CN107519853B - A kind of photocatalysis elasticity TiO2Ceramic fibre sponge and preparation method thereof - Google Patents
A kind of photocatalysis elasticity TiO2Ceramic fibre sponge and preparation method thereof Download PDFInfo
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- CN107519853B CN107519853B CN201710670278.3A CN201710670278A CN107519853B CN 107519853 B CN107519853 B CN 107519853B CN 201710670278 A CN201710670278 A CN 201710670278A CN 107519853 B CN107519853 B CN 107519853B
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- ceramic fibre
- sponge
- mashing
- elasticity
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- 239000000835 fiber Substances 0.000 title claims abstract description 642
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 69
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 64
- 239000000919 ceramic Substances 0.000 claims abstract description 508
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 277
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 263
- 238000005360 mashing Methods 0.000 claims abstract description 217
- 239000006185 dispersion Substances 0.000 claims abstract description 146
- 239000007788 liquid Substances 0.000 claims abstract description 124
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000011065 in-situ storage Methods 0.000 claims abstract description 36
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 10
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 238000010009 beating Methods 0.000 claims description 140
- 230000006835 compression Effects 0.000 claims description 69
- 238000007906 compression Methods 0.000 claims description 69
- 229910052719 titanium Inorganic materials 0.000 claims description 68
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 67
- 238000003756 stirring Methods 0.000 claims description 64
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 46
- 239000003054 catalyst Substances 0.000 claims description 46
- 230000015556 catabolic process Effects 0.000 claims description 43
- 238000006731 degradation reaction Methods 0.000 claims description 43
- 239000010936 titanium Substances 0.000 claims description 35
- 230000008014 freezing Effects 0.000 claims description 34
- 238000007710 freezing Methods 0.000 claims description 34
- 238000003837 high-temperature calcination Methods 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 32
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 32
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- 229920002554 vinyl polymer Polymers 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 20
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 20
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 20
- 229910052726 zirconium Inorganic materials 0.000 claims description 20
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- -1 hydroxyl Propyl Chemical group 0.000 claims description 16
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 12
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000036571 hydration Effects 0.000 claims description 8
- 238000006703 hydration reaction Methods 0.000 claims description 8
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- 108010010803 Gelatin Proteins 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 6
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- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 4
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 150000000703 Cerium Chemical class 0.000 claims description 4
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 4
- 229910016874 Fe(NO3) Inorganic materials 0.000 claims description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 claims description 4
- WEUCTTBUEWINIJ-UHFFFAOYSA-N acetic acid;zinc;dihydrate Chemical compound O.O.[Zn].CC(O)=O WEUCTTBUEWINIJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 235000013495 cobalt Nutrition 0.000 claims description 4
- BXRRQHBNBXJZBQ-UHFFFAOYSA-L dichloromanganese;hydrate Chemical compound O.Cl[Mn]Cl BXRRQHBNBXJZBQ-UHFFFAOYSA-L 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims description 4
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 150000002603 lanthanum Chemical class 0.000 claims description 4
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 4
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 4
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical class Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
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- 150000002815 nickel Chemical class 0.000 claims description 4
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 4
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 4
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 4
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- 239000001913 cellulose Substances 0.000 claims description 3
- MSBWDNNCBOLXGS-UHFFFAOYSA-L manganese(2+);diacetate;hydrate Chemical compound O.[Mn+2].CC([O-])=O.CC([O-])=O MSBWDNNCBOLXGS-UHFFFAOYSA-L 0.000 claims description 3
- 150000003746 yttrium Chemical class 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
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- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 claims 1
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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
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
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- B01J35/58—
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- B01J35/617—
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The present invention relates to a kind of photocatalysis elasticity TiO2Ceramic fibre sponge and preparation method thereof is made sticky dispersion liquid first with water soluble polymer, water and inorganic sol, adds by in-situ modified TiO2Intermittent mashing is carried out after ceramic fibre film and polyelectrolyte is added obtaining TiO2Ceramic fibre dispersion liquid, then curing molding obtains elastic TiO2Ceramic fibre sponge.The method of the present invention significantly improves active site quantity when catalysis material carries out catalysis reaction, final photocatalysis elasticity TiO obtained while effectively solving the problems, such as big film material existing resistance under High Speed Flow Field effect and cracky2Ceramic fibre sponge has many advantages, such as photocatalytic activity height, and stability height and resilience are high, has fabulous practical value and promotional value.
Description
Technical field
The invention belongs to ceramic porous material fields, and in particular to a kind of photocatalysis elasticity TiO2Ceramic fibre sponge and
Preparation method.
Background technique
TiO2As catalysis material due to photocatalytic activity is high, catalytic degradation is thorough, reaction condition is mildly anti-light
The advantages that corrosivity is strong, the volatility in the dyestuff and small organic molecule, industry in catalytic degradation textile printing and dyeing wastewater have
Volatile organic matter (VOCs) etc. in machine object (VOCs) and life in indoor cart has broad application prospects, therefore,
With TiO2For raw material catalysis material also increasingly by the concern of researcher.
Patent CN101318126 is by disclosing a kind of high-crystallinity, large-specific surface area nano TiO2The system of photochemical catalyst
Preparation Method, by colloidal sol, the pre- crystallization of hydro-thermal and organic amine flow back curing process etc. obtained it is a kind of with specific crystal formation structure
Porous nano TiO2Photochemical catalyst；Patent CN106732506A discloses a kind of modified TiO of carbon yttrium2The preparation process of photochemical catalyst,
Using sol-gal process, precursor sol is prepared by raw material of butyl titanate, then the doping vario-property member into precursor sol
Element stirs to get gel, by gel by dry, crushing, roasting, obtains modified TiO2.The TiO that the above method is prepared2?
For graininess, though having preferable catalytic activity, the disadvantages of there are easy to reunite, difficult recycling.
Patent CN103263902A discloses a kind of glass fabric load TiO2The preparation method of photochemical catalyst, patent
CN106423250A discloses a kind of molecular sieve carried TiO of active zeolite2The preparation method of catalysis material, the above method pass through
By TiO2Nano particle is supported on matrix, solves the problems, such as separation and recovery of catalyst to a certain extent, but reduce TiO2It receives
The specific surface area of rice grain, causes TiO2Catalytic activity reduction.
At this point, TiO2Nanofiber catalysis material is due in a degree of catalytic activity for remaining catalysis material
While have many advantages, such as that diameter is small and large specific surface area again, be increasingly becoming researcher's research and utilization TiO2Light is prepared to urge
Change one of the Main Trends of The Development of material.Such as patent CN104153123B disclose a kind of flexible TiOx nano tunica fibrosa and
Preparation method, document Scientific Reports 7 (2017) 1636 are adulterated using Zr, and are prepared by method of electrostatic spinning
Flexibility TiO out2Tunica fibrosa, although the above method prepares TiOx nano tunica fibrosa with certain self-supporting, two dimension
Membrane structure causes its porosity to be difficult to be promoted, and haves the defects that cracky under High Speed Flow Field effect, influences its service life.
Therefore, a kind of photocatalysis elasticity with high active site, high stability and high catalytic efficiency is studied
TiO2Ceramic fibre sponge and preparation method thereof has a very important significance.
Summary of the invention
The purpose of the invention is to overcome above-mentioned defect in the prior art, provide a kind of with high catalytic active site
The photocatalysis elasticity TiO of point, high stability and high catalytic efficiency2Ceramic fibre sponge and preparation method thereof.
In order to achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) sticky dispersion liquid is prepared, the viscosity dispersion liquid is made of water soluble polymer, water and inorganic sol；
The purpose that water soluble polymer is added in the present invention is to prevent subsequent step by the space steric effect of macromolecular chain
Middle inorganic sol micelle and TiO2Reunion, sedimentation phenomenon occur in pulping process for ceramic fibre, improve the equal of fiber dispersion
Even property；Utilize high molecular polymer and inorganic sol micelle, TiO2Hydrogen bond, covalent bond and physical entanglement between ceramic fibre are made
With making inorganic sol micelle be evenly distributed on fiber surface；In the calcination stage of curing molding, high molecular melt-flow is utilized
It is enriched with inorganic sol micelle at fiber overlapped points, improves the adhesive fastness of fiber overlapped points；
(2) TiO in-situ modified by modifying agent is added2Intermittent mashing is carried out after ceramic fibre film and poly- electrolysis is added
Matter obtains TiO2Ceramic fibre dispersion liquid, in-situ modified purpose are to improve the activity of ultraviolet light photocatalysis, and photocatalysis is responded
Wave-length coverage expand to visible region, the TiO2The pliability of ceramic fibre film is 5~20mN, tensile break strength 3
~5MPa；The intermittent mashing refers to successively carries out high speed mashing and low speed mashing stage by stage, and terminates in per stage laggard
It in the ranks has a rest standing, the beating rate of the high speed mashing is 1000~10000r/min, and the beating rate of the low speed mashing is
100~1000r/min；The polyelectrolyte is to carry out being added when interval is stood after high speed is beaten；Polyelectrolyte exists
Polyion and counter ion can be electrolysed out in water, wherein the oxygen-containing group of polyion can be adhered to by the hydrogen bond action between macromolecule
In fiber surface, increase the quantity of electric charge of fiber surface, increase interfibrous repulsion, prevents long fibre from sending out in the high speed mashing stage
It is raw to tangle, reunite, improve the uniformity of fiber dispersion；
(3) curing molding, which obtains fiber cross-point, has the elastic TiO for stablizing adhesion structure2Ceramic fibre sponge, elasticity
TiO2Ceramic fibre sponge is the interlaced bulk material for having multistage mesh-structured being formed there through of fiber, fiber cross-point
Be presented the bonding interconnection of effective non-hydrogen bond bonding action, the non-hydrogen bond bonding action refer between fiber by be chemically bonded into
The effective bonding interconnection of row.
As a preferred technical scheme:
A kind of photocatalysis elasticity TiO as described above2The preparation method of ceramic fibre sponge, the preparation viscosity dispersion
The concrete operations of liquid are as follows: water soluble polymer is dissolved in water after 120~480min of stirring be added inorganic sol stirring 30~
120min。
A kind of photocatalysis elasticity TiO as described above2The preparation method of ceramic fibre sponge, it is described viscosity dispersion liquid in
The content of water soluble polymer is 0.01~10wt%, and the content of inorganic sol is 0.01~5wt%.
A kind of photocatalysis elasticity TiO as described above2The preparation method of ceramic fibre sponge, the water soluble polymer
For polyacrylamide, polyacrylic acid, polymethylacrylic acid, polyvinyl alcohol, polyethylene glycol oxide, polyvinylpyrrolidone, carboxymethyl
Cellulose, methylcellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyl first
Ethylhydroxyethylcellulose or gelatin, the inorganic sol are one or more of titanium colloidal sol, silica solution and zirconium colloidal sol.
A kind of photocatalysis elasticity TiO as described above2The preparation method of ceramic fibre sponge, the modifying agent are yttrium
Salt, zirconates, zinc salt, molysite, cobalt salt, cerium salt, pink salt, manganese salt, nickel salt, lanthanum salt, thiocarbamide, carbon nanotube or g-C3N4, modifying agent with
TiO2The molar ratio of titanium atom is 0.001~0.1:1 in ceramic fibre film.
A kind of photocatalysis elasticity TiO as described above2The preparation method of ceramic fibre sponge, the yttrium salt are six hydrations
Yttrium nitrate, eight hydrated sulfuric acid yttriums or six chloride hydrate yttriums, the zirconates are zirconium acetate, zirconium nitrate or zirconium sulfate, and the zinc salt is
Acetic acid dihydrate zinc or zinc nitrate hexahydrate, the molysite be Fe(NO3)39H2O, Iron(III) chloride hexahydrate or ferric sulfate, it is described
Cobalt salt is cabaltous nitrate hexahydrate, four acetate hydrate cobalts or Cobalt monosulfate heptahydrate, and the cerium salt is six nitric hydrate ceriums, four hydration nitre
Sour cerium or cerous carbonate hydrate, the pink salt are anhydrous stannic chloride, stannous sulfate or stannous oxalate, and the manganese salt is four hydrations
Manganese acetate, Manganous sulfate monohydrate or four chloride hydrate manganese, the nickel salt are Nickel dichloride hexahydrate, nickel acetate tetrahydrate or six hydrations
Nickel sulfate, the lanthanum salt are lanthanum nitrate hexahydrate, lanthanum acetate or seven hydrated lanthanum chlorides.
A kind of photocatalysis elasticity TiO as described above2The preparation method of ceramic fibre sponge, the TiO2Ceramic fibre
The average diameter of fiber is 10~500nm in film, and relative deviation is 1~5%；
The TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 5~50nm；
The polyelectrolyte is polyacrylic acid, polymethylacrylic acid, polystyrolsulfon acid, polyvinyl sulfonic acid or polyethylene phosphorus
Acid；
The additional amount of the polyelectrolyte is TiO2The 0.01~5% of ceramic fibre film quality；
The TiO2TiO in ceramic fibre dispersion liquid2The mass fraction of ceramic fibre is 0.01~50%；
The TiO2The draw ratio of fiber is 100~10000 in ceramic fibre dispersion liquid.
A kind of photocatalysis elasticity TiO as described above2The preparation method of ceramic fibre sponge, the intermittent mashing point
For two stages, the first stage is that high speed is beaten, and is beaten number 1~5 time, beating time is 0.1~5min, when interval is stood
Between be 0.1~10min, main function is to flexible TiO2Ceramic fibre film is cut off, and TiO is formed2The pencil of ceramic fibre or
Sheet aggregation suspension；Second stage is low speed mashing, is beaten number 2~10 times, and beating time is 0.1~2min, interval
Time of repose is 0.1~5min, and main function is to break up TiO2Ceramic fiber complex and destroy it is long stapled tangle bonding knot
Structure.
The present invention is in the main function stood after high speed is beaten: when carrying out high speed mashing, the roll rate of fiber is small
In the speed of beater, at this time based on shear action, but the stress for being also easy to produce fiber radial direction is concentrated, and causes fiber to occur radial
The probability of brittle failure increases, and causes fiber length distribution irregular, the present invention dissipates ceramics by the standing in high speed pulping process
The radial stress that fiber generates in high speed pulping process reduces TiO2The randomness of ceramic fibre radial fragmentation；
The main function that the present invention is stood after low speed mashing is: in low speed pulping process, the rotary motion of fiber itself
It can make flexible TiO2Ceramic fibre glomeration, and resisting medium makes fiber after stirring stops the viscous fluid power of fiber
Get off with regard to loose, the present invention avoids causing TiO due to long agitation by the standing in low speed pulping process2Ceramic fibre is poly-
The phenomenon that integrated ball.
A kind of photocatalysis elasticity TiO as described above2The preparation method of ceramic fibre sponge, the curing molding include
Freezing, dry and high-temperature calcination.
The present invention also provides a kind of photocatalysis corresponding with above-mentioned preparation method to use elasticity TiO2 ceramic fibre sponge,
For mesh-structured, the elastic TiO of multistage2Ceramic fibre sponge with a thickness of 5~30mm, bulk density is 0.1~10mg/cm3, hole
Gap rate is 90~99%, and specific surface area is 500~1000m2/ g, in the prior art TiO2The surface of nanofiber catalysis material
Product is generally less than 500m2/ g, compression stress are less than 5KPa, and plastic deformation is less than 25% after 100 second compressions, elastic TiO2It is ceramic fine
It ties up the fiber in sponge at cross-point and passes through chemistry key connection；
Under the ultraviolet light that power is 24W, wavelength is 254nm, the Asia for being 10mg/L to concentration in 30min
The degradation rate of methyl blue solution is 90~95%, improves 5~10% compared with commercial catalyst P25；
Under the Blue-LED lamp that power is 30W, wavelength is 420nm, the Asia for being 10mg/L to concentration in 90min
The degradation rate of methyl blue solution is 90~95%, improves 85~90% compared with commercial catalyst P25；
It is 1mg/m to concentration in 30min under the ultraviolet light that power is 24W, wavelength is 254nm3First
The degradation rate of aldehyde gas is 90~95%, improves 10~15% compared with commercial catalyst P25；
It is 1mg/m to concentration in 90min under the Blue-LED lamp that power is 30W, wavelength is 420nm3First
The degradation rate of aldehyde gas is 90~95%, improves 85~90% compared with commercial catalyst P25.
The utility model has the advantages that
(1) a kind of photocatalysis elasticity TiO of the invention2Ceramic fibre sponge is the bulk material of fully fibrous structure, interior
There are controllable cell structure, resilience is high in portion.
(2) a kind of photocatalysis elasticity TiO of the invention2The preparation method of ceramic fibre sponge is guaranteeing high photocatalysis
While active, TiO is efficiently solved2The problem of easy to reunite existing for nano particle, difficult recycling.
(3) a kind of photocatalysis elasticity TiO of the invention2There is ceramic fibre sponge high porosity and fiber to take
Junction is adhered structure with stable, and it is big, fragile to efficiently solve film material existing resistance under High Speed Flow Field effect
The problem of damage.
(4) a kind of photocatalysis elasticity TiO of the invention2Ceramic fibre sponge, have extremely low bulk density be connected to
It is mesh-structured, transport for medium and provide channel abundant, significantly improve the mass transfer ability of light-catalyzed reaction, it is effective to drop
Low kinetic equation loss, has saved cost and resource.
(5) a kind of photocatalysis elasticity TiO of the invention2Ceramic fibre sponge has high specific surface area, for catalysis
Material carries out catalysis reaction and provides sufficient reactivity site, is remarkably improved catalytic efficiency.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) the obtained viscosity dispersion of silica solution stirring 120min is added after 480min being stirred in compatibilized polypropylene acidolysis in water
Liquid, the content of polyacrylic acid is 10wt% in sticky dispersion liquid, and the content of silica solution is 5wt%；
(2) TiO in-situ modified by six nitric hydrate yttriums is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 10min and polymethylacrylic acid is added simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Pottery
Porcelain fiber dispersion, the beating rate of high speed mashing are 10000r/min, and mashing number is 5 times, beating time 5min,
The beating rate of low speed mashing is 1000r/min, and mashing number is 10 times, beating time 2min, TiO2Ceramic fibre film
Pliability is 20mN, tensile break strength 5MPa, TiO2The average diameter of fiber is 10nm in ceramic fibre film, and relatively partially
Difference is 1%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 5nm, polymethyl
The additional amount of acid is TiO25%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The mass fraction of ceramic fibre
It is 50%, the draw ratio of fiber is 10, six nitric hydrate yttriums and TiO2The molar ratio of titanium atom is 0.1:1 in ceramic fibre film；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 30mm, bulk density is
10mg/cm3, porosity 90%, specific surface area 500m2/ g, compression stress 4.9KPa, plastic deformation after 100 second compressions
It is 3%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is by chemistry key connection, power is 24W, wavelength is
Under the ultraviolet light of 254nm, the elastic TiO of 10mg2Ceramic fibre sponge is 10mg/L to concentration in 30min, volume is
The degradation rate of the methylene blue solution of 100mL is 90%, improves 5% compared with commercial catalyst P25.
Comparative example 1
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, substantially with embodiment 1, the difference is that
The TiO in-situ modified by six nitric hydrate yttriums is added2High speed mashing is only carried out after ceramic fibre film, is not carried out intermittent
Mashing, pulping process are as follows: progress high speed mashing first, beating rate 10000r/min, mashing number are 5 times, beating time
For 5min, polymethylacrylic acid is then added, finally continues high speed and is beaten, beating rate 10000r/min, mashing time
Number is 10 times, beating time 2min.Final elasticity TiO obtained2Ceramic fibre sponge is stratiform packed structures, with a thickness of
10mm, bulk density 35mg/cm3, porosity 70%, specific surface area 120m2/ g, compression stress 5KPa, 100 pressures
Plastic deformation is 3% after contracting, elastic TiO2Fiber in ceramic fibre sponge at cross-point is connected to power by chemical bond and is
Under 24W, the ultraviolet light that wavelength is 254nm, the elastic TiO of 10mg2Ceramic fibre sponge is to concentration in 30min
The degradation rate for the methylene blue solution that 10mg/L, volume are 100mL is 70%, reduces 15% compared with commercial catalyst P25.It will
Embodiment 1 and the comparison of comparative example 1 are as can be seen that the present invention can be improved elastic TiO using intermittent mashing2Ceramic fibre sponge
Specific surface area, reduce its bulk density, improve its porosity, and then promote its photocatalysis performance.
Embodiment 2
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polyacrylamide is dissolved in water after stirring 120min and the obtained viscosity dispersion of titanium colloidal sol stirring 30min is added
Liquid, the content of polyacrylamide is 0.01wt% in sticky dispersion liquid, and the content of titanium colloidal sol is 0.01wt%；
(2) TiO modified by eight hydrated sulfuric acid yttriums is added2High speed mashing is first carried out after ceramic fibre film, then interval
It stands 0.1min and polyacrylic acid is added simultaneously, then carry out low speed mashing, TiO is made after standing 0.1min in last interval2It is ceramic fine
Dispersion liquid is tieed up, the beating rate of high speed mashing is 1000r/min, and mashing number is 1 time, beating time 0.1min, low
The beating rate of speed mashing is 100r/min, and mashing number is 2 times, beating time 0.1min, TiO2Ceramic fibre film it is soft
Softness is 5mN, tensile break strength 3MPa, TiO2The average diameter of fiber is 500nm in ceramic fibre film, and relatively partially
Difference is 5%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 50nm, polyacrylic acid
Additional amount be TiO20.01%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The quality of ceramic fibre point
Number is 0.01%, and the draw ratio of fiber is 10000, eight hydrated sulfuric acid yttriums and TiO2The molar ratio of titanium atom is in ceramic fibre film
0.001:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 5mm, bulk density is
0.1mg/cm3, porosity 99%, specific surface area 1000m2/ g, compression stress 2KPa, plastic deformation after 100 second compressions
It is 24%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is by chemistry key connection, power is 24W, wavelength is
Under the ultraviolet light of 254nm, the elastic TiO of 10mg2Ceramic fibre sponge is 10mg/L to concentration in 30min, volume is
The degradation rate of the methylene blue solution of 100mL is 95%, improves 10% compared with commercial catalyst P25.
Embodiment 3
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polymethylacrylic acid is dissolved in water after stirring 140min and the obtained viscosity point of zirconium colloidal sol stirring 40min is added
Dispersion liquid, the content of polymethylacrylic acid is 0.05wt% in sticky dispersion liquid, and the content of zirconium colloidal sol is 0.05wt%；
(2) TiO in-situ modified by six chloride hydrate yttriums is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 0.5min and polystyrolsulfon acid is added simultaneously, then carries out low speed mashing, and last interval is made after standing 0.5min
TiO2Ceramic fibre dispersion liquid, the beating rate of high speed mashing are 1200r/min, and mashing number is 2 times, and beating time is
0.5min, the beating rate of low speed mashing are 120r/min, and mashing number is 2 times, beating time 0.5min, TiO2It is ceramic fine
The pliability for tieing up film is 6mN, tensile break strength 3.5MPa, TiO2The average diameter of fiber is 493nm in ceramic fibre film,
And relative deviation is 4.5%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is
45nm, the additional amount of polystyrolsulfon acid are TiO20.05%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2
The mass fraction of ceramic fibre is 0.05%, and the draw ratio of fiber is 150, six chloride hydrate yttriums and TiO2Titanium in ceramic fibre film
The molar ratio of atom is 0.005:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 6mm, bulk density is
9mg/cm3, porosity 90.5%, specific surface area 550m2/ g, compression stress 2.2KPa, plastic deformation after 100 second compressions
It is 23%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is by chemistry key connection, power is 24W, wavelength is
Under the ultraviolet light of 254nm, the elastic TiO of 10mg2Ceramic fibre sponge is 10mg/L to concentration in 30min, volume is
The degradation rate of the methylene blue solution of 100mL is 92%, improves 7% compared with commercial catalyst P25.
Embodiment 4
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) it dissolves polyvinyl alcohol in water and the mixture (mass ratio of titanium colloidal sol and silica solution is added after stirring 150min
1:1) sticky dispersion liquid is made in stirring 50min, and the content of polyvinyl alcohol is 0.15wt%, titanium colloidal sol and silicon in sticky dispersion liquid
The total content of colloidal sol is 0.15wt%；
(2) TiO in-situ modified by zirconium acetate is added2High speed mashing is first carried out after ceramic fibre film, then interval is quiet
It sets 1min while polyvinyl sulfonic acid is added, then carry out low speed mashing, TiO is made after standing 1min in last interval2Ceramic fibre point
Dispersion liquid, the beating rate of high speed mashing are 1400r/min, and mashing number is 3 times, beating time 1min, low speed mashing
Beating rate be 150r/min, mashing number be 4 times, beating time 1min, TiO2The pliability of ceramic fibre film is
7mN, tensile break strength 4MPa, TiO2The average diameter of fiber is 460nm in ceramic fibre film, and relative deviation is 4%,
TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 40nm, the addition of polyvinyl sulfonic acid
Amount is TiO20.15%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The mass fraction of ceramic fibre is
0.15%, the draw ratio of fiber is 200, zirconium acetate and TiO2The molar ratio of titanium atom is 0.01:1 in ceramic fibre film；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 8mm, bulk density is
8mg/cm3, porosity 91%, specific surface area 630m2/ g, compression stress 2.4KPa, after 100 second compressions plastic deformation be
22%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is by chemistry key connection, power is 24W, wavelength is
Under the ultraviolet light of 254nm, the elastic TiO of 10mg2Ceramic fibre sponge is 10mg/L to concentration in 30min, volume is
The degradation rate of the methylene blue solution of 100mL is 92.5%, improves 7.5% compared with commercial catalyst P25.
Embodiment 5
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polyethylene glycol oxide is dissolved in water to the mixing that titanium colloidal sol, silica solution and zirconium colloidal sol are added after stirring 160min
Object (mass ratio 1:2:2) stirs 50min and sticky dispersion liquid is made, and the content of polyethylene glycol oxide is 0.2wt% in sticky dispersion liquid,
The total content of titanium colloidal sol, silica solution and zirconium colloidal sol is 0.2wt%；
(2) TiO in-situ modified by zirconium nitrate is added2High speed mashing is first carried out after ceramic fibre film, then interval is quiet
It sets 2min while polyvinyl is added, then carry out low speed mashing, TiO is made after standing 2min in last interval2Ceramic fibre point
Dispersion liquid, the beating rate of high speed mashing are 1800r/min, and mashing number is 4 times, beating time 2min, low speed mashing
Beating rate be 190r/min, mashing number be 4 times, beating time 2min, TiO2The pliability of ceramic fibre film is
8mN, tensile break strength 5MPa, TiO2The average diameter of fiber is 450nm in ceramic fibre film, and relative deviation is
3.5%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 35nm, polyvinyl
Additional amount be TiO20.2%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The quality of ceramic fibre point
Number is 0.2%, and the draw ratio of fiber is 220, zirconium nitrate and TiO2The molar ratio of titanium atom is 0.015:1 in ceramic fibre film；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 10mm, bulk density is
7.5mg/cm3, porosity 91.5%, specific surface area 650m2/ g, compression stress 2.5KPa, plasticity shape after 100 second compressions
Become 21%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is 24W, wavelength in power by chemistry key connection
For under the ultraviolet light of 254nm, the elastic TiO of 10mg2Ceramic fibre sponge is 10mg/L, volume to concentration in 30min
Degradation rate for the methylene blue solution of 100mL is 93%, improves 8% compared with commercial catalyst P25.
Embodiment 6
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polyvinylpyrrolidone is dissolved in water after stirring 180min and the obtained viscosity of titanium colloidal sol stirring 60min is added
Dispersion liquid, the content of polyvinylpyrrolidone is 1wt% in sticky dispersion liquid, and the content of titanium colloidal sol is 1wt%；
(2) TiO in-situ modified by zirconium sulfate is added2High speed mashing is first carried out after ceramic fibre film, then interval is quiet
It sets 3min while polyacrylic acid is added, then carry out low speed mashing, TiO is made after standing 3min in last interval2Ceramic fibre dispersion
Liquid, the beating rate of high speed mashing are 2000r/min, and mashing number is 3 times, beating time 4min, low speed mashing
Beating rate is 210r/min, and mashing number is 5 times, beating time 1.5min, TiO2The pliability of ceramic fibre film is
10mN, tensile break strength 4.5MPa, TiO2The average diameter of fiber is 420nm in ceramic fibre film, and relative deviation is
3%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 30nm, and polyacrylic acid adds
Entering amount is TiO20.5%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The mass fraction of ceramic fibre is
1%, the draw ratio of fiber is 250, zirconium sulfate and TiO2The molar ratio of titanium atom is 0.02:1 in ceramic fibre film；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 12mm, bulk density is
7mg/cm3, porosity 92%, specific surface area 760m2/ g, compression stress 2.7KPa, after 100 second compressions plastic deformation be
20%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is by chemistry key connection, power is 24W, wavelength is
Under the ultraviolet light of 254nm, the elastic TiO of 10mg2Ceramic fibre sponge is 1mg/m to concentration in 30min3, volume be
1m3Formaldehyde gas degradation rate be 90%, improve 10% compared with commercial catalyst P25.
Embodiment 7
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) carboxymethyl cellulose is dissolved in water after stirring 200min and the obtained viscosity point of titanium colloidal sol stirring 65min is added
Dispersion liquid, the content of carboxymethyl cellulose is 1.5wt% in sticky dispersion liquid, and the content of titanium colloidal sol is 1.5wt%；
(2) TiO in-situ modified by acetic acid dihydrate zinc is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 3.5min and polyacrylic acid is added simultaneously, then carries out low speed mashing, and TiO is made after standing 3.5min in last interval2Pottery
Porcelain fiber dispersion, the beating rate of high speed mashing are 2200r/min, and mashing number is 5 times, beating time 5min,
The beating rate of low speed mashing is 230r/min, and mashing number is 6 times, beating time 2min, TiO2Ceramic fibre film it is soft
Softness is 11mN, tensile break strength 5MPa, TiO2The average diameter of fiber is 400nm in ceramic fibre film, and relatively partially
Difference is 3.5%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 28nm, polypropylene
The additional amount of acid is TiO21%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The mass fraction of ceramic fibre
It is 1.5%, the draw ratio of fiber is 270, acetic acid dihydrate zinc and TiO2The molar ratio of titanium atom is in ceramic fibre film
0.023:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 13mm, bulk density is
8mg/cm3, porosity 92.5%, specific surface area 780m2/ g, compression stress 2.9KPa, plastic deformation after 100 second compressions
It is 19%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is by chemistry key connection, power is 24W, wavelength is
Under the ultraviolet light of 254nm, the elastic TiO of 10mg2Ceramic fibre sponge is 1mg/m to concentration in 30min3, volume be
1m3Formaldehyde gas degradation rate be 92%, improve 12% compared with commercial catalyst P25.
Embodiment 8
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) methylcellulose is dissolved in water to the mixture (quality that silica solution and zirconium colloidal sol are added after stirring 210min
Than 2:1) the obtained sticky dispersion liquid of 70min is stirred, the content of methylcellulose is 2wt%, silica solution and zirconium in sticky dispersion liquid
The total content of colloidal sol is 1.8wt%；
(2) TiO in-situ modified by zinc nitrate hexahydrate is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 4min and polymethylacrylic acid is added simultaneously, then carries out low speed mashing, and TiO is made after standing 4min in last interval2Pottery
Porcelain fiber dispersion, the beating rate of high speed mashing are 2500r/min, and mashing number is 1 time, beating time 3min,
The beating rate of low speed mashing is 240r/min, and mashing number is 7 times, beating time 2min, TiO2Ceramic fibre film it is soft
Softness is 12mN, tensile break strength 5MPa, TiO2The average diameter of fiber is 380nm in ceramic fibre film, and relatively partially
Difference is 3%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 26nm, poly- methyl-prop
The additional amount of olefin(e) acid is TiO21.5%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The quality of ceramic fibre
Score is 2%, and the draw ratio of fiber is 300, zinc nitrate hexahydrate and TiO2The molar ratio of titanium atom is in ceramic fibre film
0.026:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 15mm, bulk density is
7mg/cm3, porosity 93%, specific surface area 800m2/ g, compression stress 3KPa, after 100 second compressions plastic deformation be
18%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is by chemistry key connection, power is 24W, wavelength is
Under the ultraviolet light of 254nm, the elastic TiO of 10mg2Ceramic fibre sponge is 1mg/m to concentration in 30min3, volume be
1m3Formaldehyde gas degradation rate be 95%, improve 15% compared with commercial catalyst P25.
Embodiment 9
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) ethyl cellulose is dissolved in water after stirring 230min and the obtained viscosity dispersion of silica solution stirring 75min is added
Liquid, the content of ethyl cellulose is 2.3wt% in sticky dispersion liquid, and the content of silica solution is 2wt%；
(2) TiO in-situ modified by Fe(NO3)39H2O is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 5min and polymethylacrylic acid is added simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Pottery
Porcelain fiber dispersion, the beating rate of high speed mashing are 2800r/min, and mashing number is 5 times, beating time 5min,
The beating rate of low speed mashing is 260r/min, and mashing number is 8 times, beating time 2min, TiO2Ceramic fibre film it is soft
Softness is 13mN, tensile break strength 5MPa, TiO2The average diameter of fiber is 350nm in ceramic fibre film, and relatively partially
Difference is 2.5%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 25nm, poly- methyl
The additional amount of acrylic acid is TiO22%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The quality of ceramic fibre
Score is 5%, and the draw ratio of fiber is 500, Fe(NO3)39H2O and TiO2The molar ratio of titanium atom is in ceramic fibre film
0.029:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 16mm, bulk density is
6.5mg/cm3, porosity 93.5%, specific surface area 850m2/ g, compression stress 3.2KPa, plasticity shape after 100 second compressions
Become 17%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is 30W, wavelength in power by chemistry key connection
For under the Blue-LED lamp of 420nm, the elastic TiO of 10mg2Ceramic fibre sponge is 10mg/L, body to concentration in 90min
The degradation rate for the methylene blue solution that product is 100mL is 90%, improves 85% compared with commercial catalyst P25.
Embodiment 10
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) hydroxyethyl cellulose is dissolved in water after stirring 250min and the obtained viscosity point of silica solution stirring 80min is added
Dispersion liquid, the content of hydroxyethyl cellulose is 2.7wt% in sticky dispersion liquid, and the content of silica solution is 2.5wt%；
(2) TiO in-situ modified by Iron(III) chloride hexahydrate is added2High speed mashing is first carried out after ceramic fibre film, so
Interval stands 6min and polystyrolsulfon acid is added simultaneously afterwards, then carries out low speed mashing, and TiO is made after standing 5min in last interval2
Ceramic fibre dispersion liquid, the beating rate of high speed mashing are 3000r/min, and mashing number is 4 times, and beating time is
4min, the beating rate of low speed mashing are 280r/min, and mashing number is 9 times, beating time 1min, TiO2Ceramic fibre film
Pliability be 14mN, tensile break strength 5MPa, TiO2The average diameter of fiber is 320nm, and phase in ceramic fibre film
It is 2.3%, TiO to deviation2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 22nm, is gathered
The additional amount of styrene sulfonic acid is TiO22.2%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2Ceramic fibre
Mass fraction be 10%, the draw ratio of fiber is 1000, Iron(III) chloride hexahydrate and TiO2Titanium atom in ceramic fibre film
Molar ratio is 0.032:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 18mm, bulk density is
6mg/cm3, porosity 94%, specific surface area 880m2/ g, compression stress 3.5KPa, after 100 second compressions plastic deformation be
16%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is by chemistry key connection, power is 30W, wavelength is
Under the Blue-LED lamp of 420nm, the elastic TiO of 10mg2Ceramic fibre sponge is 10mg/L, volume to concentration in 90min
Degradation rate for the methylene blue solution of 100mL is 95%, improves 90% compared with commercial catalyst P25.
Embodiment 11
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) hydroxypropyl cellulose is dissolved in water after stirring 280min and the obtained viscosity point of silica solution stirring 90min is added
Dispersion liquid, the content of hydroxypropyl cellulose is 3wt% in sticky dispersion liquid, and the content of silica solution is 2.6wt%；
(2) TiO in-situ modified by ferric sulfate is added2High speed mashing is first carried out after ceramic fibre film, then interval is quiet
It sets 7min while polystyrolsulfon acid is added, then carry out low speed mashing, TiO is made after standing 3min in last interval2Ceramic fibre
Dispersion liquid, the beating rate of high speed mashing are 3500r/min, and mashing number is 5 times, and beating time 5min, low speed is beaten
The beating rate of slurry is 300r/min, and mashing number is 10 times, beating time 2min, TiO2The pliability of ceramic fibre film is
15mN, tensile break strength 3MPa, TiO2The average diameter of fiber is 300nm in ceramic fibre film, and relative deviation is
2%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 20nm, polystyrolsulfon acid
Additional amount be TiO22.5%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The mass fraction of ceramic fibre
It is 13%, the draw ratio of fiber is 2000, ferric sulfate and TiO2The molar ratio of titanium atom is 0.036:1 in ceramic fibre film；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 19mm, bulk density is
.5mg/cm3, porosity 94.5%, specific surface area 850m2/ g, compression stress 3.7KPa, plasticity shape after 100 second compressions
Become 15%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is 30W, wavelength in power by chemistry key connection
For under the Blue-LED lamp of 420nm, the elastic TiO of 10mg2Ceramic fibre sponge is 10mg/L, body to concentration in 90min
The degradation rate for the methylene blue solution that product is 100mL is 92%, improves 87% compared with commercial catalyst P25.
Embodiment 12
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) hydroxypropyl methyl cellulose is dissolved in water after stirring 300min that zirconium colloidal sol stirring 95min is added and is made and glued
Property dispersion liquid, the content of hydroxypropyl methyl cellulose is 3.6wt% in sticky dispersion liquid, and the content of zirconium colloidal sol is 2.8wt%；
(2) TiO in-situ modified by cabaltous nitrate hexahydrate is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 7.5min and polyvinyl sulfonic acid is added simultaneously, then carries out low speed mashing, and TiO is made after standing 3.5min in last interval2
Ceramic fibre dispersion liquid, the beating rate of high speed mashing are 4500r/min, and mashing number is 5 times, and beating time is
5min, the beating rate of low speed mashing are 400r/min, and mashing number is 10 times, beating time 2min, TiO2Ceramic fibre
The pliability of film is 16mN, tensile break strength 5MPa, TiO2The average diameter of fiber is 250nm in ceramic fibre film, and
Relative deviation is 1.9%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 18nm,
The additional amount of polyvinyl sulfonic acid is TiO22.9%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2Ceramic fibre
Mass fraction be 18%, the draw ratio of fiber is 3000, cabaltous nitrate hexahydrate and TiO2Titanium atom rubs in ceramic fibre film
You are than being 0.038:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 20mm, bulk density is
4.5mg/cm3, porosity 95%, specific surface area 600m2/ g, compression stress 3.9KPa, plastic deformation after 100 second compressions
It is 14%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is by chemistry key connection, power is 30W, wavelength is
Under the Blue-LED lamp of 420nm, the elastic TiO of 10mg2Ceramic fibre sponge is 10mg/L, volume to concentration in 90min
Degradation rate for the methylene blue solution of 100mL is 91.5%, improves 86.5% compared with commercial catalyst P25.
Embodiment 13
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) zirconium colloidal sol stirring 100min system is added after hydroxymethylhydroxyethyl cellulose dissolution being stirred 320min in water
Sticky dispersion liquid is obtained, the content of hydroxymethylhydroxyethyl cellulose is 4wt% in sticky dispersion liquid, and the content of zirconium colloidal sol is
3.0wt%；
(2) TiO in-situ modified by four acetate hydrate cobalts is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 8min and polyvinyl sulfonic acid is added simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Ceramics
Fiber dispersion, the beating rate of high speed mashing are 5000r/min, and mashing number is 5 times, beating time 5min, low
The beating rate of speed mashing is 480r/min, and mashing number is 10 times, beating time 2min, TiO2Ceramic fibre film it is soft
Softness is 16.5mN, tensile break strength 5MPa, TiO2The average diameter of fiber is 200nm in ceramic fibre film, and opposite
Deviation is 1.8%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 16nm, poly- second
The additional amount of alkene sulfonic acid is TiO23%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The quality of ceramic fibre
Score is 20%, and the draw ratio of fiber is 4000, four acetate hydrate cobalts and TiO2The molar ratio of titanium atom is in ceramic fibre film
0.041:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 21mm, bulk density is
4mg/cm3, porosity 96%, specific surface area 900m2/ g, compression stress 4KPa, after 100 second compressions plastic deformation be
12%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is by chemistry key connection, power is 30W, wavelength is
Under the Blue-LED lamp of 420nm, the elastic TiO of 10mg2Ceramic fibre sponge is 10mg/L to concentration in 90min, volume is
The degradation rate of the methylene blue solution of 100mL is 95%, improves 90% compared with commercial catalyst P25.
Embodiment 14
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) the obtained sticky dispersion liquid of titanium colloidal sol stirring 105min is added after Gelatin to be stirred to 350min in water, glues
Property dispersion liquid in the content of gelatin be 4.2wt%, the content of titanium colloidal sol is 3.2wt%；
(2) TiO in-situ modified by Cobalt monosulfate heptahydrate is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 9min and polyvinyl is added simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Ceramics
Fiber dispersion, the beating rate of high speed mashing are 6600r/min, and mashing number is 5 times, beating time 5min, low
The beating rate of speed mashing is 500r/min, and mashing number is 10 times, beating time 2min, TiO2The softness of ceramic fibre
Degree is 17mN, tensile break strength 5MPa, TiO2The average diameter of fiber is 180nm, and relative deviation in ceramic fibre film
For 1.6%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 12nm, polyethylene phosphorus
The additional amount of acid is TiO23.3%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The quality of ceramic fibre film
Score is 25%, and the draw ratio of fiber is 5000, Cobalt monosulfate heptahydrate and TiO2The molar ratio of titanium atom is in ceramic fibre film
0.044:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 23mm, bulk density is
3mg/cm3, porosity 96.5%, specific surface area 500m2/ g, compression stress 4.3KPa, plastic deformation after 100 second compressions
It is 10%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is by chemistry key connection, power is 30W, wavelength is
Under the Blue-LED lamp of 420nm, the elastic TiO of 10mg2Ceramic fibre sponge is 1mg/m to concentration in 90min3, volume be
1m3Formaldehyde gas degradation rate be 90%, improve 85% compared with commercial catalyst P25.
Embodiment 15
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) the obtained sticky dispersion liquid of titanium colloidal sol stirring 110min is added after Gelatin to be stirred to 380min in water, glues
Property dispersion liquid in the content of gelatin be 6wt%, the content of titanium colloidal sol is 3.5wt%；
(2) TiO in-situ modified by six nitric hydrate ceriums is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 9.5min and polyvinyl is added simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Pottery
Porcelain fiber dispersion, the beating rate of high speed mashing are 7000r/min, and mashing number is 5 times, beating time 5min,
The beating rate of low speed mashing is 600r/min, and mashing number is 10 times, beating time 2min, TiO2Ceramic fibre film it is soft
Softness is 17.5mN, tensile break strength 5MPa, TiO2The average diameter of fiber is 150nm in ceramic fibre film, and opposite
Deviation is 1.3%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 10nm, poly- second
The additional amount of alkenyl phosphoric acid is TiO23.5%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The matter of ceramic fibre
Measuring score is 30%, and the draw ratio of fiber is 6000, six nitric hydrate ceriums and TiO2The molar ratio of titanium atom in ceramic fibre film
For 0.047:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 25mm, bulk density is
2mg/cm3, porosity 97%, specific surface area 600m2/ g, compression stress 4.5KPa, after 100 second compressions plastic deformation be
8%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is by chemistry key connection, power is 30W, wavelength is
Under the Blue-LED lamp of 420nm, the elastic TiO of 10mg2Ceramic fibre sponge is 10mg/L to concentration in 90min, volume is
The degradation rate of the methylene blue solution of 100mL is 93%, improves 88% compared with commercial catalyst P25.
Embodiment 16
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polyacrylamide is dissolved in water after stirring 420min and the obtained viscosity dispersion of titanium colloidal sol stirring 113min is added
Liquid, the content of polyacrylamide is 8wt% in sticky dispersion liquid, and the content of titanium colloidal sol is 3.8wt%；
(2) TiO in-situ modified by four nitric hydrate ceriums is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 10min and polyvinyl is added simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Pottery
Porcelain fiber dispersion, the beating rate of high speed mashing are 8000r/min, and mashing number is 5 times, beating time 5min,
The beating rate of low speed mashing is 700r/min, and mashing number is 10 times, beating time 2min, TiO2Ceramic fibre film
Pliability is 18mN, tensile break strength 5MPa, TiO2The average diameter of fiber is 80nm in ceramic fibre film, and opposite
Deviation is 1.2%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 8nm, polyethylene
The additional amount of phosphoric acid is TiO23.95%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The matter of ceramic fibre
Measuring score is 38%, and the draw ratio of fiber is 7000, four nitric hydrate ceriums and TiO2The molar ratio of titanium atom in ceramic fibre film
For 0.05:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 27mm, bulk density is
1mg/cm3, porosity 98%, specific surface area 800m2/ g, compression stress 4.55KPa, plastic deformation after 100 second compressions
It is 5%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is by chemistry key connection, power is 30W, wavelength is
Under the Blue-LED lamp of 420nm, the elastic TiO of 10mg2Ceramic fibre sponge is 1mg/m to concentration in 90min3, volume be
1m3Formaldehyde gas degradation rate be 92.5%, improve 87.5% compared with commercial catalyst P25.
Embodiment 17
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polyacrylamide is dissolved in water after stirring 460min and the obtained viscosity dispersion of titanium colloidal sol stirring 120min is added
Liquid, the content of polyacrylamide is 9wt% in sticky dispersion liquid, and the content of titanium colloidal sol is 4.5wt%；
(2) TiO in-situ modified by cerous carbonate hydrate is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 10min and polyvinyl is added simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Pottery
Porcelain fiber dispersion, the beating rate of high speed mashing are 8200r/min, and mashing number is 5 times, beating time 5min,
The beating rate of low speed mashing is 850r/min, and mashing number is 10 times, beating time 2min, TiO2Ceramic fibre film
Pliability is 18.5mN, tensile break strength 3MPa, TiO2The average diameter of fiber is 50nm in ceramic fibre film, and opposite
Deviation is 1.1%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 7nm, polyethylene
The additional amount of phosphoric acid is TiO24%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The quality of ceramic fibre point
Number is 40%, and the draw ratio of fiber is 8000, cerous carbonate hydrate and TiO2The molar ratio of titanium atom is in ceramic fibre film
0.052:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, with a thickness of 27.5mm, bulk density
For 0.9mg/cm3, porosity 98.5%, specific surface area 850m2/ g, compression stress 4.58KPa are moulded after 100 second compressions
Property shape becomes 4.9%, elastic TiO2Fiber in ceramic fibre sponge at cross-point by chemistry key connection, power be 30W,
Wavelength is the elastic TiO of 10mg under the Blue-LED lamp of 420nm2Ceramic fibre sponge is 1mg/m to concentration in 90min3、
Volume is 1m3Formaldehyde gas degradation rate be 94%, improve 89% compared with commercial catalyst P25.
Embodiment 18
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polyacrylic acid is dissolved in water after stirring 462min and the obtained viscosity dispersion of titanium colloidal sol stirring 120min is added
Liquid, the content of polyacrylic acid is 9.1wt% in sticky dispersion liquid, and the content of titanium colloidal sol is 4.55wt%；
(2) TiO in-situ modified by anhydrous stannic chloride is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 10min and polyvinyl is added simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Pottery
Porcelain fiber dispersion, the beating rate of high speed mashing are 8300r/min, and mashing number is 5 times, beating time 5min,
The beating rate of low speed mashing is 870r/min, and mashing number is 10 times, beating time 2min, TiO2Ceramic fibre film
Pliability is 18.7mN, tensile break strength 3MPa, TiO2The average diameter of fiber is 48nm in ceramic fibre film, and opposite
Deviation is 1.08%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 6.8nm, is gathered
The additional amount of ethylene phosphoric acid is TiO24.05%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2Ceramic fibre
Mass fraction be 41%, the draw ratio of fiber is 8200, anhydrous stannic chloride and TiO2Titanium atom rubs in ceramic fibre film
You are than being 0.055:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, with a thickness of 27.8mm, bulk density
For 0.85mg/cm3, porosity 98.6%, specific surface area 860m2/ g, compression stress 4.60KPa are moulded after 100 second compressions
Property shape becomes 4.8%, elastic TiO2Fiber in ceramic fibre sponge at cross-point by chemistry key connection, power be 30W,
Wavelength is the elastic TiO of 10mg under the Blue-LED lamp of 420nm2Ceramic fibre sponge is 10mg/ to concentration in 90min
L, the degradation rate for the methylene blue solution that volume is 100mL is 93.5%, improves 88.5% compared with commercial catalyst P25.
Embodiment 19
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polyacrylic acid is dissolved in water after stirring 465min and the obtained viscosity dispersion of silica solution stirring 120min is added
Liquid, the content of polyacrylic acid is 9.2wt% in sticky dispersion liquid, and the content of silica solution is 4.57wt%；
(2) TiO in-situ modified by stannous sulfate is added2High speed mashing is first carried out after ceramic fibre film, then interval
It stands 10min and polymethylacrylic acid is added simultaneously, then carry out low speed mashing, TiO is made after standing 5min in last interval2Ceramics
Fiber dispersion, the beating rate of high speed mashing are 8500r/min, and mashing number is 5 times, beating time 5min, low
The beating rate of speed mashing is 875r/min, and mashing number is 10 times, beating time 2min, TiO2The softness of ceramic fibre film
Degree is 18.8mN, tensile break strength 3MPa, TiO2The average diameter of fiber is 45nm in ceramic fibre film, and relatively partially
Difference is 1.1%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 6.7nm, poly- methyl
The additional amount of acrylic acid is TiO24.1%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The matter of ceramic fibre
Measuring score is 41.5%, and the draw ratio of fiber is 8400, stannous sulfate and TiO2The molar ratio of titanium atom is in ceramic fibre film
0.058:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, and with a thickness of 28mm, bulk density is
0.8mg/cm3, porosity 98.7%, specific surface area 870m2/ g, compression stress 4.63KPa, plasticity after 100 second compressions
Shape becomes 4.7%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is 30W, wave in power by chemistry key connection
Under the Blue-LED lamp of a length of 420nm, the elastic TiO of 10mg2Ceramic fibre sponge in 90min to concentration be 10mg/L,
The degradation rate for the methylene blue solution that volume is 100mL is 93%, improves 88% compared with commercial catalyst P25.
Embodiment 20
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polyacrylic acid is dissolved in water after stirring 468min and the obtained viscosity dispersion of zirconium colloidal sol stirring 120min is added
Liquid, the content of polyacrylic acid is 9.3wt% in sticky dispersion liquid, and the content of zirconium colloidal sol is 4.59wt%；
(2) TiO in-situ modified by stannous oxalate is added2High speed mashing is first carried out after ceramic fibre film, then interval
It stands 10min and polymethylacrylic acid is added simultaneously, then carry out low speed mashing, TiO is made after standing 5min in last interval2Ceramics
Fiber dispersion, the beating rate of high speed mashing are 8650r/min, and mashing number is 5 times, beating time 5min, low
The beating rate of speed mashing is 855r/min, and mashing number is 10 times, beating time 2min, TiO2The softness of ceramic fibre film
Degree is 18.9mN, tensile break strength 3MPa, TiO2The average diameter of fiber is 43nm in ceramic fibre film, and relatively partially
Difference is 1.05%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 6.6nm, poly- first
The additional amount of base acrylic acid is TiO24.2%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2Ceramic fibre
Mass fraction is 42%, and the draw ratio of fiber is 8500, stannous oxalate and TiO2The molar ratio of titanium atom is in ceramic fibre film
0.061:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, with a thickness of 28.1mm, bulk density
For 0.75mg/cm3, porosity 98.8%, specific surface area 880m2/ g, compression stress 4.6KPa are moulded after 100 second compressions
Property shape becomes 4.6%, elastic TiO2Fiber in ceramic fibre sponge at cross-point by chemistry key connection, power be 30W,
Wavelength is the elastic TiO of 10mg under the Blue-LED lamp of 420nm2Ceramic fibre sponge is 1mg/m to concentration in 90min3、
Volume is 1m3Formaldehyde gas degradation rate be 93.5%, improve 88.5% compared with commercial catalyst P25.
Embodiment 21
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polyacrylic acid is dissolved in water after stirring 470min and the obtained viscosity dispersion of titanium colloidal sol stirring 120min is added
Liquid, the content of polyacrylic acid is 9.35wt% in sticky dispersion liquid, and the content of titanium colloidal sol is 4.62wt%；
(2) TiO in-situ modified by four acetate hydrate manganese is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 10min and polystyrolsulfon acid is added simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Pottery
Porcelain fiber dispersion, the beating rate of high speed mashing are 8700r/min, and mashing number is 5 times, beating time 5min,
The beating rate of low speed mashing is 860r/min, and mashing number is 8 times, beating time 2min, TiO2Ceramic fibre film it is soft
Softness is 19mN, tensile break strength 3MPa, TiO2The average diameter of fiber is 42nm, and relative deviation in ceramic fibre film
For 1.1%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 6.4nm, polyphenyl second
The additional amount of alkene sulfonic acid is TiO24.25%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2Ceramic fibre
Mass fraction is 42.5%, and the draw ratio of fiber is 8600, four acetate hydrate manganese and TiO2Titanium atom rubs in ceramic fibre film
You are than being 0.063:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, with a thickness of 28.3mm, bulk density
For 0.7mg/cm3, porosity 98.5%, specific surface area 885m2/ g, compression stress 4.62KPa are moulded after 100 second compressions
Property shape becomes 4.5%, elastic TiO2Fiber in ceramic fibre sponge at cross-point by chemistry key connection, power be 30W,
Wavelength is the elastic TiO of 10mg under the Blue-LED lamp of 420nm2Ceramic fibre sponge is 10mg/ to concentration in 90min
L, the degradation rate for the methylene blue solution that volume is 100mL is 94%, improves 89% compared with commercial catalyst P25.
Embodiment 22
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polymethylacrylic acid is dissolved in water after stirring 460min and the obtained viscosity point of zirconium colloidal sol stirring 120min is added
Dispersion liquid, the content of polymethylacrylic acid is 9.4wt% in sticky dispersion liquid, and the content of zirconium colloidal sol is 4.63wt%；
(2) TiO in-situ modified by Manganous sulfate monohydrate is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 10min and polystyrolsulfon acid is added simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Pottery
Porcelain fiber dispersion, the beating rate of high speed mashing are 8750r/min, and mashing number is 5 times, beating time 5min,
The beating rate of low speed mashing is 870r/min, and mashing number is 6 times, beating time 2min, TiO2Ceramic fibre film it is soft
Softness is 19.2mN, tensile break strength 3MPa, TiO2The average diameter of fiber is 42nm in ceramic fibre film, and relatively partially
Difference is 1.1%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 6nm, polyphenyl second
The additional amount of alkene sulfonic acid is TiO24.3%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The matter of ceramic fibre
Measuring score is 43%, and the draw ratio of fiber is 8700, Manganous sulfate monohydrate and TiO2The molar ratio of titanium atom in ceramic fibre film
For 0.065:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, with a thickness of 28.5mm, bulk density
For 0.65mg/cm3, porosity 98.6%, specific surface area 890m2/ g, compression stress 4.65KPa are moulded after 100 second compressions
Property shape becomes 4.4%, elastic TiO2Fiber in ceramic fibre sponge at cross-point by chemistry key connection, power be 30W,
Wavelength is the elastic TiO of 10mg under the Blue-LED lamp of 420nm2Ceramic fibre sponge is 1mg/m to concentration in 90min3、
Volume is 1m3Formaldehyde gas degradation rate be 95%, improve 90% compared with commercial catalyst P25.
Embodiment 23
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polymethylacrylic acid is dissolved in water after stirring 472min and the obtained viscosity point of silica solution stirring 120min is added
Dispersion liquid, the content of polymethylacrylic acid is 9.5wt% in sticky dispersion liquid, and the content of silica solution is 4.65wt%；
(2) TiO in-situ modified by four chloride hydrate manganese is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 10min and polyvinyl is added simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Ceramics
Fiber dispersion, the beating rate of high speed mashing are 8800r/min, and mashing number is 5 times, beating time 5min, low
The beating rate of speed mashing is 870r/min, and mashing number is 10 times, beating time 2min, TiO2Ceramic fibre film it is soft
Softness is 19.3mN, tensile break strength 3MPa, TiO2The average diameter of fiber is 40nm in ceramic fibre film, and relatively partially
Difference is 1.07%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 6.3nm, poly- second
The additional amount of alkenyl phosphoric acid is TiO24.35%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2Ceramic fibre
Mass fraction is 44%, and the draw ratio of fiber is 8800, with four chloride hydrate manganese TiO2Mole of titanium atom in ceramic fibre film
Than for 0.068:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, with a thickness of 28.7mm, bulk density
For 0.62mg/cm3, porosity 98.7%, specific surface area 900m2/ g, compression stress 4.68KPa are moulded after 100 second compressions
Property shape becomes 4.35%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is keyed by chemistry, is in power
Under 30W, the Blue-LED lamp that wavelength is 420nm, the elastic TiO of 10mg2Ceramic fibre sponge is to concentration in 90min
1mg/m3, volume 1m3Formaldehyde gas degradation rate be 95%, improve 90% compared with commercial catalyst P25.
Embodiment 24
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) it will contain intermingle with after 475min is stirred in metering system acidolysis in water and the obtained viscosity point of titanium colloidal sol stirring 120min is added
Dispersion liquid, the content of polymethylacrylic acid is 9.5wt% in sticky dispersion liquid, and the content of titanium colloidal sol is 4.7wt%；
(2) TiO in-situ modified by Nickel dichloride hexahydrate is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 10min and polyvinyl sulfonic acid is added simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Pottery
Porcelain fiber dispersion, the beating rate of high speed mashing are 8900r/min, and mashing number is 5 times, beating time 5min,
The beating rate of low speed mashing is 880r/min, and mashing number is 7 times, beating time 2min, TiO2Ceramic fibre film it is soft
Softness is 19.5mN, tensile break strength 3MPa, TiO2The average diameter of fiber is 38nm in ceramic fibre film, and opposite
Deviation is 1.06%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 6nm, poly- second
The additional amount of alkene sulfonic acid is TiO24.45%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2Ceramic fibre
Mass fraction is 45%, and the draw ratio of fiber is 8900, Nickel dichloride hexahydrate and TiO2Mole of titanium atom in ceramic fibre film
Than for 0.071:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, with a thickness of 28.9mm, bulk density
For 0.6mg/cm3, porosity 98.6%, specific surface area 910m2/ g, compression stress 4.70KPa, plasticity after 100 second compressions
Shape becomes 4.3%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is 30W, wave in power by chemistry key connection
Under the Blue-LED lamp of a length of 420nm, the elastic TiO of 10mg2Ceramic fibre sponge is 1mg/m to concentration in 90min3, body
Product is 1m3Formaldehyde gas degradation rate be 91%, improve 86% compared with commercial catalyst P25.
Embodiment 25
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) it dissolves polyvinyl alcohol in water after stirring 460min and the obtained viscosity dispersion of titanium colloidal sol stirring 120min is added
Liquid, the content of polyvinyl alcohol is 9.6wt% in sticky dispersion liquid, and the content of titanium colloidal sol is 4.5wt%；
(2) TiO in-situ modified by nickel acetate tetrahydrate is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 10min and polyvinyl is added simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Pottery
Porcelain fiber dispersion, the beating rate of high speed mashing are 9000r/min, and mashing number is 5 times, beating time 5min,
The beating rate of low speed mashing is 850r/min, and mashing number is 8 times, beating time 2min, TiO2Ceramic fibre film it is soft
Softness is 19mN, tensile break strength 3MPa, TiO2The average diameter of fiber is 36nm in ceramic fibre film, and relatively partially
Difference is 1.1%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 6nm, polyethylene phosphorus
The additional amount of acid is TiO24.5%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The quality of ceramic fibre
Score is 45%, and the draw ratio of fiber is 9000, nickel acetate tetrahydrate and TiO2The molar ratio of titanium atom is in ceramic fibre film
0.074:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, with a thickness of 29.1mm, bulk density
For 0.55mg/cm3, porosity 98.8%, specific surface area 920m2/ g, compression stress 4.73KPa are moulded after 100 second compressions
Property shape becomes 4.2%, elastic TiO2Fiber in ceramic fibre sponge at cross-point by chemistry key connection, power be 30W,
Wavelength is the elastic TiO of 10mg under the Blue-LED lamp of 420nm2Ceramic fibre sponge is 10mg/ to concentration in 90min
L, the degradation rate for the methylene blue solution that volume is 100mL is 95%, improves 90% compared with commercial catalyst P25.
Embodiment 26
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) it dissolves polyvinyl alcohol in water after stirring 460min and the obtained viscosity dispersion of titanium colloidal sol stirring 120min is added
Liquid, the content of polyvinyl alcohol is 9.7wt% in sticky dispersion liquid, and the content of titanium colloidal sol is 4.75wt%；
(2) TiO in-situ modified by six hydration nickel sulfate is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 10min and polyvinyl is added simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Pottery
Porcelain fiber dispersion, the beating rate of high speed mashing are 9000r/min, and mashing number is 5 times, beating time 5min,
The beating rate of low speed mashing is 900r/min, and mashing number is 9 times, beating time 2min, TiO2Ceramic fibre film it is soft
Softness is 19mN, tensile break strength 3MPa, TiO2The average diameter of fiber is 33nm in ceramic fibre film, and relatively partially
Difference is 1.05%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 6nm, polyethylene
The additional amount of phosphoric acid is TiO24.8%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The quality of ceramic fibre
Score is 45.5%, and the draw ratio of fiber is 9200, six hydration nickel sulfate and TiO2The molar ratio of titanium atom in ceramic fibre film
For 0.076:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, with a thickness of 29.3mm, bulk density
For 0.5mg/cm3, porosity 98.7%, specific surface area 930m2/ g, compression stress 4.75KPa are moulded after 100 second compressions
Property shape becomes 4.1%, elastic TiO2Fiber in ceramic fibre sponge at cross-point by chemistry key connection, power be 30W,
Wavelength is the elastic TiO of 10mg under the Blue-LED lamp of 420nm2Ceramic fibre sponge is 10mg/ to concentration in 90min
L, the degradation rate for the methylene blue solution that volume is 100mL is 93.5%, improves 88.5% compared with commercial catalyst P25.
Embodiment 27
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) it dissolves polyvinyl alcohol in water after stirring 460min and the obtained viscosity dispersion of silica solution stirring 120min is added
Liquid, the content of polyvinyl alcohol is 9.8wt% in sticky dispersion liquid, and the content of silica solution is 4.5wt%；
(2) TiO in-situ modified by lanthanum nitrate hexahydrate is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 10min and polyvinyl is added simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Pottery
Porcelain fiber dispersion, the beating rate of high speed mashing are 9100r/min, and mashing number is 5 times, beating time 5min,
The beating rate of low speed mashing is 910r/min, and mashing number is 10 times, beating time 2min, TiO2Ceramic fibre film
Pliability is 19mN, tensile break strength 3MPa, TiO2The average diameter of fiber is 30nm in ceramic fibre film, and opposite
Deviation is 1.06%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 6nm, poly- second
The additional amount of alkenyl phosphoric acid is TiO24.59%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2Ceramic fibre
Mass fraction is 46%, and the draw ratio of fiber is 9250, lanthanum nitrate hexahydrate and TiO2Mole of titanium atom in ceramic fibre film
Than for 0.079:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, with a thickness of 29.4mm, bulk density
For 0.45mg/cm3, porosity 98.7%, specific surface area 940m2/ g, compression stress 4.78KPa are moulded after 100 second compressions
Property shape becomes 4.0%, elastic TiO2Fiber in ceramic fibre sponge at cross-point by chemistry key connection, power be 30W,
Wavelength is the elastic TiO of 10mg under the Blue-LED lamp of 420nm2Ceramic fibre sponge is 10mg/ to concentration in 90min
L, the degradation rate for the methylene blue solution that volume is 100mL is 95%, improves 90% compared with commercial catalyst P25.
Embodiment 28
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polyethylene glycol oxide is dissolved in water after stirring 470min and the obtained viscosity dispersion of zirconium colloidal sol stirring 120min is added
Liquid, the content of polyethylene glycol oxide is 9.9wt% in sticky dispersion liquid, and the content of zirconium colloidal sol is 4.5wt%；
(2) TiO in-situ modified by lanthanum acetate is added2High speed mashing is first carried out after ceramic fibre film, then interval is quiet
It sets 10min while polyacrylic acid is added, then carry out low speed mashing, TiO is made after standing 5min in last interval2Ceramic fibre dispersion
Liquid, the beating rate of high speed mashing are 9200r/min, and mashing number is 5 times, beating time 5min, low speed mashing
Beating rate is 915r/min, and mashing number is 7 times, beating time 2min, TiO2The pliability of ceramic fibre film is 19mN,
Tensile break strength is 3MPa, TiO2The average diameter of fiber is 28nm in ceramic fibre film, and relative deviation is 1.05%,
TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 5.5nm, the additional amount of polyacrylic acid
For TiO24.6%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The mass fraction of ceramic fibre is
46.5%, the draw ratio of fiber is 9300, lanthanum acetate and TiO2The molar ratio of titanium atom is 0.072:1 in ceramic fibre film；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, with a thickness of 29.5mm, bulk density
For 0.4mg/cm3, porosity 98.8%, specific surface area 950m2/ g, compression stress 4.8KPa, plasticity after 100 second compressions
Shape becomes 3.9%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is 30W, wave in power by chemistry key connection
Under the Blue-LED lamp of a length of 420nm, the elastic TiO of 10mg2Ceramic fibre sponge in 90min to concentration be 10mg/L,
The degradation rate for the methylene blue solution that volume is 100mL is 94%, improves 89% compared with commercial catalyst P25.
Embodiment 29
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polyethylene glycol oxide is dissolved in water after stirring 460min and the obtained viscosity dispersion of titanium colloidal sol stirring 120min is added
Liquid, the content of polyethylene glycol oxide is 9.4wt% in sticky dispersion liquid, and the content of titanium colloidal sol is 4.5wt%；
(2) TiO in-situ modified by seven hydrated lanthanum chlorides is added2High speed mashing is first carried out after ceramic fibre film, then
Interval stands 10min and polyacrylic acid is added simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Ceramics
Fiber dispersion, the beating rate of high speed mashing are 9400r/min, and mashing number is 5 times, beating time 5min, low
The beating rate of speed mashing is 930r/min, and mashing number is 8 times, beating time 2min, TiO2The softness of ceramic fibre film
Degree is 19mN, tensile break strength 3MPa, TiO2The average diameter of fiber is 25nm, and relative deviation in ceramic fibre film
For 1.1%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 6nm, polyacrylic acid
Additional amount is TiO24.7%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The mass fraction of ceramic fibre
It is 46%, the draw ratio of fiber is 9400, seven hydrated lanthanum chlorides and TiO2The molar ratio of titanium atom is in ceramic fibre film
0.075:1；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, with a thickness of 29.6mm, bulk density
For 0.38mg/cm3, porosity 98.8%, specific surface area 955m2/ g, compression stress 4.83KPa are moulded after 100 second compressions
Property shape becomes 3.8%, elastic TiO2Fiber in ceramic fibre sponge at cross-point by chemistry key connection, power be 30W,
Wavelength is the elastic TiO of 10mg under the Blue-LED lamp of 420nm2Ceramic fibre sponge is 1mg/m to concentration in 90min3、
Volume is 1m3Formaldehyde gas degradation rate be 95%, improve 90% compared with commercial catalyst P25.
Embodiment 30
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polyvinylpyrrolidone is dissolved in water after stirring 460min that zirconium colloidal sol stirring 120min is added and is made and glued
Property dispersion liquid, the content of polyvinylpyrrolidone is 9.5wt% in sticky dispersion liquid, and the content of zirconium colloidal sol is 4.5wt%；
(2) TiO in-situ modified by thiocarbamide is added2High speed mashing is first carried out after ceramic fibre film, then interval is stood
Polyacrylic acid is added in 10min simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Ceramic fibre dispersion
Liquid, the beating rate of high speed mashing are 9500r/min, and mashing number is 5 times, beating time 5min, low speed mashing
Beating rate is 950r/min, and mashing number is 9 times, beating time 2min, TiO2The pliability of ceramic fibre film is 19mN,
Tensile break strength is 3MPa, TiO2The average diameter of fiber is 20nm in ceramic fibre film, and relative deviation is 1.1%, TiO2
The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 6nm, and the additional amount of polyacrylic acid is TiO2
4.8%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The mass fraction of ceramic fibre is 47%, fiber
Draw ratio is 9500, thiocarbamide and TiO2The molar ratio of titanium atom is 0.08:1 in ceramic fibre film；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, with a thickness of 29.65mm, bulk density
For 0.35mg/cm3, porosity 98.7%, specific surface area 960m2/ g, compression stress 4.85KPa are moulded after 100 second compressions
Property shape becomes 3.7%, elastic TiO2Fiber in ceramic fibre sponge at cross-point by chemistry key connection, power be 30W,
Wavelength is the elastic TiO of 10mg under the Blue-LED lamp of 420nm2Ceramic fibre sponge is 1mg/m to concentration in 90min3、
Volume is 1m3Formaldehyde gas degradation rate be 94.5%, improve 89.5% compared with commercial catalyst P25.
Embodiment 31
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polyvinylpyrrolidone is dissolved in water after stirring 460min that silica solution stirring 120min is added and is made and glued
Property dispersion liquid, the content of polyvinylpyrrolidone is 9.8wt% in sticky dispersion liquid, and the content of silica solution is 4.5wt%；
(2) TiO in-situ modified by carbon nanotube is added2High speed mashing is first carried out after ceramic fibre film, then interval
It stands 10min and polyvinyl is added simultaneously, then carry out low speed mashing, TiO is made after standing 5min in last interval2It is ceramic fine
Dispersion liquid is tieed up, the beating rate of high speed mashing is 9600r/min, and mashing number is 5 times, beating time 5min, low speed
The beating rate of mashing is 950r/min, and mashing number is 6 times, beating time 2min, TiO2The pliability of ceramic fibre film
For 19mN, tensile break strength 3MPa, TiO2The average diameter of fiber is 16nm in ceramic fibre film, and relative deviation is
1.1%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 6nm, polyvinyl
Additional amount is TiO24.5%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The mass fraction of ceramic fibre
It is 48%, the draw ratio of fiber is 9600, carbon nanotube and TiO2The molar ratio of titanium atom is 0.084:1 in ceramic fibre film；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, with a thickness of 29.7mm, bulk density
For 0.32mg/cm3, porosity 98.8%, specific surface area 965m2/ g, compression stress 4.88KPa are moulded after 100 second compressions
Property shape becomes 3.5%, elastic TiO2Fiber in ceramic fibre sponge at cross-point by chemistry key connection, power be 30W,
Wavelength is the elastic TiO of 10mg under the Blue-LED lamp of 420nm2Ceramic fibre sponge is 1mg/m to concentration in 90min3、
Volume is 1m3Formaldehyde gas degradation rate be 93%, improve 88% compared with commercial catalyst P25.
Embodiment 32
A kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, steps are as follows:
(1) polyvinylpyrrolidone is dissolved in water after stirring 460min that titanium colloidal sol stirring 120min is added and is made and glued
Property dispersion liquid, the content of polyvinylpyrrolidone is 9.9wt% in sticky dispersion liquid, and the content of titanium colloidal sol is 4.5wt%；
(2) it is added and passes through g-C3N4In-situ modified TiO2High speed mashing is first carried out after ceramic fibre film, then interval is stood
Polyvinyl is added in 10min simultaneously, then carries out low speed mashing, and TiO is made after standing 5min in last interval2Ceramic fibre point
Dispersion liquid, the beating rate of high speed mashing are 9700r/min, and mashing number is 5 times, beating time 5min, low speed mashing
Beating rate be 960r/min, mashing number be 10 times, beating time 2min, TiO2The pliability of ceramic fibre film is
19mN, tensile break strength 3MPa, TiO2The average diameter of fiber is 12nm in ceramic fibre film, and relative deviation is
1.1%, TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 6nm, polyvinyl
Additional amount is TiO24.9%, TiO of ceramic fibre film quality2TiO in ceramic fibre dispersion liquid2The mass fraction of ceramic fibre
It is 49%, the draw ratio of fiber is 9700, g-C3N4With TiO2The molar ratio of titanium atom is 0.089:1 in ceramic fibre film；
(3) by the way that elasticity TiO is made after freezing, dry and high-temperature calcination2Ceramic fibre sponge.
Final elasticity TiO obtained2Ceramic fibre sponge is that multistage is mesh-structured, with a thickness of 29.8mm, bulk density
For 0.30mg/cm3, porosity 98.9%, specific surface area 1000m2/ g, compression stress 4.92KPa, after 100 second compressions
Plastic deformation is 3.3%, elastic TiO2Fiber in ceramic fibre sponge at cross-point is keyed by chemistry, is in power
Under 30W, the Blue-LED lamp that wavelength is 420nm, the elastic TiO of 10mg2Ceramic fibre sponge is to concentration in 90min
1mg/m3, volume 1m3Formaldehyde gas degradation rate be 95%, improve 90% compared with commercial catalyst P25.
Claims (8)
1. a kind of photocatalysis elasticity TiO2The preparation method of ceramic fibre sponge, characterized in that steps are as follows:
(1) sticky dispersion liquid is prepared, the viscosity dispersion liquid is made of water soluble polymer, water and inorganic sol；
(2) TiO in-situ modified by modifying agent is added2Intermittent mashing is carried out after ceramic fibre film and polyelectrolyte is added obtaining
To TiO2Ceramic fibre dispersion liquid, the TiO2The pliability of ceramic fibre film be 5~20mN, tensile break strength be 3~
5MPa；The intermittent mashing refers to successively carries out high speed mashing and low speed mashing stage by stage, and carries out after per stage
Interval is stood, and the beating rate of the high speed mashing is 1000~10000r/min, and the beating rate of the low speed mashing is 100
~1000r/min；The polyelectrolyte is to carry out being added when interval is stood after high speed is beaten；
(3) curing molding obtains elastic TiO2Ceramic fibre sponge；
The water soluble polymer is polyacrylamide, polyacrylic acid, polymethylacrylic acid, polyvinyl alcohol, polyethylene glycol oxide, gathers
Vinylpyrrolidone, carboxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyl
Propyl methocel, hydroxymethylhydroxyethyl cellulose or gelatin, the inorganic sol are in titanium colloidal sol, silica solution and zirconium colloidal sol
More than one；
The modifying agent is yttrium salt, zirconates, zinc salt, molysite, cobalt salt, cerium salt, pink salt, manganese salt, nickel salt, lanthanum salt, thiocarbamide, carbon nanometer
Pipe or g-C3N4, modifying agent and TiO2The molar ratio of titanium atom is 0.001~0.1:1 in ceramic fibre film.
2. a kind of photocatalysis elasticity TiO according to claim 12The preparation method of ceramic fibre sponge, feature exist
In the concrete operations for preparing sticky dispersion liquid are as follows: add after water soluble polymer is dissolved in water 120~480min of stirring
Enter inorganic sol and stirs 30~120min.
3. a kind of photocatalysis elasticity TiO according to claim 12The preparation method of ceramic fibre sponge, feature exist
In, the content of water soluble polymer is 0.01~10wt% in the viscosity dispersion liquid, the content of inorganic sol is 0.01~
5wt%.
4. a kind of photocatalysis elasticity TiO according to claim 12The preparation method of ceramic fibre sponge, feature exist
In the yttrium salt is six nitric hydrate yttriums, eight hydrated sulfuric acid yttriums or six chloride hydrate yttriums, and the zirconates is zirconium acetate, zirconium nitrate
Or zirconium sulfate, the zinc salt are acetic acid dihydrate zinc or zinc nitrate hexahydrate, the molysite is Fe(NO3)39H2O, six hydrations three
Iron chloride or ferric sulfate, the cobalt salt are cabaltous nitrate hexahydrate, four acetate hydrate cobalts or Cobalt monosulfate heptahydrate, and the cerium salt is six
Nitric hydrate cerium, four nitric hydrate ceriums or cerous carbonate hydrate, the pink salt are that anhydrous stannic chloride, stannous sulfate or oxalic acid are sub-
Tin, the manganese salt be four acetate hydrate manganese, Manganous sulfate monohydrate or four chloride hydrate manganese, the nickel salt be Nickel dichloride hexahydrate,
Nickel acetate tetrahydrate or six hydration nickel sulfate, the lanthanum salt are lanthanum nitrate hexahydrate, lanthanum acetate or seven hydrated lanthanum chlorides.
5. a kind of photocatalysis elasticity TiO according to claim 12The preparation method of ceramic fibre sponge, feature exist
In the TiO2The average diameter of fiber is 10~500nm in ceramic fibre film, and relative deviation is 1~5%；
The TiO2The crystalline structure of ceramic fibre film is Detitanium-ore-type, and fibrous inside crystallite dimension is 5~50nm；
The polyelectrolyte is polyacrylic acid, polymethylacrylic acid, polystyrolsulfon acid, polyvinyl sulfonic acid or polyvinyl；
The additional amount of the polyelectrolyte is TiO2The 0.01~5% of ceramic fibre film quality；
The TiO2TiO in ceramic fibre dispersion liquid2The mass fraction of ceramic fibre is 0.01~50%；
The TiO2The draw ratio of fiber is 100~10000 in ceramic fibre dispersion liquid.
6. a kind of photocatalysis elasticity TiO according to claim 12The preparation method of ceramic fibre sponge, feature exist
In the intermittent mashing is divided into two stages, and the first stage is that high speed is beaten, and is beaten number 1~5 time, beating time 0.1
~5min, interval time of repose are 0.1~10min；Second stage is low speed mashing, is beaten number 2~10 times, and beating time is
0.1~2min, interval time of repose are 0.1~5min.
7. a kind of photocatalysis elasticity TiO according to claim 12The preparation method of ceramic fibre sponge, feature exist
In the curing molding includes freezing, dry and high-temperature calcination.
8. using photocatalysis elasticity TiO made from preparation method as described in any one of claims 1 to 72Ceramic fibre sea
Silk floss, it is characterized in that: being mesh-structured, the elastic TiO of multistage2Ceramic fibre sponge with a thickness of 5~30mm, bulk density 0.1
~10mg/cm3, porosity is 90~99%, and specific surface area is 500~1000m2/ g, compression stress are less than 5KPa, 100 second compressions
Plastic deformation is less than 25% afterwards, elastic TiO2Fiber in ceramic fibre sponge at cross-point passes through chemistry key connection；
Under the ultraviolet light that power is 24W, wavelength is 254nm, the methylene blue for being 10mg/L to concentration in 30min
The degradation rate of solution is 90~95%, improves 5~10% compared with commercial catalyst P25；
Under the Blue-LED lamp that power is 30W, wavelength is 420nm, the methylene for being 10mg/L to concentration in 90min
The degradation rate of blue solution is 90~95%, improves 85~90% compared with commercial catalyst P25；
It is 1mg/m to concentration in 30min under the ultraviolet light that power is 24W, wavelength is 254nm3Formaldehyde gas
Degradation rate be 90~95%, improve 10~15% compared with commercial catalyst P25；
It is 1mg/m to concentration in 90min under the Blue-LED lamp that power is 30W, wavelength is 420nm3Formaldehyde gas
Degradation rate be 90~95%, improve 85~90% compared with commercial catalyst P25.
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| CN106732506A (en) * | 2017-03-02 | 2017-05-31 | 河北麦森钛白粉有限公司 | A kind of preparation technology of carbon yttrium modified titanium dioxide photocatalyst |
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