CN105597720B - A kind of continuous SiO with photocatalysis performance2/TiO2The preparation method of airsetting glue fiber - Google Patents
A kind of continuous SiO with photocatalysis performance2/TiO2The preparation method of airsetting glue fiber Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 125
- 239000003292 glue Substances 0.000 title claims abstract description 43
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000009987 spinning Methods 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 27
- 230000001112 coagulating effect Effects 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000032683 aging Effects 0.000 claims abstract description 16
- 238000002166 wet spinning Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 235000019441 ethanol Nutrition 0.000 claims abstract description 4
- 238000006073 displacement reaction Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 61
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 23
- 238000004804 winding Methods 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 239000004115 Sodium Silicate Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 7
- 238000000352 supercritical drying Methods 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
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 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
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000003486 chemical etching Methods 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 60
- 229910052681 coesite Inorganic materials 0.000 description 38
- 229910052906 cristobalite Inorganic materials 0.000 description 38
- 239000000377 silicon dioxide Substances 0.000 description 38
- 229910052682 stishovite Inorganic materials 0.000 description 38
- 229910052905 tridymite Inorganic materials 0.000 description 38
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 22
- 229960000907 methylthioninium chloride Drugs 0.000 description 22
- 239000011148 porous material Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000002912 waste gas Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 239000004964 aerogel Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006731 degradation reaction 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
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000007654 immersion Methods 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 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
- 238000005406 washing Methods 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B01J35/39—
-
- B01J35/58—
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/647—
Abstract
The present invention relates to a kind of continuous SiO with photocatalysis performance2/TiO2The preparation method of airsetting glue fiber.Preparation method includes：Silicate or silanol colloidal sol are configured to spinning solution, TiO is added2Photochemical catalyst；TiO will be added2The spinning solution of catalyst is added in acid solution coagulating bath, carries out reaction wet spinning, must contain TiO2Orthosilicic acid/silicate fiber of photochemical catalyst is wound, and ageing is washed with deionized to neutrality, and solvent displacement is carried out with deionized water or ethyl alcohol, dry to get.The method of the present invention has the characteristics that raw material is cheap and easily-available, reaction process is simple, good spinnability；The airsetting glue fiber being prepared has abundant hole, high specific surface area, high temperature resistant, resistant to chemical etching, while TiO in pulp freeness, fiber2Content is adjustable, has application prospect in fields such as photocatalysis.
Description
Technical field
It is the invention belongs to airsetting glue fiber and its preparation field, more particularly to a kind of continuous with photocatalysis performance
SiO2/TiO2The preparation method of airsetting glue fiber.
Background technology
Aeroge (aerogel) refers to that the medium being 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
There is a kind of nano-meter porous amorphous state solid material of low-density unique structure, solid phase to form spacial framework, net
Network structure and internetwork pore structure are all Nano grade.Because of the uniqueness of its structure, making aeroge equally has much solely
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 a large amount 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；Its special nano pore and shape are that the research of cross discipline is brought and its abundant space and field
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 makes some pass through the SiO of 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 other than related with its microscopic appearance with composite porous macro morphology
Relationship.For SiO2Aerogel material nowadays has a large amount 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 in photocatalytic degradation for for pollutant treatment field, waste water and gas with
Photochemical catalyst contact complexity determines the catalytic efficiency of the photochemical catalyst of load on the porous material.With three-dimensional block-shaped material
Material and two-dimensional film material are compared, and one dimension fibre material improves the area being in direct contact with waste water and gas, and waste water and gas exists
Transmission range in material greatly shortens, it is easier to be contacted with photochemical catalyst, improve the efficiency of pollutant treatment.While by
It is far smaller than the resistance passed through in block or film in the resistance that waste water and gas passes through between fiber and fiber, reduces waste water and gas warp
Pressure drop after porous material.Compared with the powder of zero dimension, powder is difficult to be kept completely separate with gas or liquid, while powder is not having
Having can stack under outer force effect, be greatly reduced with the contact area of waste water and gas, and be stacked on intermediate photochemical catalyst profit
It is very low with rate.
At present about the continuous SiO with photocatalysis performance2/TiO2The document of airsetting glue fiber has not been reported.
Invention content
Technical problem to be solved by the invention is to provide a kind of continuous SiO with photocatalysis performance2/TiO2Aeroge
The preparation method of fiber.This method has the characteristics that raw material is cheap and easily-available, reaction process is simple, good spinnability；Obtained nothing
Machine SiO2Fiber has the abundant hole, specific surface area of superelevation, high temperature resistant, resistant to chemical etching, while pulp freeness can
It adjusts.
The continuous SiO with photocatalysis performance of the present invention2/TiO2The hole of airsetting glue fiber in nanoscale range, and
Specific surface area size can be adjusted by changing preparation condition.
A kind of SiO with photocatalysis performance of the present invention2/TiO2The preparation method of airsetting glue fiber, including：
(1) silicate or silanol colloidal sol are configured to spinning solution；
(2) TiO will be added in the spinning solution in step (1)2Photochemical catalyst；
(3) acid solution is added in coagulating basin as coagulating bath；
(4) TiO will be added in step (2)2The spinning solution of catalyst is added in coagulating bath, carries out reaction Wet-spinning
Silk, obtains containing TiO2Orthosilicic acid/silicate fiber of photochemical catalyst；Spinning solution encounters coagulating bath acid and quick strong acid occurs
Weak acid reaction processed generates solid phase orthosilicic acid, realizes that the quick liquid-solid phase transformation required by wet spinning, formation contain TiO2Light is urged
Simultaneously collosol and gel occurs for orthosilicic acid/silicate fiber of agent, this process；
(5) TiO will be contained in step (4)2The orthosilicic acid of photochemical catalyst/silicate fiber winding, it is molten to be then immersed in ageing
Liquid room temperature is aged 2-10 days, is washed with deionized to neutrality, solvent displacement is carried out with deionized water or ethyl alcohol, dry, is obtained
SiO with photocatalysis performance2/TiO2Airsetting glue fiber；Ageing makes containing TiO2Orthosilicic acid/silicate fiber of photochemical catalyst
Further occur collosol and gel, realizes from orthosilicic acid/silicate fiber to SiO2Fiber changes, and is formed simultaneously a large amount of holes.
Step (1) silicate is sodium silicate, potassium water glass or nine water sodium metasilicate；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, potassium water glass modulus be 2~3, Baume degrees 35
~50, nine water sodium metasilicate directly heat into solution and no longer need to solubilizer, and the viscosity of silanol colloidal sol is 0.01~0.1PaS, and silicon contains
Amount is more than 10 wt%.
TiO in the step (2)2Photochemical catalyst is P25 or N-TiO2；TiO2The addition of photochemical catalyst only needs 0.5wt%
~1.0wt% has good photocatalysis performance.
Acid solution is the dilution heat of sulfuric acid of a concentration of 0.2mol/L~0.8mol/L, a concentration of 0.4 in the step (3)
The acetic acid of the dilute hydrochloric acid solution of mol/L~1.2mol/L or a concentration of 12mol/L~15mol/L.
The condition of reaction wet spinning is normal temperature and pressure in the step (4).
The speed wound in the step (5) is 0.1~2m/s.
Aged solution is to prepare low concentration acid solution in the step (5)：A concentration of 0.005mol/L~0.1mol/L's
Dilution heat of sulfuric acid, the dilute hydrochloric acid solution of a concentration of 0.01mol/L~0.2mol/L or a concentration of 0.005mol/L~0.1mol/L
Oxalic acid.
The drying is freeze-drying or supercritical drying.
The present invention is in SiO2The TiO of different content is added in spinning solution used in aeroge fiber manufacturing process2Light
Catalyst realizes the continuous SiO with photocatalysis performance2/TiO2The preparation of airsetting glue fiber.
The present invention is to add the TiO of different content2The silicate and silanol colloidal sol of photochemical catalyst are spinning solution, using strong
Acid weak acid and collosol and gel principle realize continuous SiO by reacting spinning2/TiO2The preparation of airsetting glue fiber, finally leads to
It crosses freeze-drying or supercritical drying obtains the continuous SiO with photocatalysis performance2/TiO2Airsetting glue fiber has novelty.
The prepared continuous SiO with photocatalysis performance2/TiO2Airsetting glue fiber has more prominent in a series of fields such as photocatalysis
The advantage gone out has very huge potential demand, has practicability.
It is by the TiO of mixing different proportion in cheap silicate and silanol colloidal sol in the present invention2Photochemical catalyst is as spinning
Silk stock solution is occurred strong acid weak acid with acid by silicate and silanol colloidal sol and is reacted simultaneously using different acid solutions as coagulating bath
Collosol and gel occurs, part generates the orthosilicic acid of solid phase, obtains containing TiO2Orthosilicic acid/silicate fiber, pass through winding
Roller winds fiber.Then, winding is contained into TiO2Orthosilicic acid/silicate fiber be immersed in low concentration acid solution
In be aged, so that fiber is further carried out collosol and gel by ageing process, realize from orthosilicic acid/silicate fiber to
SiO2Fiber changes, and is formed simultaneously a large amount of holes.It after ageing, is washed using deionized water, is then carried out using ethyl alcohol
Solvent is replaced, and the finally continuous SiO with photocatalysis performance is obtained finally by freeze-drying or supercritical drying2/TiO2Airsetting
Glue fiber.Method used in the present invention has the characteristics that raw material is cheap and easily-available, reaction process is simple, good spinnability.It is obtained
The continuous SiO with photocatalysis performance2/TiO2Airsetting glue fiber has abundant hole, high specific surface area, high temperature resistant, resistance to
Chemical attack, while TiO in pulp freeness, fiber2Content is adjustable, has application prospect in fields such as photocatalysis.
Advantageous 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 photocatalysis performance of the invention2/TiO2Airsetting glue fiber has abundant hole, high
It is specific surface area, high temperature resistant, resistant to chemical etching, while TiO in pulp freeness, fiber2Content is adjustable, in fields such as photocatalysis
With application prospect.
Description of the drawings
Fig. 1 is in embodiment 1 through SiO2/TiO2After aeroge fiber photocatalytic degradation methylene blue different time, methylene
The outer characteristic peak high rate of royal purple manages time variation diagram everywhere；
Fig. 2 is in embodiment 1 through SiO2/TiO2After aeroge fiber photocatalytic degradation methylene blue different time, methylene
Blue solution colour is with processing time variation diagram.
Specific implementation mode
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, 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
Range.
Embodiment 1
With sodium silicate that modulus is 2,50 Baume degrees and be mixed into 0.5wt% photochemical catalyst P25 for spinning solution, with
The dilution heat of sulfuric acid of 0.8mol/L is coagulating bath, carries out reaction wet spinning.The former silicon containing P25 that will be formed in coagulating bath
Acid/silicate fiber is wound with the winding speed of 0.1m/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, and is formed simultaneously a large amount of holes.It, will be fine after ageing
Dimension is washed with deionized, until neutral.The solution in fiber is replaced using deionized water, it is freeze-dried to get SiO2/
TiO2Airsetting glue fiber.It is very smooth in spinning process, not fracture of wire.SiO obtained2/TiO2Aeroge pulp freeness is
532.4m2/ g, most probable pore size 15nm.By SiO2/TiO2Airsetting glue fiber immerses in the methylene blue solution of 7mg/L, in purple
Processing under outer light is, it can be achieved that methylene blue is degraded.Through SiO2/TiO2Aeroge fiber photocatalytic degradation methylene blue different time
Afterwards, it is as shown in Figure 1 to manage time variation diagram everywhere for the ultraviolet characteristic peak high rate of methylene blue；Through SiO2/TiO2Aeroge fiber photocatalysis
After degradation of methylene blue different time, methylene blue solution color is as shown in Figure 2 with processing time variation diagram.
Embodiment 2
With potassium water glass that modulus is 3,35 Baume degrees and be mixed into 1wt% photochemical catalyst P25 for spinning solution, with
The dilution heat of sulfuric acid of 0.2mol/L is coagulating bath, carries out reaction wet spinning.The former silicon containing P25 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, and is formed simultaneously a large amount of holes.It, will be fine after ageing
Dimension is washed with deionized, until neutral.The solution in fiber is replaced using deionized water, it is freeze-dried to get SiO2/
TiO2Airsetting glue fiber.There is fracture of wire phenomenon in spinning process once in a while.SiO obtained2/TiO2Aeroge pulp freeness is
409.6m2/ g, most probable pore size 18nm.By SiO2/TiO2Airsetting glue fiber immerses in the methylene blue solution of 7mg/L, in purple
Processing under outer light is, it can be achieved that methylene blue is degraded.
Embodiment 3
With potassium water glass that modulus is 3,35 Baume degrees and it is mixed into the photochemical catalyst N-TiO of 0.5wt%2For spinning solution,
Using the dilution heat of sulfuric acid of 0.8 mol/L as coagulating bath, reaction wet spinning is carried out.Contain N-TiO by what is formed in coagulating bath2's
Orthosilicic acid/silicate fiber is wound with the winding speed of 1m/s.Fiber after winding immerses the dilute sulfuric acid 5 of 0.1mol/L
It is aged, and is realized from orthosilicic acid/silicate fiber to SiO2Fiber changes, and is formed simultaneously a large amount of holes.It, will be fine after ageing
Dimension is washed with deionized, until neutral.The solution in fiber is replaced using deionized water, it is freeze-dried to get SiO2/
TiO2Airsetting glue fiber.There is fracture of wire phenomenon in spinning process once in a while.SiO obtained2/TiO2Aeroge pulp freeness is
425.5m2/ g, most probable pore size 37nm.By SiO2/TiO2Airsetting glue fiber immerses in the methylene blue solution of 7mg/L, can
Light-exposed lower processing is, it can be achieved that methylene blue is degraded.
Embodiment 4
It directly heats solution and to be mixed into the photochemical catalyst N-TiO of 1wt% with nine water sodium metasilicate2For spinning solution, with
The dilute hydrochloric acid solution of 0.4mol/L is coagulating bath, carries out reaction wet spinning.Contain N-TiO by what is formed in coagulating bath2Original
Silicic acid/silicate fiber is wound with the winding speed of 2m/s.The dilute hydrochloric acid of fiber immersion 0.01mol/L after winding 10 days
It is aged, is realized from orthosilicic acid/sodium metasilicate fiber to SiO2Fiber changes, and is formed simultaneously a large amount of holes.After ageing, by fiber
It is washed with deionized, until neutral.The solution in fiber is replaced using deionized water, it is freeze-dried to get SiO2/TiO2
Airsetting glue fiber.Often fracture of wire phenomenon occurs in spinning process.SiO obtained2/TiO2Aeroge pulp freeness is
250.7m2/ g, most probable pore size 33nm.By SiO2/TiO2Airsetting glue fiber immerses in the methylene blue solution of 7mg/L, can
Light-exposed lower processing is, it can be achieved that methylene blue is degraded.
Embodiment 5
It directly heats solution and to be mixed into the photochemical catalyst P25 of 0.5wt% as spinning solution using nine water sodium metasilicate, with
The dilute hydrochloric acid solution of 1.2mol/L is coagulating bath, carries out reaction wet spinning.The former silicon containing P25 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, and is formed simultaneously a large amount of holes.After ageing, fiber is spent
Ion water washing, until neutral.The solution in fiber is replaced using deionized water, it is freeze-dried to get SiO2/TiO2Airsetting
Glue fiber.Fracture of wire phenomenon occurs in spinning process once in a while.SiO obtained2/TiO2Aeroge pulp freeness is 232.3m2/
G, most probable pore size 38nm.By SiO2/TiO2Airsetting glue fiber immerses in the methylene blue solution of 7mg/L, locates under ultraviolet light
Reason is, it can be achieved that methylene blue is degraded.
Embodiment 6
With ethyl orthosilicate plus dilute hydrochloric acid be hydrolyzed into viscosity 0.01PaS, silicon content 12wt% colloidal sol and be mixed into
The photochemical catalyst P25 of 0.5wt% is that spinning solution carries out reaction wet spinning using the acetum of 12mol/L as coagulating bath.
Orthosilicic acid/the silicate fiber containing P25 formed in coagulating bath is wound with the winding speed of 1m/s.Fibre after winding
The oxalic acid that dimension immerses 0.005 mol/L is aged for 10 days, is realized from orthosilicic acid fiber to SiO2Fiber changes, and is formed simultaneously big
Metering-orifice hole.After ageing, fiber is washed with deionized, until neutral.The solution in fiber is replaced using deionized water, through super
Critical drying is to get SiO2/TiO2Airsetting glue fiber.Fracture of wire phenomenon occurs in spinning process once in a while.SiO obtained2/TiO2Gas
Gelatinous fibre specific surface area is 436.6m2/ g, most probable pore size 12nm.By SiO2/TiO2Airsetting glue fiber immerses 7mg/L's
In methylene blue solution, processing is, it can be achieved that methylene blue is degraded under ultraviolet light.
Embodiment 7
With methyltriethoxysilane plus dilute hydrochloric acid be hydrolyzed into viscosity 0.05PaS, silicon content 18wt% colloidal sol and mix
The photochemical catalyst P25 for entering 0.5 wt% is that spinning solution carries out reaction Wet-spinning using the acetum of 15mol/L as coagulating bath
Silk.Orthosilicic acid/the silicate fiber containing P25 formed in coagulating bath is wound with the winding speed of 1m/s.After winding
Fiber immerse the oxalic acid of 0.1mol/L and be aged for 5 days, realize from orthosilicic acid fiber to SiO2Fiber changes, and is formed simultaneously big
Metering-orifice hole.After ageing, fiber is washed with deionized, until neutral.The solution in fiber is replaced using absolute ethyl alcohol, through super
Critical drying is to get SiO2/TiO2Airsetting glue fiber.Fracture of wire phenomenon does not occur in spinning process.SiO obtained2/TiO2Airsetting
Glue fiber specific surface area is 628.2m2/ g, most probable pore size 14nm.By SiO2/TiO2Airsetting glue fiber immerses the Asia of 7mg/L
In methyl blue solution, processing is, it can be achieved that methylene blue is degraded under ultraviolet light.
Embodiment 8
With methyltrimethoxysilane plus dilute hydrochloric acid be hydrolyzed into viscosity 0.1PaS, silicon content 22wt% colloidal sol and be mixed into
The photochemical catalyst P25 of 0.5wt% is that spinning solution carries out reaction wet spinning using the acetum of 15mol/L as coagulating bath.
Orthosilicic acid/the silicate fiber containing P25 formed in coagulating bath is wound with the winding speed of 1m/s.Fibre after winding
The oxalic acid that dimension immerses 0.1mol/L is aged for 5 days, is realized from orthosilicic acid fiber to SiO2Fiber changes, and is formed simultaneously a large amount of
Hole.After ageing, fiber is washed with deionized, until neutral.The solution in fiber is replaced using absolute ethyl alcohol, is faced through super
It dries to get SiO on boundary2/TiO2Airsetting glue fiber.Fracture of wire phenomenon does not occur in spinning process.SiO obtained2/TiO2Aeroge
Pulp freeness is 648.4m2/ g, most probable pore size 10nm.By SiO2/TiO2Airsetting glue fiber immerses the methylene of 7mg/L
In base indigo plant solution, processing is, it can be achieved that methylene blue is degraded under ultraviolet light.
Embodiment 9
With phenyltrimethoxysila,e plus dilute hydrochloric acid be hydrolyzed into viscosity 0.08PaS, silicon content 20wt% colloidal sol and mix
The photochemical catalyst P25 for entering 0.5 wt% is that spinning solution carries out reaction wet method using the glacial acetic acid solution of 15mol/L as coagulating bath
Spinning.Orthosilicic acid/the silicate fiber containing P25 formed in coagulating bath is wound with the winding speed of 1m/s.Winding
The oxalic acid that rear fiber immerses 0.1mol/L is aged for 5 days, is realized from orthosilicic acid fiber to SiO2Fiber changes, and is formed simultaneously
A large amount of holes.After ageing, fiber is washed with deionized, until neutral.The solution in fiber, warp are replaced using absolute ethyl alcohol
Supercritical drying is to get SiO2/TiO2Airsetting glue fiber.Fracture of wire phenomenon does not occur in spinning process.SiO obtained2/TiO2Gas
Gelatinous fibre specific surface area is 579.8m2/ g, most probable pore size 8nm.By SiO2/TiO2Airsetting glue fiber immerses the Asia of 7mg/L
In methyl blue solution, processing is, it can be achieved that methylene blue is degraded under ultraviolet light.
Claims (5)
1. a kind of SiO with photocatalysis performance2/TiO2The preparation method of airsetting glue fiber, is as follows：
(1) silicate or silanol colloidal sol are configured to spinning solution；Wherein, silicate is sodium silicate, potassium water glass or nine water
Sodium metasilicate；Silanol colloidal sol is ethyl orthosilicate, methyltriethoxysilane, methyltrimethoxysilane or phenyl trimethoxy silicon
Hydrolytic sol of alkane under the conditions of diluted acid；
(2) TiO will be added in the spinning solution in step (1)2Photochemical catalyst；
(3) acid solution is added in coagulating basin as coagulating bath；Wherein, acid solution be a concentration of 0.2mol/L~
The dilution heat of sulfuric acid of 0.8mol/L, the dilute hydrochloric acid solution of a concentration of 0.4mol/L~1.2mol/L or a concentration of 12mol/L~
The acetic acid of 15mol/L；
(4) TiO will be added in step (2)2The spinning solution of catalyst is added in coagulating bath, is carried out reaction wet spinning, is obtained
Contain TiO2Orthosilicic acid/silicate fiber of photochemical catalyst；
(5) TiO will be contained in step (4)2The orthosilicic acid of photochemical catalyst/silicate fiber winding, is then immersed in aged solution room temperature
Ageing 2-10 days, is washed with deionized to neutrality, solvent displacement is carried out with deionized water or ethyl alcohol, dry, obtains with light
The SiO of catalytic performance2/TiO2Airsetting glue fiber；Wherein, the speed of winding is 0.1~2m/s；Aged solution is a concentration of
The dilution heat of sulfuric acid of 0.005mol/L~0.1mol/L, the dilute hydrochloric acid solution of a concentration of 0.01mol/L~0.2mol/L or concentration
For the oxalic acid of 0.005mol/L~0.1mol/L.
2. a kind of continuous SiO with photocatalysis performance according to claim 12/TiO2The preparation side of airsetting glue fiber
Method, which is characterized in that the specification of spinning solution in the step (1)：Sodium silicate, potassium water glass modulus be 2~3, Baume
Degree is 35~50, and nine water sodium metasilicate directly heat into solution and no longer need to solubilizer, and the viscosity of silanol colloidal sol is 0.01~0.1Pa
S, silicone content are more than 10wt%.
3. a kind of continuous SiO with photocatalysis performance according to claim 12/TiO2The preparation side of airsetting glue fiber
Method, which is characterized in that TiO in the step (2)2Photochemical catalyst is P25 or N-TiO2；TiO2The addition of photochemical catalyst only needs
0.5wt%~1.0wt% has good photocatalysis performance.
4. a kind of continuous SiO with photocatalysis performance according to claim 12/TiO2The preparation side of airsetting glue fiber
Method, which is characterized in that the condition of reaction wet spinning is normal temperature and pressure in the step (4).
5. a kind of continuous SiO with photocatalysis performance according to claim 12/TiO2The preparation side of airsetting glue fiber
Method, which is characterized in that the drying is freeze-drying or supercritical drying.
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| CN106012071B (en) * | 2016-06-24 | 2019-01-22 | 东华大学 | Continuous cellulose/TiO with photocatalysis performance2The preparation method of airsetting glue fiber |
| CN106994339B (en) * | 2017-05-25 | 2019-08-20 | 绍兴文理学院 | A kind of preparation method of silicon doped titanium dioxide photocatalyst |
| CN110170319A (en) * | 2019-05-21 | 2019-08-27 | 华东理工大学 | Bigger serface SiO2The preparation of the tungsten oxide of substrate/titanium catalysis material |
| CN111545136B (en) * | 2020-04-05 | 2021-02-19 | 北京化工大学 | Preparation method and application of self-suspended polymer aerogel with efficient photothermal conversion |
| KR102233580B1 (en) * | 2020-12-11 | 2021-03-30 | 주식회사 태성콘텍 | (Photocatalyst Coating Agent, Manufacturing Method thereof and Concrete Block Coated thereby |
| CN112808227B (en) * | 2020-12-28 | 2023-09-19 | 苏州城市学院 | Hybrid aerogel adsorbent, preparation method thereof and application thereof in wastewater treatment |
| CN115417620B (en) * | 2022-08-24 | 2023-09-15 | 南通大学 | Continuous SiO 2 Aerogel composite fiber and preparation method and application thereof |
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