CN107694551A - The preparation technology of the inorganic microspheroidal particles of surface uniform location titanium dioxide - Google Patents

The preparation technology of the inorganic microspheroidal particles of surface uniform location titanium dioxide Download PDF

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Publication number
CN107694551A
CN107694551A CN201711104044.9A CN201711104044A CN107694551A CN 107694551 A CN107694551 A CN 107694551A CN 201711104044 A CN201711104044 A CN 201711104044A CN 107694551 A CN107694551 A CN 107694551A
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titanium dioxide
inorganic
titanium
water
preparation technology
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CN107694551B (en
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伦慧东
左桂福
孟宪光
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063Titanium; Oxides or hydroxides thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D49/00Separating dispersed particles from gases, air or vapours by other methods
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01J35/39
    • B01J35/51

Abstract

The invention discloses a kind of preparation technology of the inorganic microspheroidal particles of surface uniform location titanium dioxide, category material for air purification field, technical scheme to be:Water-soluble titanium source is soluble in water, lower addition weak caustic solution is stirred, wherein, titanium source, water, the quality parts ratio of weak base are 1:10‑100:1 50,10 120min are stood, peroxide is added, obtains solation titania systems;By solation titania systems even application in inorganic microsphere surface or dipping inorganic microsphere, room temperature to 100 DEG C of dry 13 h, less than 600 800 DEG C 1 10 h of sintering.Beneficial effect is:Process of preparing is simple, and decentralization of the titanium dioxide on inorganic microsphere surface is high, does not reunite persistently, and firm position, difficult for drop-off, substantially increases catalytic efficiency;The energy is saved, it is more green.

Description

The preparation technology of the inorganic microspheroidal particles of surface uniform location titanium dioxide
Technical field
The present invention relates to material for air purification field, and in particular to photocatalyst material preparation technology, especially a kind of table The preparation technology of the inorganic microspheroidal particles of face uniform location titanium dioxide.
Background technology
TiO2As the catalysis material found earliest, there is nontoxic, catalytic activity(Degraded purification and water decomposition hydrogen manufacturing) It is high, oxidability is strong, stability is good, cost is low, the characteristic such as environment-friendly, be most possible practical catalysis material, with The rapid development of nanometer technology, preparation, modification and its application of nano titanium oxide are hot as the research of air purification field Point.However, because nano titanium oxide is easily reunited, on the other hand, TiO2Wider energy gap(3.2 eV)Determine It can only play photocatalytic activity under ultraviolet light, and very low to the utilization rate of sunshine, these all greatly limit its application.
The preparation method of titanium dioxide and modifying titanium dioxide is more, such as alkoxide hydrolysis, Hydrothermal preparation method, collosol and gel Method, chemical precipitation method and solid phase method etc., wherein, sol-gal process is prepared simply, and operation is convenient, condition is easily-controllable etc., it is conventional Preparation method.In order to improve the photocatalysis performance of titanium dioxide, be on the one hand by controlling reaction condition, such as concentration, temperature, The decentralization of titanium dioxide is improved, so as to increase contact surface to improve catalytic performance;On the other hand it is by ion doping, bears The method of modifying such as carry, defective locations can be introduced on surface by doping or change crystallinity, so as to influence answering for electronics and hole The absorption bands of light is closed or expands, so as to improve the photocatalytic activity of titanium dioxide.However, current method still have it is many Problem, as preparation process is more complicated;Titanium dioxide made from reaction can not be deposited, and with time lengthening, reunion rate greatly increases, and urges Change effect to substantially reduce, how to improve and keep the decentralization of titanium dioxide is this area technical barrier urgently to be resolved hurrily.
The content of the invention
To solve, existing titanium dioxide decentralization is poor, can not deposit the technical problem for causing activity low, this hair the long period It is bright that a kind of preparation technology of the inorganic microspheroidal particles of surface uniform location titanium dioxide is provided, by the way that colloidal sol oxide/titanium dioxide is applied Inorganic microsphere surface is overlying on, and titanium oxide dispersion is realized inorganic micro- by the technique sintered under drying, dynamic disturbances The twice dispersing of ball surface and sintering positioning, ensure that the decentralization of titanium dioxide, and substantially increase titanium dioxide and keep high The degree scattered time, so as to improve the catalytic performance of titanium dioxide.
The technical solution adopted by the present invention is:The preparation technology of the inorganic microspheroidal particles of surface uniform location titanium dioxide, Characterized in that, the preparation technology comprises the following steps:
(1)Water-soluble titanium source is soluble in water, lower addition weak caustic solution is stirred, wherein, titanium source, water, the quality parts ratio of weak base For 1:10-100:1-50,10-120min is stood, add peroxide, obtain solation titania systems;
(2)By solation titania systems even application in inorganic microsphere surface or dipping inorganic microsphere, room temperature to 100 DEG C it is dry Dry 1-3 h, less than 600-800 DEG C sintering 1-10 h, obtain the inorganic microspheroidal particles of surface uniform location titanium dioxide.
Further, the step(1)Solation titania systems through centrifuging or filtering, will precipitation or filter cake with water Resuspension is uniformly further purified, and controls the mass ratio of titanium dioxide and waterkFor 1:10~1000 .
Further, the step(2)By solation titania systems even application in inorganic microsphere surface or dipping The mass ratio relation that titanium dioxide and inorganic microsphere are controlled during inorganic microsphere is mT/mQ=KC,Whereinm TFor titanium dioxide quality,m QFor inorganic microsphere quality,CFor inorganic microsphere water absorption rate.
Further, the peroxide include but is not limited to hydrogen peroxide, sodium peroxide, potassium peroxide, calper calcium peroxide, One or more in sodium peroxydisulfate, potassium peroxydisulfate.
Further, the water-soluble titanium source is titanyl sulfate, titanium tetrachloride, titanium trichloride, titanium tetrafluoride or alkyl oxygen More than one or both of titanium, the weak base is ammoniacal liquor.
Further, the inorganic microsphere includes but is not limited to glass microballoon, silica-gel sphere, haydite, zeolite microballon, aluminum oxide Microballon, silicon-carbide particle, steel ball, aluminium pill or copper bead microballoon.
The present invention also provides the inorganic microspheroidal particles of above-mentioned surface uniform location titanium dioxide answering in fluidized bed plant With.
In above-mentioned technical proposal, there is provided a kind of preparation technology of inorganic microsphere surface positioning monodisperse titanium dioxide, specifically Comprise the following steps:Water-soluble titanium source is soluble in water, lower addition weak caustic solution is stirred, wherein, titanium source, water, the quality of weak base Portion rate is 1:10-100:1-50,10-120min is stood, is surface-treated with peroxide, obtains colloidal sol oxide/titanium dioxide body System, now the nano-particle in system is not grown up fully also, and crystallinity is very low, belongs to amorphous state mostly, scattered to ensure Degree, solation titania systems concentration general control is below 10%;By solation titania systems be uniformly coated or impregnated with Inorganic microsphere surface, room temperature to 100 DEG C of dry 1-3 h because titanium oxide is in aqueous scattered be it is very uniform, its Specific surface area is very big, after solation titania systems even application is in inorganic microsphere surface or dipping inorganic microsphere, by The suction-operated of water, form uniform water film simultaneously, colloidal sol oxide/titanium dioxide uniformly loads to inorganic microsphere surface, by model moral Magnificent power connection, with room temperature to 100 DEG C of dry 1-3 h, slowly removes moisture removal, prevents quick heating from causing vapor to surface dioxy Change the impact of titanium.And unadsorbed unnecessary titanium dioxide can be washed with water after drying at room temperature, greatly reduce titanium oxide Reunion.After deionized water gently rinses the unadsorbed titanium dioxide of removal, 0.1-10 h, the temperature are sintered at 400-800 DEG C The lower rutile titanium dioxide crystallinity that can be obtained of degree is high, and activity height, temperature will be low, causes sintering time oversize, activity Reduce, high energy consumption, and temperature is too high is also easy to produce crystal transfer, in sintering process, the peroxy of titanium dioxide surface grafting Group occurs the cross-linking reaction between particle and forms bridging oxygen chemical bond with microsphere surface, uniform, firmly negative so as to obtain surface Carry the inorganic microspheroidal particles of monodisperse titanium dioxide.
The beneficial effects of the invention are as follows:(1)Process of preparing provided by the invention is simple, and titanium dioxide is in inorganic microsphere The decentralization on surface is high, does not reunite persistently, and firm position, difficult for drop-off, substantially increases catalytic efficiency;(2)Preparation method In be not related to organic solvent, save the energy, it is more green;(3)In further improved technical scheme, by control system All moisture content are exactly equal to inorganic microsphere saturated water adsorptive value so that the moisture film on inorganic microsphere surface is stable to be adsorbed, and no free water is deposited So as to ensure that inorganic microsphere surface titanium dioxide is individual layer monodisperse status nano particle;By controlling titanium dioxide body The concentration and titanium dioxide of system and the ratio of inorganic microsphere so that the monodisperse titanium dioxide quantity of inorganic microsphere surface positioning More, decentralization height, it is evenly distributed, catalytic efficiency greatly improves.
Brief description of the drawings
Fig. 1, Fig. 2 are the glass microballoon that monodisperse titanium dioxide nanometer particle is located in the gained surface of the embodiment of the present invention 1 The scanning electron microscope (SEM) photograph of different amplification.
Fig. 3 is the datagram of embodiment 1-4 products obtained therefroms degraded acetaldehyde effect.
Embodiment
The present invention provides a kind of preparation technology of inorganic microsphere surface positioning monodisperse titanium dioxide, below by way of specific reality Apply example and describe the present invention in detail in order to understanding, but the invention is not limited in any way, in embodiment involved reagent for example without Special instruction, it can be bought and obtained by commercial sources, institute's application method, be conventional method unless otherwise instructed.
Embodiment 1:
10g titanyl sulfates are dissolved in 500ml water, the lower ammoniacal liquor for adding 110mL concentration 2.5% is stirred, staticly settles reaction 30min, being centrifuged with 8000-10000r/min, then remove supernatant, centrifugation gained solid precipitation is resuspended with 90ml water, by Stirring and ultrasound make the system after resuspension uniform, add 60g hydrogen peroxide(Mass concentration is 30%), obtain colloidal sol oxide/titanium dioxide System;
(2)The glass microsphere of 20 μm of average grain diameter is chosen, washing, alcohol are washed, oil removing and after drying, and colloidal sol oxide/titanium dioxide is sprayed In glass microballoon surface, 45 DEG C of 3 h of drying, 800 DEG C sinter 1 h, obtain the glass microsphere particle of surface uniform location titanium dioxide (S1), scanning electron microscope (SEM) photograph is visible on figure as shown in Fig. 1, Fig. 2, glass microsphere area load layer of titanium dioxide nano particle, Uniformly, monodispersity can be good for grain dispersiveness, and the particle diameters of titania nanoparticles is 50-100nm, size uniform.Further lead to Cross the front and rear contrast of quality and find that the load capacity of titania nanoparticles is the 1% of glass microsphere quality.
Embodiment 2:
10g titanium tetrachlorides are dissolved in 300ml water, the lower ammoniacal liquor for adding 100ml concentration 2.5% is stirred, staticly settles reaction 30min, being centrifuged with 8000-10000r/min, then remove upper liquid, centrifugation gained solid precipitation is resuspended with 100ml water, by Stirring and ultrasound make the system after resuspension uniform, add 50g hydrogen peroxide, obtain dissolved colloidal state titania systems;
(2)Colloidal sol oxide/titanium dioxide is sprayed to 100 μm of silica gel microball surface, 35 DEG C of 3 h of drying, 600 DEG C of 3 h of sintering, obtained The silica gel microball particle of monodisperse titanium dioxide is located in surface(S2), the front and rear contrast discovery of quality, titania nanoparticles Load capacity be silica gel microball quality 0.89%.
Embodiment 3:
10g titanium trichlorides are dissolved in 300ml water, the lower ammoniacal liquor for adding 200ml concentration 2.5% is stirred, staticly settles reaction 30min, filter, gained filter cake is resuspended with 100ml water, is made the system after resuspension uniform by stirring and ultrasound, is added 70g peroxides Change hydrogen, obtain dissolved colloidal state titania systems;
(2)Colloidal sol oxide/titanium dioxide is sprayed to 100 μm of ceramic fine bead surface, 50 DEG C of 2 h of drying, 700 DEG C of sintering 3h, obtains table Face sinters the ceramic fine bead that monodisperse titanium dioxide is located(S3), the front and rear contrast discovery of quality, titania nanoparticles Load capacity is the 0.94% of ceramic fine bead quality.
Embodiment 4:
The mixture of 10g titanium trichlorides and alkyl oxygen titanium is dissolved in 300ml water and stirred, stirs lower addition 150ml concentration 2.5% ammoniacal liquor, reaction 50min is stood, is filtered, gained filter cake is resuspended with 100ml water, and stirring and ultrasound make the system after resuspension Uniformly, 70g hydrogen peroxide is added, obtains dissolved colloidal state titania systems;
(2)Colloidal sol oxide/titanium dioxide is sprayed to 3 μm of copper bead microsphere surface, 65 DEG C of 1 h of drying, 600 DEG C of 3 h of sintering, obtains table The copper bead microsphere particle of monodisperse titanium dioxide is located in face, and the front and rear contrast of quality is found, the load of titania nanoparticles Measure as the 0.91% of ceramic fine bead quality.
Experimental performance is tested
Each product in above-described embodiment is subjected to acetaldehyde degradation performance test according to following test method respectively.
The setting of test chamber:It is 1.5m that corresponding each sample prepares volume respectively3Laboratory Module, separately prepare a 1.5m3Sky White control cabin, the inorganic microsphere of the above-mentioned surface positioning monodisperse titanium dioxides of 200g, blank are respectively put into each Laboratory Module Control is put into 2g titanium dioxide dry powder in cabin(Step 1 gained dissolved colloidal state titania systems are spray-dried, 600 DEG C of 3 h of sintering Grinding gained afterwards)And the glass microsphere in 198g embodiments 1, then it is filled with respectively into Laboratory Module and blank control cabin identical dense Degree(5mg/m3)Acetaldehyde, close test chamber;The fan of test chamber is then opened simultaneously, makes Cabin contamination thing cycle balance, 24h The concentration of pollutant in test chamber is sampled simultaneously again afterwards, analysis test, calculates acetaldehyde residual rate, computational methods are with reference to such as Lower formula:Acetaldehyde residual rate=sample experiments cabin acetaldehyde concentration value ÷ blank controls cabin acetaldehyde concentration value × 100%.As a result referring to figure 3, as shown by data, with particle obtained by the inorganic microspheroidal particles of the surface uniform location titanium dioxide of preparation method of the present invention preparation Titania nanoparticles maintain good high dispersion, it is easy to substantially improve titanium dioxide obtained by current preparation method The defects of reunion, contact area of the titanium dioxide in use with ambient atmos is improved, ensure that its efficient catalytic is imitated Rate, while caused by also largely avoided titanium dioxide micro-nano particle in itself the problems such as PM2.5 dust pollutions.
As fully visible, the inorganic microsphere of uniform location titanium dioxide in surface provided by the invention, the letter of its manufacturing process steps Victory, operation is simple, improves gained titanium dioxide monodisperse status, is stored beneficial to long-time, improves its activity and urges Change performance;It is used for fluidized bed plant as catalysis filtrate, substantially increases the catalytic efficiency of fluid bed and the service life of filtrate, It can also be filled in the devices such as air purifier, for improving IAQ.

Claims (8)

1. the preparation technology of the inorganic microspheroidal particles of surface uniform location titanium dioxide, it is characterised in that the preparation technology bag Include following steps:
(1)Water-soluble titanium source is soluble in water, lower addition weak caustic solution is stirred, wherein, titanium source, water, the quality parts ratio of weak base For 1:10-100:1-50,10-120min is stood, add peroxide, obtain solation titania systems;
(2)By solation titania systems even application in inorganic microsphere surface or dipping inorganic microsphere, room temperature to 100 DEG C it is dry Dry 1-3 h, less than 400-800 DEG C sintering 0.1-10 h, obtain the inorganic microspheroidal particles of surface uniform location titanium dioxide.
2. preparation technology according to claim 1, it is characterised in that the step(1)Solation titania systems Through centrifuging or filtering, precipitation or filter cake are resuspended with water and are uniformly further purified, controls the mass ratio of titanium dioxide and waterkFor 1: 10~1000 。
3. preparation technology according to claim 2, it is characterised in that the step(2)By solation titania systems It is m that even application controls the mass ratio relation of titanium dioxide and inorganic microsphere when inorganic microsphere surface or dipping inorganic microsphereT/ mQ=KC,Whereinm TFor titanium dioxide quality,m QFor inorganic microsphere quality,CFor inorganic microsphere water absorption rate.
4. preparation technology according to claim 1, it is characterised in that titanium member in the addition and titanium source of the peroxide The mol ratio of element is 5:1~20:1.
5. preparation technology according to claim 1, it is characterised in that the peroxide includes but is not limited to peroxidating One or more in hydrogen, sodium peroxide, potassium peroxide, calper calcium peroxide, sodium peroxydisulfate, potassium peroxydisulfate, the weak base are ammoniacal liquor.
6. preparation technology according to claim 1, it is characterised in that the water-soluble titanium source is titanyl sulfate, four chlorinations It is more than one or both of titanium, titanium trichloride, titanium tetrafluoride or alkyl oxygen titanium.
7. preparation technology according to claim 1, it is characterised in that it is micro- that the inorganic microsphere includes but is not limited to glass Pearl, silica-gel sphere, haydite, zeolite microballon, aluminum oxide microballon, silicon-carbide particle, steel ball, aluminium pill or copper bead microballoon.
A kind of 8. application of inorganic microspheroidal particles of surface uniform location titanium dioxide in fluidized bed plant.
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JPS58153950A (en) * 1982-03-08 1983-09-13 Canon Inc Capsulated toner
JPH11285635A (en) * 1997-12-26 1999-10-19 Nihon Yamamura Glass Co Ltd Photochemical reactor element containing microencapsulated titanium dioxide photocatalyst
DE19963441A1 (en) * 1999-12-28 2001-07-05 Basf Ag Regenerating copper-containing catalysts used in hydrogenation of methylol-aldehydes to methylol-alcohols involves treatment in oxygen-containing medium and re-activation in hydrogen-containing medium
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