CN105712397A - Method for preparing nano titanium dioxide through electrostatic spraying - Google Patents
Method for preparing nano titanium dioxide through electrostatic spraying Download PDFInfo
- Publication number
- CN105712397A CN105712397A CN201610268973.2A CN201610268973A CN105712397A CN 105712397 A CN105712397 A CN 105712397A CN 201610268973 A CN201610268973 A CN 201610268973A CN 105712397 A CN105712397 A CN 105712397A
- Authority
- CN
- China
- Prior art keywords
- nano titanium
- titanium oxide
- nozzle
- nano
- tio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000007590 electrostatic spraying Methods 0.000 title abstract description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title abstract 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 63
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229960000583 acetic acid Drugs 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 9
- 230000005686 electrostatic field Effects 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 36
- 239000007921 spray Substances 0.000 claims description 17
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 13
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000005030 aluminium foil Substances 0.000 claims description 4
- 230000005070 ripening Effects 0.000 claims description 4
- 230000029087 digestion Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 23
- 238000002360 preparation method Methods 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000002425 crystallisation Methods 0.000 abstract description 9
- 238000001354 calcination Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 6
- 238000003837 high-temperature calcination Methods 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 238000005507 spraying Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 230000005684 electric field Effects 0.000 description 6
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002121 nanofiber Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 238000003483 aging Methods 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000009688 liquid atomisation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing nano titanium dioxide through electrostatic spraying. The method comprises the following steps of: (1) dissolving tetrabutyl titanate into absolute ethyl alcohol and glacial acetic acid and fully stirring; (2) regulating pH of deionized water with acetic acid; (3) slowly dropwise adding a solution obtained in the step (1) into the deionized water, vigorously stirring under a heat preservation condition, and then carrying out aging treatment; (4) establishing a high-voltage electrostatic field between a propeller nozzle and a receiving device by virtue of a high-voltage electrostatic generating device and placing under a closed condition; and (5) injecting an aged solution into a propeller, controlling the device voltage, the advance speed and the temperature, and spraying by virtue of a nozzle exit, so that the nano titanium dioxide is obtained. The method provided by the invention has the advantages that the traditional nano TiO2 preparation technology requiring high-temperature calcination and crystallization is broken through, the nano TiO2 can be prepared at low temperature, agglomeration, caused by calcination, between particles is avoided, and the application range of the nano TiO2 is greatly broadened.
Description
Technical field
The invention belongs to field of nano material preparation, especially relate to a kind of method that electrostatic spray prepares nano titanium oxide.
Background technology
Electrostatic spray is a kind of method utilizing electrohydrodynamics fluidics that polymer solution is prepared into nanoparticle, it rationale here is that: applies high pressure to the polymer solution flowed out with certain flow rate, under DC Electric Field, owing to being subject to the induction of electric field force, make a large amount of electric charge of polymer fluid accumulated inside, macromolecule drop is maintained at nozzle exit by surface tension effects, and meanwhile, drop is subject to an electric field force in opposite direction with surface tension.Along with electric field intensity is gradually increased, the drop at nozzle place is taper by spherical elongation, is referred to as taylor cone.When electric field intensity reaches a marginal value, when the electrostatic force that namely electric charge produces is enough to the surface tension overcoming fluid, drop just sprays from " taylor cone ".Due to the repulsive interaction between like charges, there is concussion and unstable in injection stream, the scrambling screw of generation very high frequency, jet is drawn and attenuated rapidly, and solvent also volatilizees rapidly under the effect of electric field.When thread cleaves to a certain extent, along with the volatilization of solvent, and it is solidified into nano-particle, falls immediately on reception device.
Photocatalyst material TiO2Because its photocatalytic activity is high, stability and heat-resist, non-secondary pollution, nonirritant, to human non-toxic and the advantage such as inexpensive, become the environmental protection catalysis material currently most with DEVELOPMENT PROSPECT.
Synthesize nano-TiO both at home and abroad at present2Method mainly have metal alkoxide Hydrolyze method, hydrothermal crystallization method and sol-gal process.
Utilize metal alkoxide hydrolysis preparation TiO2Nanoparticle approach is simple and easy to do, and energy consumption is low, good process repeatability, gained TiO2Close to single dispersing, purity is high.But technological process is long, auxiliary material is expensive, and ethanol, toluene or solvent naphtha, ammonia etc. are all inflammable substance or toxic, and Safety production questions is very prominent.Organic compound that hydro-thermal method prepares nano-powder many employings titanium or the intermediate product that is difficult to prepare are as predecessor, relatively costly, preparation technology is also more complicated, and most important two parameters are exactly temperature and pressure in the method, nucleation rate and size are had a significant impact by temperature.In theory, temperature is more high more is conducive to generating little particle, and pressure raising can improve nucleation rate, is conducive to generating the powder body of little particle diameter, and energy consumption is big, and production cost is high, and working condition is wayward.Peptization gel method prepares nanoscale TiO2Compared with metal alkoxide Hydrolyze method and hydro-thermal method, there is more significant advantage: cost of material is low, apparatus and process is simple, the powder purity produced is high, granularity is little, particle size distribution is narrow, granularmetric composition controllability is good, but there is the reunion that factor more rambunctious is exactly powder, and the powder body of preparation needs to obtain finished product through ageing, drying, calcination, limit its application on non-refractory base material.
Chinese patent CN102586948A discloses anatase type titanium dioxide nano-fiber photocatalyst and preparation method, belongs to nano material and photocatalysis technology field.The present invention prepares composite nano fiber first with electrostatic spinning technique, then titanium dioxide nanofiber photocatalyst is obtained through calcining in atmosphere, and centre does not introduce sol-gel technique, make technological parameter more easy-regulating, eliminate the several factors affecting final titanium dioxide nanofiber degree of crystallinity, crystal formation and distribution of particle sizes and size, it is more conducive to obtain the efficient catalysis material of catalysis, but this patent need nonetheless remain for carrying out high temperature sintering.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and provide one to breach Conventional nano TiO2Need the preparation technology of high-temperature calcination crystallization, nano-TiO can be prepared at low temperatures2Method, it is to avoid because of the interparticle reunion that calcining causes, significantly widened nano-TiO2Range of application.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of electrostatic spray prepares the method for nano titanium oxide, adopts following steps:
(1) butyl titanate it is dissolved in dehydrated alcohol and glacial acetic acid and is sufficiently stirred for；
(2) pH to 2-4 of deionized water is regulated with acetic acid；
(3) solution that step (1) obtains is slowly added dropwise in above-mentioned deionized water, is stirred vigorously under heat-retaining condition, then carry out ripening；
(4) setting up a high-voltage electrostatic field by high-voltage electrostatic generator between propeller nozzle and reception device, the metal guide flow tube on nozzle connects negative pole, receives device ground connection and forms positive pole, nozzle and the reception airtight placement of device；
(5) aged solution is injected into propeller, controls device voltage, fltting speed, temperature, prepare nano titanium oxide by jet hole ejection.
The molar ratio of the butyl titanate described in step (1), dehydrated alcohol and glacial acetic acid is 1:2-4:5-7.
In the solution that step (3) obtains, the mole of deionized water is 70-220 times of butyl titanate mole, and when 30-40 DEG C insulated and stirred 2.5-3.5h, digestion time is 19-24h.
The flat mouth dispensing needle head that nozzle is 14G-27G described in step (4), described reception device is aluminium-foil paper.
In step (5), the voltage of device is 20-30KV, and the fltting speed of aged solution is 0.01-0.02mm/s, and temperature is 100 DEG C-150 DEG C, and nozzle and the receiving range received between device are 15-20cm.Under electrostatic field force effect, the TiO ejected2There is unstable explosion in gel solution, forms nano level droplet, and at the temperature of about 150 DEG C, solvent volatilization, is solidified into nano-particle, and owing to the drop being atomized is with same sex electric charge, the repulsion effect between same sex electric charge makes the TiO collected2Particle diameter is little, not easily reunite and good dispersion.This preparation method breaches Conventional nano TiO2Need the preparation technology of high-temperature calcination crystallization, nano-TiO can be prepared the temperature of about 150 DEG C2, simplify production technology, saved the energy, for nano-TiO2Application and preparation of industrialization on non-refractory base material provide technological guidance, avoid the interparticle reunion because calcining causes simultaneously, have significantly widened nano-TiO2Range of application.
Preparation technology parameter of the present invention, is specific to the present invention, is also difference and prior art, possesses certain creationary technical essential place.
Under the situation that other conditions are constant, voltage progressively increases to 30kV from 20kV, the TiO of preparation2Granule will be gradually reduced, and this Scaling rule with Hartman is consistent, obtains formula (1) and (2) according to Scaling rule.
In formula (1) and (2), d is liquid-drop diameter, and α is a constant, and Q is flow velocity, and ρ is solution density, and I is electric current, and ε is permittivity of vacuum, and γ is the aerial surface tension of liquid, and K is the electric conductivity of liquid.Formula (1) and (2) represent, the diameter of EFI granule and electric current I are inversely proportional to, and electric current is more big, and EFI particle diameter is also more little, and electric current is more little, and its diameter is also more big.And electric current is directly proportional to the voltage being applied between syringe and collecting board, namely voltage is more big, and EFI particle diameter is more little.This is because when voltage reaches certain value, after overcoming surface tension of liquid to form jet, along with the increase of voltage, occur the coulomb division in EFI process also more many, the TiO finally collected on collecting board2Particle size is more little.But, when voltage is more than 30kV, liquid coulomb division performance in EFI process acutely, not easily receiving collection on plate, is lost bigger；If pressing less than 20kV, then liquid coulomb division performance in EFI process is inconspicuous, the TiO collected2Particle size is bigger.
Under the situation that other conditions are constant, electrostatic flow velocity increases to 0.02mm/s from 0.01mm/s, TiO prepared by electrostatic2Granule will be gradually increased, and this and the formula (1) of Hartman, (2) are consistent with, and namely press formula (1), (2), along with the increase of EFI flow velocity, the EFI TiO obtained2The particle diameter of granule will increase.When flow velocity is more than 0.02mm/s, the liquid at EFI jet hole place vertically flows out, and could not produce atomizing effect.If flow velocity is less than 0.01mm/s, the liquid atomization DeGrain that EFI jet hole place ejects.
Under the situation that other conditions are constant, along with receiving range increases to 20cm, TiO from 15cm2Grain diameter constantly reduces.This with EFI process in coulomb division be about: the process that EFI liquid moves from syringe needle to collecting board, first jet is split into charged drop, volatilization along with solvent, the density of charged drop increases, surface charge density also increases, charge repulsion increases therewith, causes coulomb to divide, and forms less charged drop.If receiving range is less than 15cm, TiO2Also not exclusively, along with the increase of receiving range, solvent volatilizees completely in the solvent volatilization of particle surface, occurs the number of times of coulomb division to increase so that particle diameter reduces.When receiving range is more than 20cm, continue to increase receiving range, the TiO obtained2Grain diameter size is held essentially constant.
Compared with prior art, the invention have the advantages that
1, the present invention is directed to sol-gel process and prepare TiO2There is the reunion of powder and prepare powder body and need the shortcoming through ageing drying, calcination, use electrostatic Spraying technique by TiO 2 sol in the airtight oven of about 150 DEG C, being injected into nanosized liquid droplets, solvent volatilizees, and is finally directly collected into the TiO of well-crystallized2, it is to avoid the defects such as the reunion that the calcining of TiO 2 sol integral high-temperature causes, production technology is simple, excellent stability, consuming time short, it is simple to operation, it is easy to carry out large-scale production, and TiO2Even particle distribution, mean diameter is less than about 40nm.
2, the nano-TiO prepared by the present invention2Visible ray is had stronger absorption, improves the utilization rate to luminous energy.Meanwhile, breach conventional sol-gel processes and prepare nano-TiO2Need the preparation technology of high-temperature calcination crystallization, make guidance for its application on non-refractory base material.
3, the hydrosol method that it is solvent with water under cryogenic that the present invention adopts prepares TiO2Colloidal sol, its dominant response step is that predecessor is dissolved in aqueous solvent and forms uniform solution, and solute produces hydrolysis and polycondensation reaction in aqueous solvent, and reaction product is gathered into particle and forms colloidal sol.Owing in course of reaction, the amount of water is significantly larger than theoretical amount, when the consumption of water is more, presoma butyl titanate is fully hydrolyzed generation inorganic matter, inorganic matter spontaneous crystallization, in conjunction with electrostatic spraying processes, dry at 100-150 DEG C of temperature good dispersion can be obtained, particle diameter is little, photocatalysis performance is excellent Detitanium-ore-type TiO2Granule.
Accompanying drawing explanation
Fig. 1 is TiO2Aerosol particle size figure；
Fig. 2 is TiO2The XRD figure of powder body；
Fig. 3 is TiO2Powder body transmission electron microscope shines；
Fig. 4 is TiO2Powder body UV-Vis DRS collection of illustrative plates；
Fig. 5 is TiO2The powder body photocatalytic activity to methylene blue；
Fig. 6 is the structural representation of static water-spraying system.
In figure, 1-propeller, 2-nozzle, 3-receive device, 4-high-voltage electrostatic generator
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
By nano-TiO2Colloidal sol after high speed centrifugation when 7000r/min, takes supernatant, and dilutes 1,000 times, with dynamic light scattering laser particle size analyzer, aerosol particle size and particle size distribution are tested, and result is as shown in Figure 1.
By curve in figure it can be seen that the particle diameter of colloidal sol is at below 100nm, TiO2Colloidal sol mean diameter is at 31.23nm, and coefficient of dispersion pdi is below 0.3, and dispersibility is better.
Embodiment 2
By nano-TiO2Colloidal sol passes through electrostatic spray, and on the collector, in the air dry oven of 150 DEG C, thermal crystallisation obtains nano-TiO after processing 6h simultaneously in injection2Powder body, then characterizes its crystal formation with X-ray diffractometer (X'pertPowder), and result is as shown in Figure 2.
Nano-TiO in Fig. 22It is that stronger diffraction maximum occurs near 25.3,37.8,48.0 at 2 θ, (101) of the corresponding Detitanium-ore-type of this difference, (004), (200) crystal face, and crystal property is better.TiO is estimated according to Scherrer formula2Average grain size be 9.1nm.
Embodiment 3
By nano-TiO2After powder body ultrasonic disperse, it is diluted to 0.5g/L, then Japan's JEM-2100F type transmission electron microscope observing nano-TiO2Pattern and particle size.
Nano-TiO prepared as seen from Figure 32Powder body crystallization degree is good, and crystal formation is perfect, and particle size is between 5～10nm, and has good dispersibility.
Embodiment 4
By nano-TiO2Colloidal sol passes through electrostatic spray, and on the collector, in the air dry oven of 150 DEG C, thermal crystallisation obtains nano-TiO after processing 6h simultaneously in injection2Powder body, then Japan's Shimadzu UV-3600 ultraviolet-uisible spectrophotometer analyzes their Ultraviolet-visible Spectroscopic Characteristics amount.
By in Fig. 4 it can be seen that nano-TiO2In ultra-violet (UV) band, (200-400nm) has very strong uv absorption, starts that visible ray is had response at 406nm place.Formula (1) is utilized to calculate, nano-TiO2Band-gap energy be 3.05eV, with standard Detitanium-ore-type TiO2Band-gap energy be that 3.2eV compares, experiment prepare Detitanium-ore-type TiO2There is red shift, it may be possible to owing to the impact of lattice structure makes its band-gap energy reduce, red shift occurs.
Embodiment 5
By nano-TiO2Colloidal sol passes through electrostatic spray, and on the collector, in the air dry oven of 150 DEG C, thermal crystallisation obtains nano-TiO after processing 6h simultaneously in injection2Powder body, then its light-catalysed activity size is reflected with the degradation rate of methylene blue, the photocatalysis performance of powder body is characterized by the requirement purifying method of testing according to GB23762-2009-T catalysis material water solution system in the photocatalytic reaction device oneself built, with uviol lamp for light source.
Fig. 5 is nano-TiO2The powder body photocatalytic degradation curve to methylene blue solution.As seen from the figure, nano-TiO2The degradation rate of methylene blue is 82.3% by powder body in 90min, and is not added with nano-TiO2The methylene blue blank solution of powder body is hardly degraded under ultraviolet light.
Embodiment 6
A kind of electrostatic spray prepares the method for nano titanium oxide, adopts following steps:
(1) mol ratio butyl titanate being dissolved in dehydrated alcohol and glacial acetic acid and being sufficiently stirred for butyl titanate, dehydrated alcohol and glacial acetic acid is 1:2:5；
(2) pH to 2 of deionized water is regulated with acetic acid；
(3) being slowly added dropwise in above-mentioned deionized water by the solution that step (1) obtains, in the solution obtained, the mole of deionized water is 70 times of butyl titanate mole, insulated and stirred 3.5h, then ripening 19h when 30 DEG C；
(4) by the high-voltage electrostatic generator 4 nozzle 2 at propeller 1 and receive and set up a high-voltage electrostatic field between device 3, thus defining static water-spraying system, as shown in Figure 6, the flat mouth dispensing needle head that nozzle 2 is 14G used, its metal guide flow tube connects negative pole, receiving device 3 and form positive pole for aluminium-foil paper ground connection, device 3 is airtight is placed in transparent roasting box for nozzle 2 and reception；
(5) aged solution is injected into propeller, control device voltage be 20kV, aged solution fltting speed be 0.01mm/s, controlling whole transparent roasting box temperature is 100 DEG C, nozzle and the receiving range received between device are 15cm, prepare nano titanium oxide by jet hole ejection.
Embodiment 7
A kind of electrostatic spray prepares the method for nano titanium oxide, adopts following steps:
(1) mol ratio butyl titanate being dissolved in dehydrated alcohol and glacial acetic acid and being sufficiently stirred for butyl titanate, dehydrated alcohol and glacial acetic acid is 1:4:7；
(2) pH to 4 of deionized water is regulated with acetic acid；
(3) being slowly added dropwise in above-mentioned deionized water by the solution that step (1) obtains, in the solution obtained, the mole of deionized water is 220 times of butyl titanate mole, insulated and stirred 2.5h, then ripening 24h when 40 DEG C；
(4) between angle of rake nozzle and reception, a high-voltage electrostatic field is set up by high-voltage electrostatic generator, the flat mouth dispensing needle head that nozzle is 27G used, its metal guide flow tube connects negative pole, receiving device is that aluminium-foil paper ground connection forms positive pole, nozzle with receive that device is airtight is placed in transparent roasting box；
(5) aged solution is injected into propeller, control device voltage be 30kV, aged solution fltting speed be 0.02mm/s, controlling whole transparent roasting box temperature is 150 DEG C, nozzle and the receiving range received between device are 20cm, prepare nano titanium oxide by jet hole ejection.
Claims (7)
1. the method that an electrostatic spray prepares nano titanium oxide, it is characterised in that the method adopts following steps:
(1) butyl titanate it is dissolved in dehydrated alcohol and glacial acetic acid and is sufficiently stirred for；
(2) pH to 2-4 of deionized water is regulated with acetic acid；
(3) solution that step (1) obtains is slowly added dropwise in above-mentioned deionized water, is stirred vigorously under heat-retaining condition, then carry out ripening；
(4) setting up a high-voltage electrostatic field by high-voltage electrostatic generator between propeller nozzle and reception device, the metal guide flow tube on nozzle connects negative pole, receives device ground connection and forms positive pole, nozzle and the reception airtight placement of device；
(5) aged solution is injected into propeller, controls device voltage, fltting speed, temperature, prepare nano titanium oxide by jet hole ejection.
2. the method that a kind of electrostatic spray according to claim 1 prepares nano titanium oxide, it is characterised in that the molar ratio of the butyl titanate described in step (1), dehydrated alcohol and glacial acetic acid is 1:2-4:5-7.
3. the method that a kind of electrostatic spray according to claim 1 prepares nano titanium oxide, it is characterised in that in the solution that step (3) obtains, the mole of deionized water is 70-220 times of butyl titanate mole.
4. the method that a kind of electrostatic spray according to claim 1 prepares nano titanium oxide, it is characterised in that step (3) insulated and stirred 2.5-3.5h when 30-40 DEG C.
5. the method that a kind of electrostatic spray according to claim 1 prepares nano titanium oxide, it is characterised in that the digestion time of step (3) is 19-24h.
6. the method that a kind of electrostatic spray according to claim 1 prepares nano titanium oxide, it is characterised in that the flat mouth dispensing needle head that nozzle is 14G-27G described in step (4), described reception device is aluminium-foil paper.
7. the method that a kind of electrostatic spray according to claim 1 prepares nano titanium oxide, it is characterized in that, in step (5), the voltage of device is 20-30KV, the fltting speed of aged solution is 0.01-0.02mm/s, temperature is 100 DEG C-150 DEG C, and nozzle and the receiving range received between device are 15-20cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610268973.2A CN105712397B (en) | 2016-04-27 | 2016-04-27 | A kind of method that electrostatic spray prepares nano titanium oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610268973.2A CN105712397B (en) | 2016-04-27 | 2016-04-27 | A kind of method that electrostatic spray prepares nano titanium oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105712397A true CN105712397A (en) | 2016-06-29 |
| CN105712397B CN105712397B (en) | 2018-03-13 |
Family
ID=56162130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610268973.2A Expired - Fee Related CN105712397B (en) | 2016-04-27 | 2016-04-27 | A kind of method that electrostatic spray prepares nano titanium oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105712397B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836846A (en) * | 2019-03-21 | 2019-06-04 | 北京理工大学 | A kind of micro-nano fluorescence pigment and preparation method thereof |
| CN109870488A (en) * | 2017-12-04 | 2019-06-11 | 中国科学院大连化学物理研究所 | A kind of preparation method of alcohol gas sensor |
| CN113083268A (en) * | 2021-04-02 | 2021-07-09 | 西安建筑科技大学 | Crystal form controllable TiO2Preparation method of photocatalytic material |
| CN114988466A (en) * | 2022-05-20 | 2022-09-02 | 佛山(华南)新材料研究院 | Mesoporous TiO with high tap density 2 Microspheres and method for preparing same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104176761A (en) * | 2014-08-01 | 2014-12-03 | 长春理工大学 | Preparation method of cerium oxide porous microspheres |
| CN104538189A (en) * | 2014-12-04 | 2015-04-22 | 湘潭大学 | Spongy TiO2/ZnO porous nanometer ring material, and preparation and application methods thereof |
| CN104891566A (en) * | 2015-06-10 | 2015-09-09 | 辽宁工业大学 | Method for preparing anatase nano titanium dioxide in pulse electromagnetic field |
-
2016
- 2016-04-27 CN CN201610268973.2A patent/CN105712397B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104176761A (en) * | 2014-08-01 | 2014-12-03 | 长春理工大学 | Preparation method of cerium oxide porous microspheres |
| CN104538189A (en) * | 2014-12-04 | 2015-04-22 | 湘潭大学 | Spongy TiO2/ZnO porous nanometer ring material, and preparation and application methods thereof |
| CN104891566A (en) * | 2015-06-10 | 2015-09-09 | 辽宁工业大学 | Method for preparing anatase nano titanium dioxide in pulse electromagnetic field |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109870488A (en) * | 2017-12-04 | 2019-06-11 | 中国科学院大连化学物理研究所 | A kind of preparation method of alcohol gas sensor |
| CN109836846A (en) * | 2019-03-21 | 2019-06-04 | 北京理工大学 | A kind of micro-nano fluorescence pigment and preparation method thereof |
| CN109836846B (en) * | 2019-03-21 | 2021-04-13 | 北京理工大学 | Micro-nano fluorescent pigment and preparation method thereof |
| CN113083268A (en) * | 2021-04-02 | 2021-07-09 | 西安建筑科技大学 | Crystal form controllable TiO2Preparation method of photocatalytic material |
| CN114988466A (en) * | 2022-05-20 | 2022-09-02 | 佛山(华南)新材料研究院 | Mesoporous TiO with high tap density 2 Microspheres and method for preparing same |
| CN114988466B (en) * | 2022-05-20 | 2024-04-09 | 佛山(华南)新材料研究院 | Mesoporous TiO with high tap density 2 Microsphere and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105712397B (en) | 2018-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105712397B (en) | A kind of method that electrostatic spray prepares nano titanium oxide | |
| US9656874B2 (en) | Method for producing metal oxide-containing particles, and method for producing aggregates of metal oxide colloidal particles | |
| CN101607735B (en) | Zinc oxide and titanium dioxide composite film material and preparation method thereof | |
| CN104386746B (en) | Method for preparing small-size bismuth oxychloride wafer by use of hydrothermal method | |
| CN110152641A (en) | A kind of amorphous photonic crystal schemochrome material and preparation method thereof with photocatalytic effect | |
| Arunmetha et al. | Effect of processing methods on physicochemical properties of titania nanoparticles produced from natural rutile sand | |
| CN104192907B (en) | The preparation method of a kind of γ-bismuth molybdate nanotube | |
| CN110201655B (en) | One-step method for preparing hollow TiO2Method and application of nano-microspheres | |
| Dwivedi et al. | Size controlled synthesis and photocatalytic activity of anatase TiO2 hollow microspheres | |
| CN101891974B (en) | Method for preparing TiO2/SiO2 composite powder | |
| CN103877959A (en) | Hydrogenated titanium dioxide nanotube/nano-particle composite photocatalytic material and preparation method thereof | |
| CN106492779B (en) | Core-shell structure rare earth titanate-dioxide composite nanofiber catalysis material preparation method | |
| CN104071836A (en) | Titanium dioxide hollow nanosphere and preparation method thereof | |
| CN112107873A (en) | Vertical device and method for preparing superfine powder through spray pyrolysis | |
| CN104772149B (en) | Bi2O3/BiFeO3/TiO2 nano-flower photocatalytic material and preparation method thereof | |
| CN104690295A (en) | Method for preparing monodispersed ultrafine particles | |
| CN109205667A (en) | A kind of preparation method of nano-titanium dioxide | |
| CN103979599B (en) | A kind of preparation method of bi component oxide nano belt | |
| CN103920505A (en) | Cadmium sulfide inverse opal structure capable of producing hydrogen in high-efficiency manner through visible light photocatalysis and preparation method thereof | |
| Kudhier et al. | Novel and simple method to synthesize donut-like TiO2 with photocatalytic activity | |
| CN106311100B (en) | A kind of production method of photocatalysis complex microsphere | |
| CN101654280B (en) | Preparation method of titanium dioxide nano powder | |
| Majumder | Synthesis methods of nanomaterials for visible light photocatalysis | |
| CN104891566B (en) | The method that pulse electromagnetic field prepares anatase-type nanometer titanium dioxide | |
| CN112142104A (en) | Preparation of nano black TiO by aerosol method2Method (2) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180313 |