CN104532479B - A kind of photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film and preparation method thereof - Google Patents
A kind of photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film and preparation method thereof Download PDFInfo
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- CN104532479B CN104532479B CN201410717882.3A CN201410717882A CN104532479B CN 104532479 B CN104532479 B CN 104532479B CN 201410717882 A CN201410717882 A CN 201410717882A CN 104532479 B CN104532479 B CN 104532479B
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- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 239000000835 fiber Substances 0.000 title claims abstract description 47
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 29
- 239000011159 matrix material Substances 0.000 title claims abstract description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000012528 membrane Substances 0.000 claims abstract description 28
- 239000002121 nanofiber Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 12
- 238000001994 activation Methods 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229920000433 Lyocell Polymers 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000011425 bamboo Substances 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 230000004913 activation Effects 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000004043 dyeing Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- 241001330002 Bambuseae Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- -1 dimethyl methyl Chemical group 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- 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
- D01D5/0007—Electro-spinning
-
- 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
- D01F1/10—Other agents for modifying properties
-
- 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
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/425—Cellulose series
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
- D06C7/04—Carbonising or oxidising
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film and preparation method thereof, first faint yellow TiO is made in butyl titanate by this method2Vitreosol, then be added in the cellulose fibre solution prepared, it is fully reacted, stir transparent to solution, TiO is made by electrostatic spinning in mixing2/ cellulosic fibrous substrates composite nano-fiber membrane.Composite nano-fiber membrane is prepared into the photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film with efficient absorption and catalytic performance through pre-oxidation, charing and activation process again.Preparation method process of the present invention is simple, and obtaining photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film has stronger absorption property and preferable Photocatalytic Degradation Property, and has the advantages that to be catalyzed in waste water or organic pollution in air.
Description
Technical field
The present invention relates to photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film and preparation method thereof, belong to activity
Carbon composite technology of preparing.
Background technology
The processing of traditional dyeing and finishing method of wastewater treatment is not ideal, is primarily due to Wastewater Dyes molecular structure stabilized, into
Divide complexity, percent of decolourization, COD clearances be not high, easily produces secondary pollution.Using the photocatalysis performance of semi-conducting material in room temperature
Under the conditions of the organic matter that many chemical methods and bioanalysis be able to can not be removed be completely decomposed into carbon dioxide and water, and do not cause
Secondary pollution, it can make excitaton source with the ultraviolet light contained in sunshine and fluorescent lamp.Currently, for environmental contaminants of degrading
In catalyst, titanium dioxide turns into most application prospect by its photocatalytic activity height, indissoluble, the low feature of nontoxic and cost
One of photochemical catalyst, and with purification air, kill bacterium, the effect such as degraded hardly degraded organic substance.But traditional nanometer
TiO2Suspended phase photochemical catalyst easy in inactivation, easy cohesion, the difficult shortcoming reclaimed, therefore searching one kind has large specific surface area, again
With TiO2The high-efficient carrier material of strong bonded is the key of practical technology.Absorbent charcoal material is used as a kind of preferable adsorption material
Material, grows up on the basis of Carbon fibe technology and activated carbon technology are combined.Activated carbon has larger pore capacities
And specific surface area, and based on micropore, therefore, be conducive to adsorbate to diffuse into hole and active surface, activated carbon is shown
Higher adsorption capacity and faster adsorption/desorption speed.The dye in sewage will be effectively adsorbed and removes using the activated carbon
Material, slurry, auxiliary agent, finish, soda acid, fiber impurity, inorganic salts etc..
Because dyeing waste water is often containing organic substances such as very high suspensions and pigment, the processing of any monotechnics is past
It is past not reach preferable effect.Current membrane separation technique and the integrated technique of other water technologies are studied, and play various technologies
Advantage, formed dyeing waste water advanced treating new technology.The advanced country of economically developed in the world, science and technology in recent years will
Membrane separation technique, such as ultrafiltration (UF), counter-infiltration (RO) and nanofiltration (NF) are applied to the processing of printing and dyeing industrial waste water, can be significantly
Energy consumption is reduced, investment is reduced.Because membrane filtration technique has the advantages that high separative efficiency, energy-conservation, equipment are simple and convenient to operate,
It is set to have very big development potentiality in field of waste water treatment.But in current MF and UF films progress sewage disposal process more or less all
Problem is blocked up in the presence of a dirt, this problem is also very serious sometimes, causes water rate degradation, directly influences this system
Operational efficiency and its success or failure.It is TiO using the special surface chemical structure of NACF and strong physical adsorbability2Light urge
Change the reaction environment there is provided high concentration, organic pollutants are efficiently removed with its absorption and catalyzing cooperation effect, significantly carried
The reclamation rate of high dyeing and printing sewage.Dyeing waste water circulating and recovering is realized by photocatalytic active carbon nano fibrous membrane, to water pollution
Control and the sustainable development of dyeing industry all have very positive meaning.
The content of the invention
The present invention is in order to overcome the above-mentioned deficiencies of the prior art, it is therefore an objective to lived there is provided a kind of photocatalytic fiber cellulose fiber base
Property carbon nanofibers composite membrane and preparation method thereof, composite is made in this way has stronger absorption property and preferably
Photocatalytic Degradation Property.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of preparation method of photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film, this method is first by metatitanic acid
Faint yellow TiO is made in four butyl esters2Vitreosol, then be added in the cellulose fibre solution prepared, being stirred continuously makes
It is fully reacted, transparent to solution, and mixed liquor is made into TiO by electrostatic spinning2/ cellulose fibre based composite nano fiber
Film；Again by TiO2/ cellulosic fibrous substrates composite nano-fiber membrane is prepared into efficient through pre-oxidation, charing and activation process
Absorption and the photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film of catalytic performance；This method comprises the following steps：
1) prepared by TiO 2 sol：15~30 parts of butyl titanates and 5~15 parts of glacial acetic acid are dissolved in 50~80 parts of nothings
In water-ethanol, 0.5~2h of magnetic agitation is allowed to well mixed, is slowly dropped into 80~95 parts of absolute ethyl alcohols and 5~20 parts of distilled water
Mixed solution in, control buret drop speed, sealing stirring obtain faint yellow TiO2Vitreosol, still aging 2~4h；
2) prepared by cellulose fibre solution：Cellulose fibre is dissolved in corresponding solvent at room temperature, adult is prepared
Product mass fraction (g/L) is 1~20% solution, and magnetic agitation is transparent to solution；
3) prepared by cellulosic fibrous substrates composite nano-fiber membrane：By step 1) made from titania solution and step 2) system
The cellulose fibre solution obtained is mixed according to the mass ratio 0.01: 1~0.5: 1 of solute, fully reaction, is stirred to completely mixed
Close uniformly and solution is transparent, pass through electrostatic spinning apparatus and TiO is made2/ cellulosic fibrous substrates composite nano-fiber membrane；
4) prepared by activated carbon composite nano-fiber membrane：By step 3) made from TiO2/ cellulose fibres base composite nano it is fine
Film is tieed up through pre-oxidation, charing and activation process, photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film is prepared into.
The cellulosic fibre material is native cellulose fibre and regenerated celulose fibre, and native cellulose fibre includes
Flaxen fiber, bamboo fibre, cotton；It is fine that regenerated celulose fibre includes viscose rayon, Tencel fibers, Lyocell fiber, Modal
Dimension.
The step 2) solvent used in cellulose fibre be dimethyl sulfoxide (DMSO), dimethylformamide, dimethyl acetamide,
N-methylmorpholine-N- oxides, etamon chloride solution, ammonium thiocyanate solution, triethanolamine, ammonia spirit, alkalescence are water-soluble
One or more of mixed solvent systems in liquid.
The alkaline aqueous solution is alkali metal hydroxide aqueous solution, specially sodium hydroxide, potassium hydroxide.
Described electrostatic spinning apparatus is made up of high-voltage generator, syringe pump and fiber receiver；Spinning voltage：10
~30kV, rate of extrusion：0.05~2.0ML/h, receives distance：10~30cm.
Described Pre oxidation is controlled at 50~350 DEG C；Activate the H in 5~20wt%3PO4Solution and 5~20wt%
KOH solution in carry out；Charing is in tubular type Muffle furnace, (e.g., N in atmosphere of inert gases2Deng), 400~600 DEG C of temperature control
Calcination, to obtain the TiO with catalytic activity2Crystal formation.
The inert gas is nitrogen, argon gas.
Present invention additionally comprises the photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film prepared using the above method.
Preparation method process of the present invention is simple, obtains photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film tool
There is stronger absorption property and preferable Photocatalytic Degradation Property.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
A kind of preparation method of photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film, this method is first by metatitanic acid
Faint yellow TiO is made in four butyl esters2Vitreosol, then be added in the cellulose fibre solution prepared, being stirred continuously makes
It is fully reacted, transparent to solution, and mixed liquor is made into TiO by electrostatic spinning2/ cellulose fibre based composite nano fiber
Film；Again by TiO2/ cellulosic fibrous substrates composite nano-fiber membrane is prepared into efficient through pre-oxidation, charing and activation process
Absorption and the photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film of catalytic performance；Preparation method process letter of the present invention
It is single, obtain photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film and urged with stronger absorption property and preferable light
Change degradation property.
Embodiment 1：
A kind of preparation method of photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film, this method includes following step
Suddenly：
1) prepared by TiO 2 sol：15 parts of butyl titanates and 5 parts of glacial acetic acid are dissolved in 50 parts of absolute ethyl alcohols, magnetic force
Stirring 0.5h is allowed to well mixed, in the mixed solution for being slowly dropped into 80 parts of absolute ethyl alcohols and 5 parts of distilled water, control buret drop
Speed, sealing stirring obtains faint yellow TiO2Vitreosol, still aging 2h；
2) prepared by cellulose fibre solution：Cellulose fibre (flaxen fiber) is dissolved in dimethyl sulfoxide (DMSO) at room temperature,
The solution that volume mass fraction (g/L) is 1% is configured to, magnetic agitation is transparent to solution；
3) prepared by cellulosic fibrous substrates composite nano-fiber membrane：By step 1) made from titania solution and step 2) system
Cellulose fibre solution mixed according to the mass ratio 0.01: 1 of solute, fully reaction is stirred to being mixed thoroughly
And solution is transparent, TiO is made by electrostatic spinning apparatus2/ cellulosic fibrous substrates composite nano-fiber membrane；
4) prepared by activated carbon composite nano-fiber membrane：By step 3) made from TiO2/ cellulose fibres base composite nano it is fine
Film is tieed up through pre-oxidation, charing and activation process, Pre oxidation is 150 DEG C, in 5wt% H3PO4Solution and 5wt% KOH are molten
Activated in liquid；In tubular type Muffle furnace, inert gas N2Carbonized in atmosphere, 450 DEG C of calcination of temperature control are prepared into
Photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film.
Embodiment 2：
A kind of preparation method of photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film, this method includes following step
Suddenly：
1) prepared by TiO 2 sol：20 parts of butyl titanates and 10 parts of glacial acetic acid are dissolved in 60 parts of absolute ethyl alcohols, magnetic
Power stirring 1h is allowed to well mixed, in the mixed solution for being slowly dropped into 85 parts of absolute ethyl alcohols and 10 parts of distilled water, controls buret
Drop speed, sealing stirring obtains faint yellow TiO2Vitreosol, still aging 3h；
2) prepared by cellulose fibre solution：Cellulose fibre (Lyocell fiber) is dissolved in dimethyl methyl at room temperature
In acid amides, the solution that volume mass fraction (g/L) is 8% is configured to, magnetic agitation is transparent to solution；
3) prepared by cellulosic fibrous substrates composite nano-fiber membrane：By step 1) made from titania solution and step 2) system
Cellulose fibre solution mixed according to the mass ratio 0.1: 1 of solute, fully reaction, stir to being mixed thoroughly and
Solution is transparent, and TiO is made by electrostatic spinning apparatus2/ cellulosic fibrous substrates composite nano-fiber membrane；
4) prepared by activated carbon composite nano-fiber membrane：By step 3) made from TiO2/ cellulose fibres base composite nano it is fine
Film is tieed up through pre-oxidation, charing and activation process, Pre oxidation is 180 DEG C, in 10wt% H3PO4The KOH of solution and 10wt%
Activated in solution；In tubular type Muffle furnace, carbonized in inert gas (argon gas) atmosphere, 450 DEG C of calcination of temperature control,
It is prepared into photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film.
Embodiment 3：
A kind of preparation method of photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film, this method includes following step
Suddenly：
1) prepared by TiO 2 sol：25 parts of butyl titanates and 15 parts of glacial acetic acid are dissolved in 70 parts of absolute ethyl alcohols, magnetic
Power stirring 1.5h is allowed to well mixed, in the mixed solution for being slowly dropped into 90 parts of absolute ethyl alcohols and 15 parts of distilled water, control titration
Pipe drop speed, sealing stirring obtains faint yellow TiO2Vitreosol, still aging 3h；
2) prepared by cellulose fibre solution：At room temperature by cellulose fibre (Modal fibers) be dissolved in N-methylmorpholine-
In N- oxides, the solution that volume mass fraction (g/L) is 15% is configured to, magnetic agitation is transparent to solution；
3) prepared by cellulosic fibrous substrates composite nano-fiber membrane：By step 1) made from titania solution and step 2) system
Cellulose fibre solution mixed according to the mass ratio 0.3: 1 of solute, fully reaction, stir to being mixed thoroughly and
Solution is transparent, and TiO is made by electrostatic spinning apparatus2/ cellulosic fibrous substrates composite nano-fiber membrane；
4) prepared by activated carbon composite nano-fiber membrane：By step 3) made from TiO2/ cellulose fibres base composite nano it is fine
Film is tieed up through pre-oxidation, charing and activation process, Pre oxidation is 200 DEG C, in 15wt% H3PO4The KOH of solution and 15wt%
Activated in solution；In tubular type Muffle furnace, inert gas N2Carbonized in atmosphere, prepared by 500 DEG C of calcination of temperature control
Into photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film.
Embodiment 4：
A kind of preparation method of photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film, this method includes following step
Suddenly：
1) prepared by TiO 2 sol：30 parts of butyl titanates and 15 parts of glacial acetic acid are dissolved in 80 parts of absolute ethyl alcohols, magnetic
Power stirring 2h is allowed to well mixed, in the mixed solution for being slowly dropped into 95 parts of absolute ethyl alcohols and 20 parts of distilled water, controls buret
Drop speed, sealing stirring obtains faint yellow TiO2Vitreosol, still aging 4h；
2) prepared by cellulose fibre solution：Cellulose fibre (bamboo fibre) is dissolved in ammonia/ammonium thiocyanate at room temperature molten
Liquid (NH3/NH4SCN/H2O systems) in, the solution that volume mass fraction (g/L) is 8% is configured to, magnetic agitation is saturating to solution
It is bright；
3) prepared by cellulosic fibrous substrates composite nano-fiber membrane：By step 1) made from titania solution and step 2) system
Cellulose fibre solution mixed according to the mass ratio 0.5: 1 of solute, fully reaction, stir to being mixed thoroughly and
Solution is transparent, and TiO is made by electrostatic spinning apparatus2/ cellulosic fibrous substrates composite nano-fiber membrane；
4) prepared by activated carbon composite nano-fiber membrane：By step 3) made from TiO2/ cellulose fibre base composite nano is fine
Film is tieed up through pre-oxidation, charing and activation process, Pre oxidation is 250 DEG C, in 20wt% H3PO4The KOH of solution and 20wt%
Activated in solution；In tubular type Muffle furnace, carbonized in inert gas (argon gas) atmosphere, 550 DEG C of calcination of temperature control,
It is prepared into photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film.
Claims (1)
1. a kind of preparation method of photocatalytic fiber cellulose fiber matrix activated carbon nano-fiber composite film, this method is first by metatitanic acid four
Faint yellow TiO is made in butyl ester<sub>2</sub>Vitreosol, then be added in the cellulose fibre solution prepared,
Being stirred continuously makes it fully react, transparent to solution, and mixed liquor is made into TiO by electrostatic spinning<sub>2</sub>/ fine
Cellulose fiber based composite nano fiber film；Again by TiO<sub>2</sub>/ cellulosic fibrous substrates composite nano-fiber membrane is through pre-
Oxidation, charing and activation process, are prepared into the photocatalytic fiber cellulose fiber matrix activated carbon with efficient absorption and catalytic performance and receive
Rice composite fiber membrane；This method comprises the following steps：
1) prepared by TiO 2 sol：15~30 parts of butyl titanates and 5~15 parts of glacial acetic acid are dissolved in 50~80 parts of anhydrous second
In alcohol, the h of magnetic agitation 0.5~2 is allowed to well mixed, is slowly dropped into the mixed of 80~95 parts of absolute ethyl alcohols and 5~20 parts of distilled water
Close in solution, control buret drop speed, sealing stirring obtains faint yellow TiO<sub>2</sub>Vitreosol, still aging 2
~4h；
2) prepared by cellulose fibre solution：Cellulose fibre is dissolved in corresponding solvent at room temperature, volume matter is configured to
The solution that fraction is 1~20%g/L is measured, magnetic agitation is transparent to solution；The cellulosic fibre material is that native cellulose is fine
Peacekeeping regenerated celulose fibre, native cellulose fibre includes flaxen fiber, bamboo fibre, cotton；Regenerated celulose fibre includes viscous
Glue fiber, Tencel fibers, Lyocell fiber, Modal fibers；Solvent is dimethyl sulfoxide (DMSO), dimethyl acetamide, N- methyl
One in methylmorpholine-N-oxide, etamon chloride solution, ammonium thiocyanate solution, triethanolamine, ammonia spirit, alkaline aqueous solution
Plant or several mixed solvent systems；Alkaline aqueous solution is alkali metal hydroxide aqueous solution, specially sodium hydroxide, hydroxide
Potassium；
3) prepared by cellulosic fibrous substrates composite nano-fiber membrane：By step 1) made from TiO 2 sol and step 2) system
The cellulose fibre solution obtained is mixed according to the mass ratio 0.01: 1~0.5: 1 of solute, fully reaction, is stirred to completely mixed
Close uniformly and solution is transparent, pass through electrostatic spinning apparatus and TiO is made<sub>2</sub>/ cellulose fibre based composite nano fiber
Film；Described electrostatic spinning apparatus is made up of high-voltage generator, syringe pump and fiber receiver；Spinning voltage：10~30
KV, rate of extrusion：0.05~2.0ML/h, receives distance：10~30 cm；
4) prepared by activated carbon composite nano-fiber membrane：By step 3) made from TiO<sub>2</sub>/ cellulosic fibrous substrates are multiple
Nano fibrous membrane is closed through pre-oxidation, charing and activation process, photocatalytic fiber cellulose fiber matrix activated carbon nanofiber is prepared into and answers
Close film；Described Pre oxidation is controlled at 50~350 DEG C；Activation is the H in 5~20wt%<sub>3</sub>PO<sub>4
</sub>Carried out in solution and 5~20wt% KOH solution；Charing is in tubular type Muffle furnace, in atmosphere of inert gases, temperature control
400~600 DEG C of calcination of system, to obtain the TiO with catalytic activity<sub>2</sub>Crystal formation；The inert gas be nitrogen,
Argon gas.
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| CN105413752A (en) * | 2015-11-05 | 2016-03-23 | 浙江理工大学 | Preparation method of photo-catalyzed collodion cellulose-based activated carbon nano-fiber composite membrane |
| CN105435849A (en) * | 2015-11-05 | 2016-03-30 | 浙江理工大学 | Preparation method of photocatalytic ramie cellulose based activated carbon-nano fiber composite film |
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