CN106012071A - Preparation method of continuous cellulose/TiO2 aerogel fiber with photocatalytic performance - Google Patents

Preparation method of continuous cellulose/TiO2 aerogel fiber with photocatalytic performance Download PDF

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CN106012071A
CN106012071A CN201610472058.5A CN201610472058A CN106012071A CN 106012071 A CN106012071 A CN 106012071A CN 201610472058 A CN201610472058 A CN 201610472058A CN 106012071 A CN106012071 A CN 106012071A
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cellulose
tio
solution
fiber
spinning
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CN106012071B (en
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朱美芳
张君妍
陈文萍
成艳华
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Donghua University
National Dong Hwa University
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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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • 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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • 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
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D7/00—Collecting the newly-spun products
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention discloses a preparation method of continuous cellulose/TiO2 aerogel fiber with photocatalytic performance. The preparation method comprises steps as follows: a spinning solution is prepared from cellulose, and a TiO2 photocatalyst is added; an acid solution, an ethanol solution or an acetone solution is added to a coagulating basin and taken as coagulating bath; the spinning solution with the TiO2 photocatalyst added is added to the coagulating bath and subjected to wet spinning, and cellulose gel fiber containing the TiO2 photocatalyst is obtained; the fiber is wound and soaked in an ageing solution for constant-temperature ageing, then the fiber is washed with deionized water to be neutral and is subjected to solvent replacement and drying, and the continuous cellulose/TiO2 aerogel fiber with the photocatalytic performance is obtained. The continuous cellulose/TiO2 aerogel fiber with the photocatalytic performance prepared with the method is rich in holes and has a large specific surface area, the specific surface area of the fiber and the content of TiO2 in the fiber are adjustable, and the continuous cellulose/TiO2 aerogel fiber has the characteristics that the raw materials are cheap and easily available, the preparation process is simple, green and pollution-free and the spinning property is good.

Description

There is the continuous cellulose/TiO of photocatalysis performance2The preparation method of aeroge fiber
Technical field
The invention belongs to the preparation field of aeroge fiber, particularly to a kind of, there is the continuous fine of photocatalysis performance Dimension element/TiO2The preparation method of aeroge fiber.
Background technology
Aeroge (aerogel) is a kind of highly porous solid, in the hole and network structure of solid matrix Gassy (typically air).Because having high porosity, low-density, lower thermal conductivity, the low velocity of sound, low The characteristic of a series of excellences such as refractive index and big specific surface area, aeroge has a wide range of applications in many fields Prospect.
Aeroge is divided into inorganic aerogels and organic aerogel, compared to frangible inorganic aerogels, organic airsetting It is preferable that glue has mechanical property, the advantage that pliability is good.TiO2The carrier of photocatalyst not only has good machine Tool performance and pliability, and its raw material sources are the most renewable, rich reserves, nontoxic and can be with biodegradation.
The TiO of relevant cellulose aerogels load at present2The research of photocatalyst has focused largely on two dimension, three-dimensional fibre On dimension element aerogel material, learn Olli Ikkala seminar by lyophilization cellulose Nanowire as A Er gives oneself airs It is 20m that dimension suspension is prepared for specific surface area2The nano-cellulose aerogel film of/g, then pass through CVD, with Tetraisopropyl titanate is that presoma deposited the thick TiO of one layer of 7nm on cellulose nano-fibrous network skeleton2, Obtain that not only there is light-operated hydrophilicity and hydrophobicity but also there is the nano-cellulose/TiO of good photocatalysis performance2Gas Gel film, is placed in 3mg aerogel film in 3ml 0.03mmol/L methylene blue solution, shines at Weak ultraviolet After lower 24h, methylene blue degraded nearly 70%.Li Jian seminar of Northeast Forestry University is cellulose and nano-silica Change titanium mix homogeneously in ionic liquid, after regeneration, prepare cellulose/TiO through supercritical drying2Aerogel film, Can be used for portable and flexible light catalytic field.But the one dimension fibre fiber-loaded TiO of element aeroge at present2Light Catalyst but has no report.This is because compared to the aerogel material of other dimensions, threadiness aerogel material Raw material and preparation condition are required harsher.But, threadiness aerogel material is compared to gas two-dimentional, three-dimensional Gel rubber material has the advantage of uniqueness.The aerogel material photocatalytic degradation to waste water and gas of agent is urged with load light As a example by, waste water and gas contacts complexity and determines the catalytic efficiency of material with photocatalyst.With block and thin film Shape material is compared, and fibrous material further increases the contact area with waste water and gas, and waste water and gas exists simultaneously Diffusional resistance in material is substantially reduced with transmission range so that it is be easier to contact with catalytic active center, improves Catalytic efficiency, and zero dimension catalysis material may cause reunion in use so that it is catalytic efficiency is significantly Reduce, and zero dimension dusty material is difficult to be kept completely separate, and easily causes secondary pollution.
At present about the continuous cellulose/TiO with photocatalysis performance2The document of aeroge fiber yet there are no report Road.
Summary of the invention
The technical problem to be solved is to provide a kind of continuous cellulose/TiO with photocatalysis performance2 The preparation method of aeroge fiber.
In order to solve the problems referred to above, the invention provides a kind of continuous cellulose/TiO with photocatalysis performance2 The preparation method of aeroge fiber, it is characterised in that comprise the following steps:
Step 1): preparation cellulose dispersion liquid, as spinning solution, adds TiO in spinning solution2Photocatalysis Agent, adds acid solution, ethanol solution or acetone soln as coagulating bath in coagulating basin；
Step 2): by step 1) middle addition TiO2The spinning solution of catalyst is expressed into step 1) in coagulating bath In, carry out wet spinning, obtain containing TiO2The cellulose gel glue fiber of catalyst；
Step 3): by step 2) in containing TiO2The cellulose gel glue fiber of photocatalyst is rolled up in coagulating bath Around；Immerse room temperature ageing 15min～1h in aged solution, be washed with deionized to neutrality, then spend from Sub-water, ethanol or the tert-butyl alcohol carry out solvent displacement, are dried, obtain the continuous cellulose with photocatalysis performance /TiO2Aeroge fiber.
Preferably, described step 1) in cellulose in cellulose dispersion liquid be cotton pulp cellulose or bacterial fibers Element, its mass concentration in cellulose dispersion liquid is 2%～7%.
Preferably, described step 1) in dispersant in cellulose dispersion liquid be with in cellulose dispersion liquid The 4.2%LiOH/12% carbamide of mass concentration meter, 7%NaOH/12% carbamide, 9.5%NaOH/4.5% thiourea or NaOH (7%～8%)/carbamide 8%/thiourea (6.5%～10%) system.
Preferably, described step 1) in TiO2Photocatalyst is P25 or N-TiO2；It is with spinning solution Mass percent is 0.5%～1.0%.
Preferably, described step 1) in acid solution use 2%～5% sulphuric acid in terms of mass concentration, 3～5% Aqueous sodium persulfate solution or 1%～3% dilute acetic acid solution；The ethanol that ethanol solution uses volume fraction to be 10%～50% Aqueous solution；The aqueous acetone solution that acetone soln uses volume fraction to be 10%～30%.
Preferably, described step 2) in the condition of wet spinning be normal temperature and pressure.
Preferably, described step 2) in the extruded velocity of spinning solution be 0.6m/min～6m/min.
Preferably, described step 2) in winding speed be 0.6m/min～24m/min.
Preferably, described step 3) in aged solution use 0.5%～1% dilute sulfuric acid in terms of mass concentration, 0.5%～1% dilute acetic acid solution, straight alcohol solution or pure acetone solution.
Preferably, described step 3) in the method that is dried use lyophilization or supercritical drying.
A kind of continuous cellulose/TiO with photocatalysis performance prepared by the present invention2Aeroge fiber hole is being received Metrical scale scope, and specific surface area size can be regulated by changing preparation condition.
The present invention adds the TiO of different content in used spinning solution prepared by cellulose aerogels fiber2 Photocatalyst, it is achieved there is the continuous cellulose/TiO of photocatalysis performance2The preparation of aeroge fiber.
The present invention is the TiO of different content2Photocatalyst adds cellulose spin dope to, in wet spinning The principle of spinning solution rapid solidification regeneration in coagulating bath and cellulose directly dissolve regeneration prepares cellulose gas The method of gel combines, and realizes continuous cellulose/TiO by wet spinning2The preparation of aeroge fiber, Continuous cellulose/the TiO with photocatalysis performance is obtained afterwards by lyophilization or supercritical drying2Aeroge is fine Dimension, has novelty.Prepared continuous cellulose/the TiO with photocatalysis performance2Aeroge fiber is at light A series of fields such as catalysis have more prominent advantage, have the hugest potential demand, have practicality.
Continuous cellulose/TiO in the present invention2The preparation method of aeroge fiber, is by the TiO of different content2 Photocatalyst adds in cellulose spin dope, using acid solution, ethanol solution or acetone soln as solidification Bath, occurs quick solventnonsolvent double by cellulose spin dope and the acid in coagulating bath, ethanol or acetone Diffusion makes cellulose solidification regeneration, obtains containing TiO2The cellulose gel glue fiber of photocatalyst, by winding Fiber is carried out rolling by roller.Subsequently, by rolling containing TiO2The cellulose gel glue fiber of photocatalyst soaks In ageing bath, cellulose is made to form intermolecular and intramolecular hydrogen bond further and gelation by ageing, finally Obtain stable three-dimensional net structure, form more hole.After ageing, deionized water is used to wash, Then deionized water, ethanol or the tert-butyl alcohol is used to carry out solvent displacement, the most freeze-dried or supercritical drying Obtain the continuous cellulose/TiO with photocatalysis performance2Aeroge fiber.Method used in the present invention has The extensive low cost of raw material sources, preparation process be simple and green non-pollution, the feature of good spinnability.Obtained Cellulose/TiO2Aeroge fiber has good pliability, and has abundant hole and high specific surface area, TiO in pulp freeness, fiber simultaneously2Photocatalyst content is adjustable, has wide in fields such as photocatalysis Application prospect.
Method used in the present invention has the extensive low cost of raw material sources, preparation process is simple and green is without dirty Dye, the feature of good spinnability.Obtained cellulose/TiO2Aeroge fiber has good pliability, and There is abundant hole and high specific surface area, simultaneously TiO in pulp freeness, fiber2Photocatalyst contains Measure adjustable, in fields such as photocatalysis, there is broad prospect of application.
Accompanying drawing explanation
Fig. 1 is through cellulose/TiO in embodiment 12Aeroge fiber optic catalytic degradation methylene blue different time After, methylene blue solution color is with processing time variation diagram；
Fig. 2 is through cellulose/TiO in embodiment 12Aeroge fiber optic catalytic degradation methylene blue different time After, methylene blue ultraviolet characteristic peak high rate is with processing time variation diagram.
Detailed description of the invention
For making the present invention become apparent, hereby with preferred embodiment, and accompanying drawing is coordinated to be described in detail below.
Embodiment 1
Bacterial cellulose (Hainan hundred million moral Food Co., Ltd, particle compressed coconut) is dispersed in mass concentration In the low-temperature solvent system of 7%NaOH/8% carbamide/10% thiourea of meter, the wherein mass concentration of Bacterial cellulose It is 2%, adds the photocatalyst P25 (all percentage ratios all include itself, lower same) that mass fraction is 0.5%, Machinery strong stirring 30min, carries out deaeration process 20min with centrifuge 10000r/min and obtains spinning solution, will Spinning solution is expressed in coagulating bath and carries out wet spinning under normal temperature and pressure, obtains the cellulose gel containing P25 Fiber；Described coagulating bath be volume fraction be the ethanol water of 10%；The extrusion speed of described spinning solution Degree is 0.6m/min；After gelatinous fibre is wound with the winding speed of 0.6m/min in coagulating bath, leaching Enter to be aged liquid ethanol is aged at normal temperatures 1h so that it is gelation completely；After ageing, by fiber deionization Water washing is to neutral, then replaces deionized water with the tert-butyl alcohol, freeze-dried, obtains cellulose/TiO2Airsetting Glue fiber.The successive silk of spinning process, prepared cellulose/TiO2Aeroge pulp freeness is 175 m2/ g, most probable pore size is 6nm.By cellulose/TiO2Aeroge fiber immerses the methylene blue of 10mg/L In solution, process under ultraviolet light, methylene blue degraded can be realized.Through cellulose/TiO2Aeroge fiber optic After catalytic degradation methylene blue different time, methylene blue solution color is with processing time variation diagram as shown in Figure 1 (processing the time from left to right from short to long)；Through cellulose/TiO2Aeroge fiber optic catalytic degradation methylene blue After different time, methylene blue ultraviolet characteristic peak high rate is with processing time variation diagram as shown in Figure 2.
Embodiment 2
Cotton pulp cellulose after processing is dispersed in 8%NaOH/8% carbamide/6.5% thiourea in terms of mass concentration Low-temperature solvent system in, wherein cotton pulp cellulose mass fraction is 7%, add mass fraction be the light of 1% Catalyst P25 catalyst, machinery strong stirring 30min, carry out deaeration process with centrifuge 10000r/min 20min obtains spinning solution, is expressed into by spinning solution in coagulating bath and carries out wet spinning under normal temperature and pressure, obtains Cellulose gel glue fiber containing P25；Described coagulating bath be volume fraction be the ethanol water of 50%； The extruded velocity of described spinning solution is 3m/min；By gelatinous fibre winding with 6m/min in coagulating bath After speed is wound, immerses in ageing liquid ethanol and be aged 1h at normal temperatures so that it is gelation completely；Ageing After, fiber is washed with deionized to neutrality, then uses ethanol replacement deionized water, through supercritical drying, i.e. Obtain cellulose/TiO2Aeroge fiber.The successive silk of spinning process, prepared cellulose/TiO2Aeroge Pulp freeness is 405m2/ g, most probable pore size is 3nm.By cellulose/TiO2Aeroge fiber immerses In the methylene blue solution of 10mg/L, process under ultraviolet light, methylene blue degraded can be realized.By cellulose /TiO2Aeroge fiber immerses in the methylene blue solution of 10mg/L, processes under ultraviolet light, can realize Asia Methyl blue degradation.
Embodiment 3
Bacterial cellulose is dispersed in the low-temperature solvent system of 9.5%NaOH/4.5% thiourea in terms of mass concentration In, wherein Bacterial cellulose mass fraction is 7%, machinery strong stirring 30min, and adding mass fraction is 0.5% Photocatalyst N-TiO2, carry out deaeration process 20min with centrifuge 10000r/min and obtain spinning solution, will Spinning solution is expressed in coagulating bath and carries out wet spinning under normal temperature and pressure, obtains containing N-TiO2Cellulose Gelatinous fibre；Described coagulating bath be volume fraction be the aqueous acetone solution of 10%；Squeezing of described spinning solution Going out speed is 2.4m/min；After gelatinous fibre is wound with the winding speed of 6m/min in coagulating bath, Immerse in ageing liquid acetone and be aged 20min at normal temperatures so that it is gelation completely；After ageing, fiber is spent Ionized water washing is to neutral, freeze-dried, obtains cellulose/TiO2Aeroge fiber.Spinning process is continuous Not fracture of wire, prepared cellulose/TiO2Aeroge pulp freeness is 99m2/ g, most probable pore size is 9nm. By cellulose/TiO2Aeroge fiber immerses in the methylene blue solution of 10mg/L, processes under ultraviolet light, Methylene blue degraded can be realized.
Embodiment 4
Bacterial cellulose is dispersed in the low-temperature solvent system of 4.2%LiOH/12% carbamide in terms of mass concentration In, wherein Bacterial cellulose mass fraction is 3%, machinery strong stirring 30min, and adding mass fraction is 1% Photocatalyst N-TiO2, carry out deaeration process 20min with centrifuge 10000r/min and obtain spinning solution, will Spinning solution is expressed in coagulating bath and carries out wet spinning under normal temperature and pressure, obtains containing N-TiO2Cellulose Gelatinous fibre；Described coagulating bath be volume fraction be the aqueous acetone solution of 30%；Squeezing of described spinning solution Going out speed is 1.8m/min；After gelatinous fibre is wound with the winding speed of 6m/min in coagulating bath, Immerse in ageing liquid acetone and be aged 20min at normal temperatures so that it is gelation completely；After ageing, fiber is spent Ionized water washing is to neutral, then replaces deionized water with the tert-butyl alcohol, freeze-dried, obtains cellulose/TiO2 Aeroge fiber.The successive silk of spinning process, prepared cellulose/TiO2Aeroge pulp freeness is 121m2/ g, most probable pore size is 6nm.By cellulose/TiO2Aeroge fiber immerses the methylene of 10mg/L In blue solution, process under ultraviolet light, methylene blue degraded can be realized.
Embodiment 5
Cotton pulp cellulose after process is dispersed in the low temperature of the 4.2%LiOH/12% carbamide in terms of mass concentration In dicyandiamide solution, wherein cotton pulp cellulose mass fraction is 4%, and adding mass fraction is the photocatalyst of 0.5% P25, machinery strong stirring 30min, carry out deaeration with centrifuge 10000r/min and process 20min to obtain spinning former Liquid, is expressed into spinning solution in coagulating bath and carries out wet spinning under normal temperature and pressure, obtain the fiber containing P25 Element gelatinous fibre；Described coagulating bath is to be the sulfur of 5% containing the sulphuric acid that mass fraction is 5% and mass fraction The aqueous solution of acid sodium；The extruded velocity of described spinning solution is 3m/min；By gelatinous fibre in coagulating bath After being wound with the winding speed of 18m/min, immerse and be aged in the dilute sulfuric acid that liquid mass fraction is 0.5% 20min it is aged so that it is gelation completely under room temperature；After ageing, fiber is washed with deionized to neutrality, Use ethanol replacement deionized water again, through supercritical drying, obtain cellulose/TiO2Aeroge fiber.Spinning The successive silk of journey, prepared cellulose/TiO2Aeroge pulp freeness is 359m2/ g, most probable hole Footpath is 3nm.By cellulose/TiO2Aeroge fiber immerses in the methylene blue solution of 10mg/L, in ultraviolet Process under light, methylene blue degraded can be realized.
Embodiment 6
Cotton pulp cellulose after processing is dispersed in 8%NaOH/8% carbamide/6.5% thiourea in terms of mass concentration Low-temperature solvent system in, wherein cotton pulp cellulose mass fraction is 7%, add mass fraction be the light of 0.5% Catalyst P25, machinery strong stirring 30min, carry out deaeration with centrifuge 10000r/min and process 20min Obtain spinning solution, spinning solution is expressed in coagulating bath and under normal temperature and pressure, carries out wet spinning, contained The cellulose gel glue fiber of P25；Described coagulating bath be mass fraction be the dilute acetic acid solution of 3%；Described The extruded velocity of spinning solution is 6m/min；By gelatinous fibre winding speed with 24m/min in coagulating bath After being wound, immerse in the spirit of vinegar that ageing liquid mass fraction is 0.5% and be aged 20min at normal temperatures, make Its complete gelation；After ageing, fiber is washed with deionized to neutrality, freeze-dried, obtain fiber Element/TiO2Aeroge fiber.The successive silk of spinning process, prepared cellulose/TiO2Aeroge fiber ratio Surface area is 113m2/ g, most probable pore size is 9nm.By cellulose/TiO2Aeroge fiber immerses 10mg/L Methylene blue solution in, process under ultraviolet light, can realize methylene blue degraded.
Embodiment 7
Low temperature cotton pulp cellulose after processing being dispersed in 7%NaOH/12% carbamide in terms of mass concentration is molten In agent system, wherein cotton pulp cellulose mass fraction is 4%, and adding mass fraction is the photocatalyst of 0.5% P25, machinery strong stirring 30min, carry out deaeration with centrifuge 10000r/min and process 20min to obtain spinning former Liquid, is expressed into spinning solution in coagulating bath and carries out wet spinning under normal temperature and pressure, obtain the fiber containing P25 Element gelatinous fibre；Described coagulating bath is to be the sulfur of 3% containing the sulphuric acid that mass fraction is 2% and mass fraction The aqueous solution of acid sodium；The extruded velocity of described spinning solution is 3m/min；By gelatinous fibre in coagulating bath After being wound with the winding speed of 12m/min, immerse in the dilute sulfuric acid that ageing liquid mass fraction is 1% often It is aged 15min so that it is gelation completely under temperature；After ageing, fiber is washed with deionized to neutrality, then Deionized water is replaced with the tert-butyl alcohol, freeze-dried, obtain cellulose/TiO2Aeroge fiber.Spinning process Successively silk, prepared cellulose/TiO2Aeroge pulp freeness is 264m2/ g, most probable pore size For 6nm.By cellulose/TiO2Aeroge fiber immerses in the methylene blue solution of 10mg/L, at ultraviolet light Lower process, can realize methylene blue degraded.
Embodiment 8
Cotton pulp cellulose after processing is dispersed in 8%NaOH/8% carbamide/6.5% thiourea in terms of mass concentration Low-temperature solvent system in, wherein cotton pulp cellulose mass fraction is 6%, add mass fraction be the light of 0.5% Catalyst P25, machinery strong stirring 30min, carry out deaeration with centrifuge 10000r/min and process 20min Obtain spinning solution, spinning solution is expressed in coagulating bath and under normal temperature and pressure, carries out wet spinning, contained The cellulose gel glue fiber of P25；Described coagulating bath be mass fraction be 1% dilute acetic acid solution；Described spins The extruded velocity of silk stock solution is 4.8m/min；By gelatinous fibre winding speed with 18m/min in coagulating bath After being wound, immerse in the spirit of vinegar that ageing liquid mass fraction is 1% and be aged 15min at normal temperatures so that it is Gelation completely；After ageing, fiber is washed with deionized to neutrality, freeze-dried, obtain cellulose /TiO2Aeroge fiber.The successive silk of spinning process, prepared cellulose/TiO2Aeroge fiber compares table Area is 117m2/ g, most probable pore size is 9nm.By cellulose/TiO2Aeroge fiber immerses 10mg/L's In methylene blue solution, process under ultraviolet light, methylene blue degraded can be realized.

Claims (10)

1. continuous cellulose/TiO with photocatalysis performance2The preparation method of aeroge fiber, it is characterised in that Comprise the following steps:
Step 1): preparation cellulose dispersion liquid, as spinning solution, adds TiO in spinning solution2Photocatalysis Agent, adds acid solution, ethanol solution or acetone soln as coagulating bath in coagulating basin；
Step 2): by step 1) middle addition TiO2The spinning solution of catalyst is expressed into step 1) in coagulating bath In, carry out wet spinning, obtain containing TiO2The cellulose gel glue fiber of catalyst；
Step 3): by step 2) in containing TiO2The cellulose gel glue fiber of photocatalyst is rolled up in coagulating bath Around；Immerse room temperature ageing 15min～1h in aged solution, be washed with deionized to neutrality, then spend from Sub-water, ethanol or the tert-butyl alcohol carry out solvent displacement, are dried, obtain the continuous cellulose with photocatalysis performance /TiO2Aeroge fiber.
There is the continuous cellulose/TiO of photocatalysis performance the most as claimed in claim 12The preparation side of aeroge fiber Method, it is characterised in that described step 1) in cellulose in cellulose dispersion liquid be cotton pulp cellulose or antibacterial Cellulose, its mass concentration in cellulose dispersion liquid is 2%～7%.
There is the continuous cellulose/TiO of photocatalysis performance the most as claimed in claim 12The preparation side of aeroge fiber Method, it is characterised in that described step 1) in dispersant in cellulose dispersion liquid be with at cellulose dispersion liquid In the 4.2%LiOH/12% carbamide of mass concentration meter, 7%NaOH/12% carbamide, 9.5%NaOH/4.5% sulfur Urea or NaOH (7%～8%)/carbamide 8%/thiourea (6.5%～10%) system.
There is the continuous cellulose/TiO of photocatalysis performance the most as claimed in claim 12The preparation side of aeroge fiber Method, it is characterised in that described step 1) in TiO2Photocatalyst is P25 or N-TiO2；It is former with spinning The mass percent of liquid is 0.5%～1.0%.
There is the continuous cellulose/TiO of photocatalysis performance the most as claimed in claim 12The preparation side of aeroge fiber Method, it is characterised in that described step 1) in acid solution use 2%～5% sulphuric acid in terms of mass concentration, 3～5% aqueous sodium persulfate solution or 1%～3% dilute acetic acid solution；Ethanol solution uses volume fraction to be 10%～50% Ethanol water；The aqueous acetone solution that acetone soln uses volume fraction to be 10%～30%.
There is the continuous cellulose/TiO of photocatalysis performance the most as claimed in claim 12The preparation side of aeroge fiber Method, it is characterised in that described step 2) in the condition of wet spinning be normal temperature and pressure.
There is the continuous cellulose/TiO of photocatalysis performance the most as claimed in claim 12The preparation side of aeroge fiber Method, it is characterised in that described step 2) in the extruded velocity of spinning solution be 0.6m/min～6m/min.
There is the continuous cellulose/TiO of photocatalysis performance the most as claimed in claim 12The preparation side of aeroge fiber Method, it is characterised in that described step 2) in winding speed be 0.6m/min～24m/min.
There is the continuous cellulose/TiO of photocatalysis performance the most as claimed in claim 12The preparation side of aeroge fiber Method, it is characterised in that described step 3) in aged solution use 0.5%～1% dilute sulfuric acid in terms of mass concentration, 0.5%～1% dilute acetic acid solution, straight alcohol solution or pure acetone solution.
There is the continuous cellulose/TiO of photocatalysis performance the most as claimed in claim 12The preparation of aeroge fiber Method, it is characterised in that described step 3) in the method that is dried use lyophilization or supercritical drying.
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