CN105603577B - A kind of addition nano metal in situ prepares the continuous SiO with catalytic performance2The method of/nano metal airsetting glue fiber - Google Patents
A kind of addition nano metal in situ prepares the continuous SiO with catalytic performance2The method of/nano metal airsetting glue fiber Download PDFInfo
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- CN105603577B CN105603577B CN201511027703.4A CN201511027703A CN105603577B CN 105603577 B CN105603577 B CN 105603577B CN 201511027703 A CN201511027703 A CN 201511027703A CN 105603577 B CN105603577 B CN 105603577B
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- sio
- airsetting glue
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- 239000000835 fiber Substances 0.000 title claims abstract description 138
- 239000003292 glue Substances 0.000 title claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 13
- 238000009987 spinning Methods 0.000 claims abstract description 32
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 31
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000001112 coagulating effect Effects 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000004804 winding Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003863 metallic catalyst Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000002166 wet spinning Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 238000006073 displacement reaction Methods 0.000 claims abstract description 4
- 239000002105 nanoparticle Substances 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 41
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 15
- 239000004115 Sodium Silicate Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 8
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 8
- 238000000352 supercritical drying Methods 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000011943 nanocatalyst Substances 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000003486 chemical etching Methods 0.000 abstract description 4
- 239000012467 final product Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 116
- 229910052681 coesite Inorganic materials 0.000 description 63
- 229910052906 cristobalite Inorganic materials 0.000 description 63
- 239000000377 silicon dioxide Substances 0.000 description 63
- 229910052682 stishovite Inorganic materials 0.000 description 63
- 229910052905 tridymite Inorganic materials 0.000 description 63
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 51
- 239000000047 product Substances 0.000 description 29
- 239000003054 catalyst Substances 0.000 description 21
- 239000007789 gas Substances 0.000 description 20
- 239000011148 porous material Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000010926 purge Methods 0.000 description 18
- 235000012239 silicon dioxide Nutrition 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000004587 chromatography analysis Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000010453 quartz Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000007790 solid phase Substances 0.000 description 4
- 239000004964 aerogel Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of addition nano metal in situ to prepare the continuous SiO with catalytic performance2The method of/nano metal airsetting glue fiber.Method includes：By silicate or it is configured to spinning solution, then metallic catalyst is added, then add in coagulating bath, carry out reaction wet spinning, obtain orthosilicic acid/silicate fiber containing metallic catalyst, winding, room temperature is aged, and is washed with deionized to neutrality, solvent displacement is carried out with deionized water or ethanol, it is dry, to obtain the final product.The method of the present invention has the characteristics that raw material is cheap and easily-available, reaction process is simple, good spinnability.Continuous SiO with catalytic performance prepared by the present invention2/ nano metal airsetting glue fiber has abundant hole, high specific surface area, high temperature resistant, resistant to chemical etching, while nano metal content is adjustable in pulp freeness, fiber, has application prospect in fields such as catalysis.
Description
Technical field
The invention belongs to the preparation field of aeroge, prepared by more particularly to a kind of addition nano metal in situ have catalytic
The continuous SiO of energy2The method of/nano metal airsetting glue fiber.
Background technology
It is flat without changing chemistry that reactant chemical reaction rate (can improve can also reduce) can be changed in chemical reaction
Weighing apparatus, and the material that the quality of itself and chemical property all do not change before and after chemical reaction is catalyst.In actual life
In production, catalyst is often costly.To reduce the dosage of catalyst as far as possible, the efficiency of catalyst is improved, is generally required
Expand it than surface, be made into nano particle.In order to support active component, make catalyst that there is specific physical behavior, it is past
Past that catalyst is supported on to the porous material with open hole that can realize material in internal transmission, aeroge is exactly to have
There is the Typical Representative of the porous material of open hole.
The medium that aeroge (aerogel) refers to be full of in the spacial framework in gel is not solvent but gas,
Appearance is in the special gel of solid-like, because almost without solvent composition inside it, therefore also referred to as xerogel.Aeroge is
A kind of nano-meter porous amorphous state solid material of low-density, has unique structure, its solid phase forms spacial framework, net
Network structure and internetwork pore structure are all Nano grade.Because of the uniqueness of its structure, aeroge is set equally to have many only
Characteristic energy, such as high porosity, high-ratio surface, strong adsorptivity, low-density, low acoustic impedance, low heat conductivity, low refraction.
SiO2Its high-specific surface area of aeroge can provide substantial amounts of reaction/interaction activated centre, be particularly conducive to
With the relevant process of interface interaction, such as absorption, catalysis and electrochemical action；Its duct can be used as Multifunctional memory and single point
Scattered nano-reactor；The space and field that its special nano pore and shape bring and its enrich for the research of cross discipline
Institute, such as the dispersal behavior of biomolecule, drug molecule, reactant molecule in nano pore, the contact with activated centre
Energy, reactivity etc. all have close relationship with pore structure；And skin effect caused by the network structure of its nanoscale and
Quantum size effect, the SiO for making some pass through functional modification2Aerogel material is in sensor, lithium battery and nano-device
Show excellent performance；Before its lower thermal conductivity makes it have huge applications in fields such as insulated wall, heat-insulation window, tent thermal insulation layers
Scape.Exactly unique advantage of the aeroge in micro interface structure and material property, makes them become the heat in investigation of materials field
One of point.
The performance of aeroge also has important in addition to related with its microscopic appearance with composite porous macro morphology
Relation.For SiO2Aerogel material, nowadays has substantial amounts of document report zero dimension powder, two-dimensional film, three-dimensional block,
But to one-dimensional SiO2Airsetting glue fiber is but seldom reported.The porous material of this other dimension that are primarily due to compare, fiber
Shape porous material has more requirements to preparing raw material, preparation condition etc..However, fibrous porous material but have it is other
Excellent properties not available for dimension material.By taking the porous material of carried metal Pd carrys out catalytic methane conversion reaction as an example, methane
The catalytic efficiency that complexity determines material is contacted with catalyst Pd.With three-dimensional bulk material and the film material phase of two dimension
Than, fibrous material improves the area directly contacted with methane gas, while transmission range of the methane in material greatly shortens,
Easily contacted with catalyst Pd, improve catalyst action efficiency.Compared with the powder of zero dimension, powder is in no extraneous support
It can stack under material and external force effect, be greatly reduced with the contact area of methane, and the catalyst for being stacked on centre utilizes
Rate is very low.In addition, powdered be also not convenient to use, liquid catalyst field is especially embodied in.
At present on the continuous SiO with catalytic performance2The document of/nano metal airsetting glue fiber has not been reported.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of addition nano metal in situ and prepare with catalytic performance
Continuous SiO2The method of/nano metal airsetting glue fiber, this method is with raw material is cheap and easily-available, reaction process is simple, spinnability
The characteristics of good；Obtained inorganic SiO2Fiber has the abundant hole, specific surface area of superelevation, high temperature resistant, resistant to chemical etching,
Pulp freeness is adjustable at the same time.
A kind of addition nano metal in situ of the present invention prepares the continuous SiO with catalytic performance2/ nano metal aeroge
The method of fiber, including：
(1) by silicate or spinning solution is configured to, then adds metallic catalyst；
(2) acid solution is added in coagulating basin as coagulating bath；
(3) spinning solution after addition nanocatalyst in step (1) is added in the coagulating bath in step (2), carried out
Wet spinning is reacted, obtains orthosilicic acid/silicate fiber containing metallic catalyst；Spinning solution runs into coagulating bath acid hair
Raw quick strong acid weak acid reaction generation solid phase orthosilicic acid, realizes the quick liquid-solid phase transformation required by wet spinning, is formed
Collosol and gel occurs at the same time for orthosilicic acid/silicate fiber containing metallic catalyst, this process；
(4) orthosilicic acid containing metallic catalyst in step (3)/silicate fiber is wound, immerses aged solution
Middle room temperature is aged 2~10 days, is washed with deionized to neutrality, solvent displacement is carried out with deionized water or ethanol, dry, is obtained
Continuous SiO with catalytic performance2/ nano metal airsetting glue fiber；Ageing make the orthosilicic acid containing metallic catalyst/
Collosol and gel further occurs for silicate fiber, realizes from orthosilicic acid/silicate fiber to SiO2Fiber changes, and is formed at the same time
A large amount of holes.
Silicate is sodium silicate, potassium water glass or nine water sodium metasilicate in the step (1)；Silanol colloidal sol is positive silicic acid second
The hydrolytic sol of ester, methyltriethoxysilane, methyltrimethoxysilane or phenyltrimethoxysila,e under the conditions of diluted acid.
The specification of spinning solution in the step (1)：Sodium silicate, the modulus of potassium water glass are 2~3, Baume degrees 35
~50, nine water sodium metasilicate directly heat into solution without solubilizer again, and the viscosity of silanol colloidal sol is 0.01~0.1PaS, and silicon contains
Amount is more than 10wt%.
Metallic catalyst is Pt nano particle, nano Pd particle, nanometer Au, nanometer Ag or nanometer Cu in the step (1)；Nanometer
The addition of metallic catalyst only needs 0.5wt%~1.0wt% to have good catalytic effect.
In the step (2) acid solution be concentration be 0.2mol/L~0.8mol/L dilution heat of sulfuric acid, concentration 0.4
The dilute hydrochloric acid solution or concentration of mol/L~1.2mol/L is the acetic acid of 12mol/L~15mol/L.
The condition of reaction wet spinning is normal temperature and pressure in the step (3).
The speed of winding is 0.1~2m/s in the step (4).
Aged solution is preparation low concentration acid solution in the step (4)：Concentration is 0.005mol/L~0.1mol/L's
The dilute hydrochloric acid solution or concentration that dilution heat of sulfuric acid, concentration are 0.01mol/L~0.2mol/L are 0.005mol/L~0.1mol/L
Oxalic acid.
It is dry for freeze-drying or supercritical drying in the step (4).
The present invention is in SiO2The nanometer of different content is added in spinning solution used in aeroge fiber manufacturing process
Metallic catalyst, realizes the continuous SiO with catalytic performance2The preparation of/nano metal airsetting glue fiber.
Continuous SiO with catalytic performance prepared by the addition nano metal in situ of the present invention2/ nano metal aeroge is fine
The hole of dimension can adjust specific surface area size in nanoscale scope by varying preparation condition.
The present invention is utilized using the silicate and silanol colloidal sol of the metallic catalyst that adds different content as spinning solution
Strong acid weak acid and collosol and gel principle, continuous SiO is realized by reacting spinning2The preparation of/nano metal airsetting glue fiber,
The continuous SiO with catalytic performance is obtained finally by freeze-drying or supercritical drying2/ nano metal airsetting glue fiber, tool
There is novelty.The prepared continuous SiO with catalytic performance2/ nano metal airsetting glue fiber is in a series of fields such as catalysis
In have more prominent advantage, have very huge potential demand, there is practicality.
There is the continuous SiO of catalytic performance in the present invention2The preparation method of/nano metal airsetting glue fiber, being will be cheap
Silicate and silanol colloidal sol in mix different proportion metallic catalyst be used as spinning solution, with different acid solutions work
For coagulating bath, reacted by silicate and silanol colloidal sol with acid generation strong acid weak acid and collosol and gel occurs, part generates
The orthosilicic acid of solid phase, obtains orthosilicic acid/silicate fiber containing nano metal, is wound fiber by take-up roll.With
Afterwards, orthosilicic acid/silicate fiber containing nano metal of winding is immersed in low concentration acid solution and is aged, passed through
Ageing process makes fiber further carry out collosol and gel, realizes from orthosilicic acid/silicate fiber to SiO2Fiber changes, at the same time
Form a large amount of holes.After ageing, washed using deionized water, then carry out solvent displacement using ethanol, finally by
Freeze-drying or supercritical drying obtain the continuous SiO finally with catalytic performance2/ nano metal airsetting glue fiber.The present invention
Used method has the characteristics that raw material is cheap and easily-available, reaction process is simple, good spinnability.Obtained has catalytic performance
Continuous SiO2/ nano metal airsetting glue fiber has abundant hole, high specific surface area, high temperature resistant, resistant to chemical etching, together
When pulp freeness, nano metal content is adjustable in fiber, there is application prospect in fields such as catalysis.
Beneficial effect
(1) method used in the present invention has the characteristics that raw material is cheap and easily-available, reaction process is simple, good spinnability；
(2) the continuous SiO with catalytic performance of the invention2/ nano metal airsetting glue fiber has abundant hole, height
Specific surface area, high temperature resistant, resistant to chemical etching, while nano metal content is adjustable in pulp freeness, fiber, in catalysis etc.
Field has application prospect.
Brief description of the drawings
Fig. 1 is to use SiO in embodiment 12Methane converts during the catalyst of/Pt nano particle airsetting glue fiber as methane reaction
For the column diagram of the long product of different carbon chain.
Embodiment
With reference to specific embodiment, the present invention is further explained.It is to be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people 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
Scope.
Embodiment 1
Using modulus as 2, the sodium silicate of the 50 Baume degrees and catalyst nano Pt for being mixed into 0.5wt% is spinning solution, with
The dilution heat of sulfuric acid of 0.8 mol/L is coagulating bath, carries out reaction wet spinning.The original containing Pt nano particle that will be formed in coagulating bath
Silicic acid/silicate fiber is wound with the winding speed of 0.1m/s.Fiber after winding immerses the dilute sulfuric acid of 0.005mol/L
It is aged within 10 days, is realized from orthosilicic acid/silicate fiber to SiO2Fiber changes, while forms a large amount of holes.After ageing,
Fiber is washed with deionized, until neutral.The solvent in fiber is replaced using deionized water, it is freeze-dried, to obtain the final product
SiO2/ Pt nano particle airsetting glue fiber.It is very smooth in spinning process, not fracture of wire.Obtained SiO2/ Pt nano particle airsetting glue fiber ratio
Surface area is 543.5m2/ g, most probable pore size 16nm.By SiO2/ Pt nano particle airsetting glue fiber is placed in quartz reactor, is made
Use H2To SiO2/ Pt nano particle airsetting glue fiber is pre-processed, and then uses N2Purging.At 150 DEG C, methane is with 100ml/min
Flow enter reactor, after 10min, close methane gas circuit, open N2Gas circuit, purges 1min, then is passed through hydrogen, and uses liquid
The U-tube of nitrogen cold-trap collects all Cn(n >=2) product.Chromatography is carried out to product, wherein C2 yield is 42.7%, never
Understood with carbon chain length efficiency of pcr product, SiO2/ Pt nano particle airsetting glue fiber has catalytic effect.Fig. 1 is the methane under this system
It is converted into the situation of the long product of different carbon chain.
Embodiment 2
Using modulus as 3, the potassium water glass of the 35 Baume degrees and catalyst nano Pt for being mixed into 1wt% is spinning solution, with 0.2
The dilution heat of sulfuric acid of mol/L is coagulating bath, carries out reaction wet spinning.The former silicon containing Pt nano particle that will be formed in coagulating bath
Acid/silicate fiber is wound with the winding speed of 0.5m/s.Fiber after winding immerses the dilute sulfuric acid 10 of 0.005mol/L
It is aged, and is realized from orthosilicic acid/silicate fiber to SiO2Fiber changes, while forms a large amount of holes.After ageing, by fibre
Dimension is washed with deionized, until neutral.The solvent in fiber is replaced using deionized water, it is freeze-dried, up to SiO2/
Pt nano particle airsetting glue fiber.There is fracture of wire phenomenon in spinning process once in a while.Obtained SiO2/ Pt nano particle aeroge pulp freeness
For 452.3m2/ g, most probable pore size 17nm.By SiO2/ Pt nano particle airsetting glue fiber is placed in quartz reactor, uses H2It is right
SiO2/ Pt nano particle airsetting glue fiber is pre-processed, and then uses N2Purging.At 150 DEG C, methane is with the flow of 100 ml/min
Into reactor, after 10min, methane gas circuit is closed, opens N2Gas circuit, purges 1min, then is passed through hydrogen, and uses liquid nitrogen cold trap
U-tube collect all Cn(n >=2) product.Chromatography is carried out to product, wherein C2 yield is 64.3%, from different carbon chain
Knowable to long efficiency of pcr product, SiO2/ Pt nano particle airsetting glue fiber has catalytic effect.
Embodiment 3
Using modulus as 3, the potassium water glass of the 35 Baume degrees and catalyst nano Pd for being mixed into 0.5wt% is spinning solution, with
The dilution heat of sulfuric acid of 0.8 mol/L is coagulating bath, carries out reaction wet spinning.The original containing nano Pd particle that will be formed in coagulating bath
Silicic acid/silicate fiber is wound with the winding speed of 1m/s.Fiber after winding immerse the dilute sulfuric acid 5 days of 0.1mol/L into
Row ageing, is realized from orthosilicic acid/silicate fiber to SiO2Fiber changes, while forms a large amount of holes.After ageing, fiber is used
Deionized water is washed, until neutral.The solvent in fiber is replaced using deionized water, it is freeze-dried, up to SiO2/ nanometer
Pd airsetting glue fibers.There is fracture of wire phenomenon in spinning process once in a while.Obtained SiO2/ nano Pd particle aeroge pulp freeness is
423.8m2/ g, most probable pore size 14nm.By SiO2/ nano Pd particle airsetting glue fiber is placed in quartz reactor, uses H2It is right
SiO2/ nano Pd particle airsetting glue fiber is pre-processed, and then uses N2Purging.At 150 DEG C, methane is with the flow of 100 ml/min
Into reactor, after 10min, methane gas circuit is closed, opens N2Gas circuit, purges 1min, then is passed through hydrogen, and uses liquid nitrogen cold trap
U-tube collect all Cn(n >=2) product.Chromatography is carried out to product, wherein C2 yield is 48.5%, from different carbon chain
Knowable to long efficiency of pcr product, SiO2/ nano Pd particle airsetting glue fiber has catalytic effect.
Embodiment 4
Directly heat solution and to be mixed into the catalyst Pd of 1wt% as spinning solution using nine water sodium metasilicate, with 0.4mol/L
Dilute hydrochloric acid solution be coagulating bath, carry out reaction wet spinning.Orthosilicic acid/the silicic acid containing nano Pd particle that will be formed in coagulating bath
Salt fiber is wound with the winding speed of 2m/s.The dilute hydrochloric acid that fiber after winding immerses 0.01mol/L is aged for 10 days,
Realize from orthosilicic acid/sodium metasilicate fiber to SiO2Fiber changes, while forms a large amount of holes.After ageing, by fiber deionization
Water washing, until neutral.The solvent in fiber is replaced using deionized water, it is freeze-dried, up to SiO2The airsetting of/nano Pd particle
Glue fiber.Often fracture of wire phenomenon occurs in spinning process.Obtained SiO2/ nano Pd particle aeroge pulp freeness is
268.4m2/ g, most probable pore size 26nm.By SiO2/ nano Pd particle airsetting glue fiber is placed in quartz reactor, uses H2It is right
SiO2/ nano Pd particle airsetting glue fiber is pre-processed, and then uses N2Purging.At 150 DEG C, methane is with the flow of 100ml/min
Into reactor, after 10min, methane gas circuit is closed, opens N2Gas circuit, purges 1min, then is passed through hydrogen, and uses liquid nitrogen cold trap
U-tube collect all Cn(n >=2) product.Chromatography is carried out to product, wherein C2 yield is 53.1%, from different carbon chain
Knowable to long efficiency of pcr product, SiO2/ nano Pd particle airsetting glue fiber has catalytic effect.
Embodiment 5
Directly heat solution and to be mixed into the catalyst nano Pt of 0.5wt% as spinning solution using nine water sodium metasilicate, with 1.2
The dilute hydrochloric acid solution of mol/L is coagulating bath, carries out reaction wet spinning.The former silicon containing Pt nano particle that will be formed in coagulating bath
Acid/silicate fiber is wound with the winding speed of 1m/s.The dilute hydrochloric acid that fiber after winding immerses 0.2mol/L carries out for 2 days
Ageing, is realized from orthosilicic acid/sodium metasilicate fiber to SiO2Fiber changes, while forms a large amount of holes.After ageing, fiber is spent
Ion water washing, until neutral.The solvent in fiber is replaced using deionized water, it is freeze-dried, up to SiO2/ Pt nano particle
Airsetting glue fiber.Fracture of wire phenomenon occurs in spinning process once in a while.Obtained SiO2/ Pt nano particle aeroge pulp freeness is
262.6m2/ g, most probable pore size 27nm.By SiO2/ Pt nano particle airsetting glue fiber is placed in quartz reactor, uses H2It is right
SiO2/ Pt nano particle airsetting glue fiber is pre-processed, and then uses N2Purging.At 150 DEG C, methane is with the flow of 100 ml/min
Into reactor, after 10min, methane gas circuit is closed, opens N2Gas circuit, purges 1min, then is passed through hydrogen, and uses liquid nitrogen cold trap
U-tube collect all Cn(n >=2) product.Chromatography is carried out to product, wherein C2 yield is 36.3%, from different carbon chain
Knowable to long efficiency of pcr product, SiO2/ Pt nano particle airsetting glue fiber has catalytic effect.
Embodiment 6
The colloidal sol of viscosity 0.01PaS, silicon content 12wt% are hydrolyzed into ethyl orthosilicate plus dilute hydrochloric acid, and is mixed into
The catalyst nano Pt of 0.5wt% is spinning solution, using the acetum of 12mol/L as coagulating bath, carries out reaction wet spinning.
Orthosilicic acid/the silicate fiber containing Pt nano particle formed in coagulating bath is wound with the winding speed of 1m/s.After winding
Fiber immerse the oxalic acid of 0.005mol/L and be aged for 10 days, realize from orthosilicic acid fiber to SiO2Fiber changes, while shape
Into a large amount of holes.After ageing, fiber is washed with deionized, until neutral.The solvent in fiber is replaced using deionized water,
Through supercritical drying, up to SiO2/ Pt nano particle airsetting glue fiber.Fracture of wire phenomenon occurs in spinning process once in a while.Obtained SiO2/
Pt nano particle aeroge pulp freeness is 422.6m2/ g, most probable pore size 5nm.By SiO2/ Pt nano particle airsetting glue fiber is put
In quartz reactor, H is used2To SiO2/ Pt nano particle airsetting glue fiber is pre-processed, and then uses N2Purging.At 150 DEG C
Under, methane enters reactor with the flow of 100ml/min, after 10min, closes methane gas circuit, opens N2Gas circuit, purges 1min,
Hydrogen is passed through again, and collects all C using the U-tube of liquid nitrogen cold trapn(n >=2) product.Chromatography is carried out to product, wherein
C2 yield is 50.2%, it was found from different carbon chain length efficiency of pcr product, SiO2/ Pt nano particle airsetting glue fiber has catalytic effect.
Embodiment 7
The colloidal sol of viscosity 0.05PaS, silicon content 18wt% are hydrolyzed into as spinning using methyltriethoxysilane plus dilute hydrochloric acid
Silk stock solution, and the catalyst nano Pt for being mixed into 0.5wt% is spinning solution, using the acetum of 15mol/L as coagulating bath, is carried out
React wet spinning.By the orthosilicic acid/silicate fiber containing Pt nano particle formed in coagulating bath with the winding speed of 1m/s into
Row winding.The oxalic acid that fiber after winding immerses 0.1mol/L is aged for 5 days, is realized from orthosilicic acid fiber to SiO2Fiber turns
Become, while form a large amount of holes.After ageing, fiber is washed with deionized, until neutral.Fiber is replaced using absolute ethyl alcohol
In solvent, through supercritical drying, up to SiO2/ Pt nano particle airsetting glue fiber.Fracture of wire phenomenon does not occur in spinning process.It is made
SiO2/ Pt nano particle aeroge pulp freeness is 643.1m2/ g, most probable pore size 8nm.By SiO2The airsetting of/Pt nano particle
Glue fiber is placed in quartz reactor, uses H2To SiO2/ Pt nano particle airsetting glue fiber is pre-processed, and then uses N2Purging.
At 150 DEG C, methane enters reactor with the flow of 100ml/min, after 10min, closes methane gas circuit, opens N2Gas circuit, purging
1min, then hydrogen is passed through, and collect all C using the U-tube of liquid nitrogen cold trapn(n >=2) product.Chromatography point is carried out to product
Analysis, wherein C2 yield are 58.4%, it was found from different carbon chain length efficiency of pcr product, SiO2/ Pt nano particle airsetting glue fiber has catalysis
Effect.
Embodiment 8
The colloidal sol of viscosity 0.1PaS, silicon content 22wt% are hydrolyzed into methyltrimethoxysilane plus dilute hydrochloric acid, and is mixed
The catalyst nano Pt for entering 0.5wt% is spinning solution, using the acetum of 15mol/L as coagulating bath, carries out reaction Wet-spinning
Silk.Orthosilicic acid/the silicate fiber containing Pt nano particle formed in coagulating bath is wound into the winding speed of 1m/s.Volume
The oxalic acid that fiber after immerses 0.1mol/L is aged for 5 days, is realized from orthosilicic acid fiber to SiO2Fiber changes, while shape
Into a large amount of holes.After ageing, fiber is washed with deionized, until neutral.The solvent in fiber is replaced using absolute ethyl alcohol,
Through supercritical drying, up to SiO2/ Pt nano particle airsetting glue fiber.Fracture of wire phenomenon does not occur in spinning process.Obtained SiO2/ receive
Rice Pt aeroges pulp freeness is 662.9m2/ g, most probable pore size 5nm.By SiO2/ Pt nano particle airsetting glue fiber is placed in
In quartz reactor, H is used2To SiO2/ Pt nano particle airsetting glue fiber is pre-processed, and then uses N2Purging.At 150 DEG C,
Methane enters reactor with the flow of 100ml/min, after 10min, closes methane gas circuit, opens N2Gas circuit, purges 1min, then leads to
Enter hydrogen, and all C are collected using the U-tube of liquid nitrogen cold trapn(n >=2) product.Chromatography is carried out to product, wherein C2 is obtained
Rate is 55.1%, it was found from different carbon chain length efficiency of pcr product, SiO2/ Pt nano particle airsetting glue fiber has catalytic effect.
Embodiment 9
The colloidal sol of viscosity 0.08PaS, silicon content 20wt% are hydrolyzed into phenyltrimethoxysila,e plus dilute hydrochloric acid, and is mixed
The catalyst nano Pt for entering 0.5wt% is spinning solution, using the glacial acetic acid solution of 15mol/L as coagulating bath, carries out reaction wet method
Spinning.Orthosilicic acid/the silicate fiber containing Pt nano particle formed in coagulating bath is wound with the winding speed of 1m/s.Volume
The oxalic acid that fiber after immerses 0.1mol/L is aged for 5 days, is realized from orthosilicic acid fiber to SiO2Fiber changes, while shape
Into a large amount of holes.After ageing, fiber is washed with deionized, until neutral.The solvent in fiber is replaced using absolute ethyl alcohol,
Through supercritical drying, up to SiO2/ Pt nano particle airsetting glue fiber.Fracture of wire phenomenon does not occur in spinning process.Obtained SiO2/ receive
Rice Pt aeroges pulp freeness is 546.9m2/ g, most probable pore size 7nm.By SiO2/ Pt nano particle airsetting glue fiber is placed in
In quartz reactor, H is used2To SiO2/ Pt nano particle airsetting glue fiber is pre-processed, and then uses N2Purging.At 150 DEG C,
Methane enters reactor with the flow of 100ml/min, after 10min, closes methane gas circuit, opens N2Gas circuit, purges 1min, then leads to
Enter hydrogen, and all C are collected using the U-tube of liquid nitrogen cold trapn(n >=2) product.Chromatography is carried out to product, wherein C2 is obtained
Rate is 53.6%, it was found from different carbon chain length efficiency of pcr product, SiO2/ Pt nano particle airsetting glue fiber has catalytic effect.
Claims (6)
1. a kind of addition nano metal in situ prepares the continuous SiO with catalytic performance2The method of/nano metal airsetting glue fiber,
Including：
(1) silicate or silanol colloidal sol are configured to spinning solution, then add metallic catalyst；Wherein, silicate is
Sodium silicate, potassium water glass or nine water sodium metasilicate；Silanol colloidal sol is ethyl orthosilicate, methyltriethoxysilane, methyl trimethoxy
The hydrolytic sol of oxysilane or phenyltrimethoxysila,e under the conditions of diluted acid；
(2) acid solution is added in coagulating basin as coagulating bath；Wherein, acid solution be concentration be 0.2mol/L~
The dilute hydrochloric acid solution or concentration that the dilution heat of sulfuric acid of 0.8mol/L, concentration are 0.4mol/L~1.2mol/L be 12mol/L~
The acetic acid of 15mol/L；
(3) spinning solution after addition nanocatalyst in step (1) is added in the coagulating bath in step (2), is reacted
Wet spinning, obtains orthosilicic acid/silicate fiber containing metallic catalyst；
(4) orthosilicic acid containing metallic catalyst in step (3)/silicate fiber is wound, immersed in aged solution often
Temperature ageing 2~10 days, is washed with deionized to neutrality, solvent displacement is carried out with deionized water or ethanol, dry, is had
The continuous SiO of catalytic performance2/ nano metal airsetting glue fiber；Wherein, the speed of winding is 0.1~2m/s.
2. a kind of addition nano metal in situ according to claim 1 prepares the continuous SiO with catalytic performance2/ nanogold
Belong to the method for airsetting glue fiber, it is characterised in that the specification of spinning solution in the step (1)：Sodium silicate, potassium water glass
Modulus is 2~3, and Baume degrees is 35~50, and nine water sodium metasilicate directly heat into solution without solubilizer again, the viscosity of silanol colloidal sol
For 0.01~0.1PaS, silicone content is more than 10wt%.
3. a kind of addition nano metal in situ according to claim 1 prepares the continuous SiO with catalytic performance2/ nanogold
Belong to the method for airsetting glue fiber, it is characterised in that metallic catalyst is Pt nano particle, nano Pd particle, nanometer in the step (1)
Au, nanometer Ag or nanometer Cu；The addition of metallic catalyst only needs 0.5wt%~1.0wt% to have catalysis effect well
Fruit.
4. a kind of addition nano metal in situ according to claim 1 prepares the continuous SiO with catalytic performance2/ nanogold
Belong to the method for airsetting glue fiber, it is characterised in that the condition of reaction wet spinning is normal temperature and pressure in the step (3).
5. a kind of addition nano metal in situ according to claim 1 prepares the continuous SiO with catalytic performance2/ nanogold
Belong to airsetting glue fiber method, it is characterised in that in the step (4) aged solution be concentration be 0.005mol/L~
The dilute hydrochloric acid solution or concentration that the dilution heat of sulfuric acid of 0.1mol/L, concentration are 0.01mol/L~0.2mol/L are 0.005mol/L
The oxalic acid of~0.1mol/L.
6. a kind of addition nano metal in situ according to claim 1 prepares the continuous SiO with catalytic performance2/ nanogold
Belong to the method for airsetting glue fiber, it is characterised in that dry for freeze-drying or supercritical drying in the step (4).
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