) includes: that dispersing agent is added in cellulose, is made into cellulose dispersion liquid, and dispersing agent includes matter
Measure score 4.2%LiOH/12% urea, mass fraction 7%NaOH/12% urea, mass fraction 9.5%NaOH/4.5% thiocarbamide
With mass fraction (7%~8%) NaOH/8% urea/(6.5%~10%) Thiourea.
Preferably, in step (1): metallic catalyst includes Pt nano particle, nano Pd particle, nanometer Au, nanometer Ag or nanometer
One of Cu or a variety of, metallic catalyst additional amount are the 0.1%~1.0% of cellulose dispersion liquid gross mass.
Preferably, in step (2): acid solution includes that mass fraction is 2%~5% sulfuric acid/3~5% aqueous sodium sulfate
Liquid, mass fraction are one or both of 1%~3% dilute acetic acid solution, ethanol solution include volume fraction be 10%~
50% ethanol water, acetone soln include the aqueous acetone solution that volume fraction is 10%~30%.
Preferably, in step (3): the condition of wet spinning is normal temperature and pressure, and the extruded velocity of spinning solution is 0.6m/
Min~6m/min.
Preferably, in step (4): the winding speed of the cellulose gel glue fiber containing metallic catalyst is 0.6m/
Min~24m/min.
Preferably, in step (4): aged solution includes the dilute sulfuric acid that mass fraction is 0.5%~1%, 0.5%~1%
Dilute acetic acid solution, straight alcohol solution, pure acetone solution.
Preferably, in step (4): drying mode is freeze-drying or supercritical drying.
Preferably, plant cellulose is cotton pulp cellulose.
Continuous cellulose of the invention-nano metal composite aerogel fiber is cellulose and the compound production of nano metal
Object, the present invention add the nano metal of different content in the spinning solution used in cellulose aerogels fiber manufacturing process
Catalyst realizes the preparation of continuous cellulose-nano metal composite aerogel fiber.
The present invention adds the compound airsetting of continuous cellulose-nano metal with catalytic performance of nano metal preparation in situ
The hole of glue fiber can adjust specific surface area size by changing preparation condition in nanoscale range.
The metallic catalyst of different content is added to cellulose spin dope by the present invention, spinning in wet spinning
The principle of stoste quick solidification regeneration in coagulating bath directly dissolves the method phase of regeneration preparation cellulose aerogels with cellulose
In conjunction with realizing the preparation of continuous cellulose-nano metal gelatinous fibre by wet spinning, finally by freeze-drying or super face
Boundary is dried to obtain the continuous cellulose with catalytic performance-nano metal composite aerogel fiber, has novelty.Prepared
Continuous cellulose with catalytic performance-nano metal composite aerogel fiber has more outstanding excellent in the fields such as catalysis
Gesture has very huge potential demand, has practicability.
With continuous cellulose-nano metal composite aerogel fiber preparation method of catalytic performance in the present invention, it is
The metallic catalyst of different content is added in cellulose spin dope, it is molten with acid solution, ethanol solution or acetone
As coagulating bath, by acid, ethyl alcohol or the acetone in cellulose spin dope and coagulating bath quick solventnonsolvent occurs for liquid
Double diffusion makes cellulose solidification regeneration, obtains the cellulose gel glue fiber containing nano metal, is carried out fiber by take-up roll
Winding.Then, the cellulose gel glue fiber containing nano metal of winding is immersed in ageing bath, cellulose is made by ageing
It is further formed intermolecular and intramolecular hydrogen bond and gelation, finally obtains stable three-dimensional net structure, form more holes
Hole.It after ageing, is washed using deionized water, then carries out solvent displacement using deionized water, ethyl alcohol or the tert-butyl alcohol, most
The continuous cellulose with catalytic performance-nano metal composite aerogel fiber is obtained by freeze-drying or supercritical drying.
Method used in the present invention has a raw material sources at low cost, preparation process is simple extensively and green non-pollution, can
The good feature of the property spun.The obtained cellulose-nano metal composite airsetting glue fiber with catalytic performance has good soft
Toughness, and there is hole abundant and high specific surface area, while nano metal content is adjustable in pulp freeness, fiber,
There is broad prospect of application in fields such as catalysis.
Detailed description of the invention
Fig. 1 is continuous cellulose/nanometer Ag composite aerogel fiber morphology scanning electron microscope (SEM) photograph in embodiment 1；
Fig. 2 is continuous cellulose/nanometer Ag composite aerogel fibrous inside hole pattern scanning electron microscope (SEM) photograph in embodiment 1.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
A kind of continuous cellulose of embodiment 1/nanometer Ag composite aerogel fiber preparation method 1
Preparation process: it is that 7%NaOH/8% urea/10% thiocarbamide low temperature is molten that bacteria cellulose, which is dispersed in mass fraction,
Spinning solution is used as in agent system, wherein bacteria cellulose mass fraction is 2%, and mass fraction is added in spinning solution and is
0.8% nanometer Ag catalyst, mechanical strong stirring 30min carry out deaeration processing 20min with centrifuge 10000r/min,
It is 10% ethanol water as coagulating bath that volume fraction is added in coagulating basin, and deaeration is added in the coagulating bath, and treated
Spinning solution, carries out wet spinning, and the extruded velocity of spinning solution is 0.6m/min.Contain nanometer Ag for what is formed in coagulating bath
Cellulose gel glue fiber be wound with the winding speed of 0.6m/min.Fiber after winding, which immerses in straight alcohol solution, to be aged
1h makes its complete gelation.After ageing, fiber is washed with deionized to neutrality, then replaces deionized water, warp with the tert-butyl alcohol
Freeze-drying is to get cellulose/nanometer Ag composite aerogel fiber.
As a result it detects:
1, the successive silk of spinning process, cellulose/nanometer Ag composite aerogel pulp freeness obtained are
175m2/ g, most probable pore size 6nm.
2, continuous cellulose obtained/nanometer Ag composite aerogel fiber morphology microscope figure is as shown in Figure 1；It is obtained
Continuous cellulose/nanometer Ag composite aerogel fibrous inside hole pattern scanning electron microscope (SEM) photograph is as shown in Figure 2.
3, the chloroacetic acid weak solution of 0.0001mol/L is added in four-hole boiling flask, be added at room temperature cellulose obtained/
Nanometer Ag composite aerogel fiber, mixing speed 500r/min.N is passed through into reaction solution2, after flow velocity 50ml/min, 30min
Air-flow is switched to H2, flow velocity 250ml/min, and start timing, it is sampled by certain time interval, detects sample with ion chromatography
Ion concentration in product.Through analyzing, the latter chloroacetic conversion ratio of 3h is 75%, reaction front and back, and continuous cellulose/nanometer Ag is multiple
The amount for closing airsetting glue fiber does not change, and when without adding continuous cellulose/nanometer Ag composite aerogel fiber, chloroacetic acid exists
It is hardly converted in 3h, illustrates that cellulose/nanometer Ag composite aerogel fiber has catalytic effect.
A kind of continuous cellulose of embodiment 2/nanometer Au composite aerogel fiber preparation method 2
Preparation process:
Treated cotton pulp cellulose, (cellulose cotton pulp is mechanically pulverized, in vacuum after repeatedly being washed with water and ethyl alcohol
50 DEG C of drying in baking oven) mass fraction is dispersed in as conduct in 8%NaOH/8% urea/6.5% thiocarbamide low-temperature solvent system
Spinning solution, wherein cotton pulp cellulose mass fraction is 7%, and the nanometer Au that mass fraction is 0.5% is added in spinning solution
Catalyst, mechanical strong stirring 30min carry out deaeration processing 20min with centrifuge 10000r/min, are 50% by volume fraction
Ethanol water pour into coagulating basin, as coagulating bath, be added deaeration in coagulating bath treated spinning solution, carry out wet
Method spinning, the extruded velocity of spinning solution are 3m/min.The cellulose gel glue fiber containing nanometer Au that will be formed in coagulating bath
It is wound with the winding speed of 6m/min.Fiber after winding, which immerses in straight alcohol solution, is aged 1h, makes its complete gelation.
After ageing, fiber is washed with deionized to neutrality, then with ethanol replacement deionized water, through supercritical drying to get continuous
Cellulose/nanometer Au composite aerogel fiber.
As a result it detects:
1, the successive silk of spinning process, continuous cellulose obtained/nanometer Au composite aerogel pulp freeness are
401m2/ g, most probable pore size 3nm.
2, the chloroacetic acid weak solution of 0.0001mol/L is added in four-hole boiling flask, be added at room temperature cellulose obtained/
Nanometer Au composite aerogel fiber, mixing speed 500r/min.N is passed through into reaction solution2, after flow velocity 50ml/min, 30min
Air-flow is switched to H2, flow velocity 250ml/min, and start timing, it is sampled by certain time interval, detects sample with ion chromatography
Ion concentration in product.Through analyzing, the latter chloroacetic conversion ratio of 3h is 85%, reaction front and back, and continuous cellulose/nanometer Au is multiple
The amount for closing airsetting glue fiber does not change, and when without adding continuous cellulose/nanometer Au composite aerogel fiber, chloroacetic acid exists
It is hardly converted in 3h, illustrates that cellulose/nanometer Au composite aerogel fiber has catalytic effect.
A kind of continuous cellulose of embodiment 3/nano Pd particle composite aerogel fiber preparation method 3
Preparation process:
Bacteria cellulose is dispersed in the low-temperature solvent system that mass fraction is 9.5%NaOH/4.5% thiocarbamide, as
Spinning solution, wherein bacteria cellulose mass fraction is 3%, and the nano Pd catalyst that mass fraction is 0.1% is added, mechanical strong
Power stirs 30min, carries out deaeration processing 20min, the aqueous acetone solution for being 10% by volume fraction with centrifuge 10000r/min
It pours into coagulating basin as coagulating bath, the spinning solution after deaeration is poured into coagulating bath, carry out wet spinning, spinning solution
Extruded velocity is 1.8m/min.By the cellulose gel glue fiber containing nano Pd particle formed in coagulating bath with the winding speed of 2m/min
Degree is wound.Fiber after winding, which immerses in pure acetone solution, is aged 20min, makes its complete gelation.After ageing, by fiber
It is washed with deionized to neutrality, it is freeze-dried to get cellulose/nanometer Pd composite aerogel fiber.
As a result it detects:
1, the successive silk of spinning process, cellulose/nanometer Pd composite aerogel pulp freeness obtained are
101m2/ g, most probable pore size 9nm.
2, the chloroacetic acid weak solution of 0.0001mol/L is added in four-hole boiling flask, be added at room temperature cellulose obtained/
Nano Pd particle composite aerogel fiber, mixing speed 500r/min.N is passed through into reaction solution2, after flow velocity 50ml/min, 30min
Air-flow is switched to H2, flow velocity 250mi/min, and start timing, it is sampled by certain time interval, detects sample with ion chromatography
Ion concentration in product.Through analyzing, the latter chloroacetic conversion ratio of 3h is 91%, reaction front and back, and continuous cellulose/nano Pd particle is multiple
The amount for closing airsetting glue fiber does not change, and when without adding continuous cellulose/nano Pd particle composite aerogel fiber, chloroacetic acid exists
It is hardly converted in 3h, illustrates that cellulose/nanometer Pd composite aerogel fiber has catalytic effect.
A kind of continuous cellulose of embodiment 4/Pt nano particle composite aerogel fiber preparation method 4
Preparation process:
It is in the low-temperature solvent system of 4.2%LiOH/12% urea, as spinning bacteria cellulose dispersion quality score
Silk stock solution, wherein bacteria cellulose mass fraction is 2%, and the Pt nano particle that mass fraction is 0.4% is added in the spinning solution
Catalyst, mechanical strong stirring 30min carry out deaeration processing 20min with centrifuge 10000r/min, are 30% by volume fraction
Aqueous acetone solution pour into coagulating basin as coagulating bath, by deaeration, treated that spinning solution is added in coagulating bath, carries out wet
Method spinning, the extruded velocity of spinning solution are 1.8m/min.The cellulose gel containing Pt nano particle formed in coagulating bath is fine
Dimension is wound with the winding speed of 2m/min.Fiber after winding, which immerses in pure acetone solution, is aged 20min, keeps it completely solidifying
Gelatinization.After ageing, fiber is washed with deionized to neutrality, then with the tert-butyl alcohol replace deionized water, it is freeze-dried to get
Cellulose/nanometer Pt composite aerogel fiber.
As a result it detects:
1, the successive silk of spinning process, cellulose/nanometer Pt composite aerogel pulp freeness obtained are
165m2/ g, most probable pore size 6nm.
2, the chloroacetic acid weak solution of 0.0001mol/L is added in four-hole boiling flask, be added at room temperature cellulose obtained/
Pt nano particle composite aerogel fiber, mixing speed 500r/min.N is passed through into reaction solution2, after flow velocity 50ml/min, 30min
Air-flow is switched to H2, flow velocity 250ml/min, and start timing, it is sampled by certain time interval, detects sample with ion chromatography
Ion concentration in product.Through analyzing, the latter chloroacetic conversion ratio of 3h is 87%, reaction front and back, and continuous cellulose/Pt nano particle is multiple
The amount for closing airsetting glue fiber does not change, and when without adding continuous cellulose/Pt nano particle composite aerogel fiber, chloroacetic acid exists
It is hardly converted in 3h, illustrates that cellulose/nanometer Pt composite aerogel fiber has catalytic effect.
A kind of continuous cellulose of embodiment 5/nanometer Cu composite aerogel fiber preparation method 5
Preparation process:
Treated cotton pulp cellulose, (cellulose cotton pulp is mechanically pulverized, in vacuum after repeatedly being washed with water and ethyl alcohol
50 DEG C of drying in baking oven) it is dispersed in the low-temperature solvent system that mass fraction is 4.2%LiOH/12% urea, as spinning original
Liquid, wherein cotton pulp cellulose mass fraction is 4%, and the nanometer Cu catalyst that mass fraction is 1% is added in the spinning solution,
Mechanical strong stirring 30min carries out deaeration processing 20min with centrifuge 10000r/min, is 5% sulfuric acid/5% by mass fraction
Aqueous sodium persulfate solution pours into coagulating basin as coagulating bath, and by deaeration, treated that spinning solution is added in coagulating bath, carries out
Wet spinning, the extruded velocity of spinning solution are 3m/min.The cellulose gel containing Pt nano particle formed in coagulating bath is fine
Dimension is wound with the winding speed of 18m/min.Fiber after winding immerses the dilute sulfuric acid that mass fraction is 0.5% and is aged
20min makes its complete gelation.After ageing, fiber is washed with deionized to neutrality, then with ethanol replacement deionized water,
Through supercritical drying to get continuous cellulose/nanometer Cu composite aerogel fiber.
As a result it detects:
1, the successive silk of spinning process, continuous cellulose obtained/nanometer Cu composite aerogel pulp freeness are
395m2/ g, most probable pore size 3nm.
2, the chloroacetic acid weak solution of 0.0001mol/L is added in four-hole boiling flask, be added at room temperature cellulose obtained/
Nanometer Cu composite aerogel fiber, mixing speed 500r/min.N2 is passed through into reaction solution, after flow velocity 50ml/min, 30min
Air-flow is switched to H2, flow velocity 250ml/min, and start timing, it is sampled by certain time interval, detects sample with ion chromatography
Ion concentration in product.Through analyzing, the latter chloroacetic conversion ratio of 3h is 70%, reaction front and back, and continuous cellulose/nanometer Cu is multiple
The amount for closing airsetting glue fiber does not change, and when without adding continuous cellulose/nanometer Cu composite aerogel fiber, chloroacetic acid exists
It is hardly converted in 3h, illustrates that continuous cellulose/nanometer Cu composite aerogel fiber has catalytic effect.
A kind of continuous cellulose of embodiment 6/nano Pd particle composite aerogel fiber preparation method 6
Preparation process:
Treated cotton pulp cellulose, (cellulose cotton pulp is mechanically pulverized, in vacuum after repeatedly being washed with water and ethyl alcohol
In baking oven 50 DEG C drying) be dispersed in mass fraction be 8%NaOH/8% urea/6.5% thiocarbamide low-temperature solvent system in, as
Spinning solution, wherein cotton pulp cellulose mass fraction is 6%, and the nanometer that mass fraction is 0.2% is added in the spinning solution
Pd catalyst, mechanical strong stirring 30min carry out deaeration processing 20min with centrifuge 10000r/min, are by mass fraction
3% dilute acetic acid solution pours into coagulating basin as coagulating bath, by deaeration treated spinning solution pours into coagulating bath carry out it is wet
Method spinning, the extruded velocity of spinning solution are 4.8m/min.The continuous cellulose containing nano Pd particle formed in coagulating bath is coagulated
Glue fiber is wound with the winding speed of 18m/min.It is in 0.5% dilute acetic acid solution that fiber after winding, which immerses mass fraction,
It is aged 20min, makes its complete gelation.After ageing, fiber is washed with deionized to neutrality, it is freeze-dried to get even
Continuous cellulose/nanometer Pd composite aerogel fiber.
As a result it detects:
1, the successive silk of spinning process, continuous cellulose obtained/nano Pd particle composite aerogel pulp freeness are
115m2/ g, most probable pore size 9nm.
2, the chloroacetic acid weak solution of 0.0001mol/L is added in four-hole boiling flask, be added at room temperature cellulose obtained/
Nano Pd particle composite aerogel fiber, mixing speed 500r/min.N is passed through into reaction solution2, after flow velocity 50ml/min, 30min
Air-flow is switched to H2, flow velocity 250ml/min, and start timing, it is sampled by certain time interval, detects sample with ion chromatography
Ion concentration in product.Through analyzing, the latter chloroacetic conversion ratio of 3h is 85%, reaction front and back, and continuous cellulose/nano Pd particle is multiple
The amount for closing airsetting glue fiber does not change, and when without adding continuous cellulose/nano Pd particle composite aerogel fiber, chloroacetic acid exists
It is hardly converted in 3h, illustrates that continuous cellulose/nano Pd particle composite aerogel fiber has catalytic effect.
A kind of continuous cellulose of embodiment 7/nanometer Ag composite aerogel fiber preparation method 7
Preparation process:
Treated cotton pulp cellulose, (cellulose cotton pulp is mechanically pulverized, in vacuum after repeatedly being washed with water and ethyl alcohol
50 DEG C of drying in baking oven) it is dispersed in the low-temperature solvent system that mass fraction is 7%NaOH/12% urea, as spinning solution,
Wherein cotton pulp cellulose mass fraction is 2%, and the nanometer Ag catalyst that mass fraction is 1%, mechanical strong stirring is added
30min carries out deaeration processing 20min with centrifuge 10000r/min, is 2% sulfuric acid/3% aqueous sodium persulfate solution by mass fraction
It pours into coagulating basin as coagulating bath, by deaeration, treated that spinning solution pours into coagulating bath, carries out wet spinning, spinning is former
The extruded velocity of liquid is 3m/min.By the cellulose gel glue fiber containing nanometer Ag formed in coagulating bath with the volume of 12m/min
It is wound around speed.Fiber after winding immerses the dilute sulfuric acid that mass fraction is 1% and is aged 15min, makes its complete gelation.
After ageing, fiber is washed with deionized to neutrality, then replaces deionized water with the tert-butyl alcohol, it is freeze-dried to get fiber
Element/nanometer Ag composite aerogel fiber.
As a result it detects:
1, the successive silk of spinning process, cellulose/nanometer Ag composite aerogel pulp freeness obtained are
275m2/ g, most probable pore size 6nm.
2, the chloroacetic acid weak solution of 0.0001mol/L is added in four-hole boiling flask, be added at room temperature cellulose obtained/
Nanometer Ag composite aerogel fiber, mixing speed 500r/min.N is passed through into reaction solution2, after flow velocity 50ml/min, 30min
Air-flow is switched to H2, flow velocity 250ml/min, and starts timing, is sampled by certain time interval, detects sample with ion chromatography
Ion concentration in product.Through analyzing, the latter chloroacetic conversion ratio of 3h is 85%, reaction front and back, and continuous cellulose/nanometer Ag is multiple
The amount for closing airsetting glue fiber does not change, and when without adding continuous cellulose/nanometer Ag composite aerogel fiber, chloroacetic acid exists
It is hardly converted in 3h, illustrates that cellulose/nanometer Ag composite aerogel fiber has catalytic effect.
A kind of continuous cellulose of embodiment 8/Pt nano particle composite aerogel fiber preparation method
Preparation process:
Treated cotton pulp cellulose, (cellulose cotton pulp is mechanically pulverized, in vacuum after repeatedly being washed with water and ethyl alcohol
In baking oven 50 DEG C drying) be dispersed in mass fraction be 8%NaOH/8% urea/6.5% thiocarbamide low-temperature solvent system in, as
Spinning solution, wherein cotton pulp cellulose mass fraction is 7%, and the nanometer that mass fraction is 0.6% is added in the spinning solution
Pt catalyst, mechanical strong stirring 30min carry out deaeration processing 20min with centrifuge 10000r/min, are by mass fraction
1% dilute acetic acid solution pours into coagulating basin as coagulating bath, and by deaeration, treated that spinning solution pours into coagulating bath, carries out wet
Method spinning, the extruded velocity of spinning solution are 6m/min.The cellulose gel glue fiber containing Pt nano particle that will be formed in coagulating bath
It is wound with the winding speed of 24m/min.Fiber after winding, which immerses in 1% dilute acetic acid solution, is aged 15min, makes it completely
Gelation.After ageing, fiber is washed with deionized to neutrality, it is freeze-dried to get the compound airsetting of cellulose/nanometer Pt
Glue fiber.
As a result it detects:
1, the successive silk of spinning process, cellulose/nanometer Pt composite aerogel pulp freeness obtained are
126m2/ g, most probable pore size 9nm.
2, the chloroacetic acid weak solution of 0.0001mol/L is added in four-hole boiling flask, be added at room temperature cellulose obtained/
Pt nano particle composite aerogel fiber, mixing speed 500r/min.N is passed through into reaction solution2, after flow velocity 50ml/min, 30min
Air-flow is switched to H2, flow velocity 250ml/min, and starts timing, is sampled by certain time interval, detects sample with ion chromatography
Ion concentration in product.Through analyzing, the latter chloroacetic conversion ratio of 3h is 87%, due to not adding continuous cellulose/Pt nano particle
When composite aerogel fiber, chloroacetic acid hardly converts in 3h, and reacts front and back, and continuous cellulose/Pt nano particle is compound
The amount of airsetting glue fiber does not change, and illustrates that cellulose/nanometer Pt composite aerogel fiber has catalytic effect.
In conclusion method used in the present invention has, raw material sources are at low cost extensively, preparation process is simple and green
The characteristics of pollution-free, good spinnability.The obtained cellulose-nano metal composite composite aerogel fiber with catalytic performance
With good flexibility, and there is hole abundant and high specific surface area, while nanogold in pulp freeness, fiber
It is adjustable to belong to content, there is broad prospect of application in fields such as catalysis.
Claims (10)
1. a kind of continuous cellulose-nano metal composite aerogel fiber manufacturing method, which is characterized in that including following step
It is rapid:
(1) cellulose dispersion liquid is prepared as spinning solution, and metallic catalyst is then added；
(2) acid solution, ethanol solution or acetone soln are added in coagulating basin as coagulating bath；
(3) spinning solution after addition metallic catalyst in step (1) is expressed into the coagulating bath in step (2), into
Row wet spinning obtains the cellulose gel glue fiber containing metallic catalyst；
(4) the cellulose gel glue fiber in step (3) containing metallic catalyst is wound in coagulating bath, it is molten immerses ageing
Room temperature is aged 15min~1h in liquid, is washed with deionized to neutrality, is then carried out with deionized water, ethyl alcohol or the tert-butyl alcohol molten
Agent displacement, it is dry, obtain the continuous cellulose-nano metal composite aerogel fiber.
2. manufacturing method as described in claim 1, which is characterized in that the step (1) includes:
Dispersing agent is added in plant cellulose or bacteria cellulose, is made into the cellulose dispersion liquid, the cellulose dispersion
The mass fraction of liquid is 2%~7%.
3. manufacturing method as described in claim 1, which is characterized in that the step (1) includes:
Dispersing agent is added in cellulose, is made into the cellulose dispersion liquid, the dispersing agent includes mass fraction 4.2%
LiOH/12% urea, mass fraction 7%NaOH/12% urea, mass fraction 9.5%NaOH/4.5% thiocarbamide and mass fraction
7%~8%NaOH/8% urea/6.5%~10% Thiourea.
4. manufacturing method as described in claim 1, which is characterized in that in the step (1):
The metallic catalyst includes one of Pt nano particle, nano Pd particle, nanometer Au, nanometer Ag or nanometer Cu or a variety of,
The metallic catalyst additional amount is the 0.1%~1.0% of cellulose dispersion liquid gross mass.
5. manufacturing method as described in claim 1, which is characterized in that in the step (2):
The acid solution include mass fraction be 2%~5% sulfuric acid/3~5% aqueous sodium persulfate solution, mass fraction be 1%~
One or both of 3% dilute acetic acid solution, the ethanol solution include the ethanol water that volume fraction is 10%~50%,
The acetone soln includes the aqueous acetone solution that volume fraction is 10%~30%.
6. manufacturing method as described in claim 1, which is characterized in that in the step (3):
The condition of wet spinning is normal temperature and pressure, and the extruded velocity of spinning solution is 0.6m/min~6m/min.
7. manufacturing method as described in claim 1, which is characterized in that in the step (4):
The winding speed of the cellulose gel glue fiber containing metallic catalyst is 0.6m/min~24m/min.
8. manufacturing method as described in claim 1, which is characterized in that in the step (4):
The aged solution include mass fraction be 0.5%~1% dilute sulfuric acid, mass fraction be that 0.5%~1% spirit of vinegar is molten
Liquid, straight alcohol solution, pure acetone solution.
9. manufacturing method as described in claim 1, which is characterized in that in the step (4):
Drying mode is freeze-drying or supercritical drying.
10. manufacturing method as claimed in claim 2, which is characterized in that
The plant cellulose is cotton pulp cellulose.
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| CN105463603A (en) * | 2015-12-31 | 2016-04-06 | 东华大学 | Preparing method for SiO2/cellulose tough aerogel fibers |
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