CN101234783B - Method for preparing nano titanium dioxide by using surfactant peptization method - Google Patents
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- CN101234783B CN101234783B CN200810026488XA CN200810026488A CN101234783B CN 101234783 B CN101234783 B CN 101234783B CN 200810026488X A CN200810026488X A CN 200810026488XA CN 200810026488 A CN200810026488 A CN 200810026488A CN 101234783 B CN101234783 B CN 101234783B
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Abstract
The invention belongs to a field for preparing nano titanium dioxide, which discloses a method for preparing the nano titanium dioxide by using a surfactant colloidal chemical method with simple process and low cost. The method adopts meta-titanic acid as raw material; acetate, oxalate, citric acid, tween 20, span 40, polyethylene glycol 2,000 and polyvinyl alcohol 2,000 are added to be carried out peptization reaction under water bath temperature of 30-90 DEG C to obtain nano meta-titanic acid colloidal solution; then precursor of titanium dioxide nano-particle is prepared by drying; the precursor is calcinated and heat preserved to obtain nano titanium dioxide powder. The method for preparing the nano titanium dioxide has wide material source, low cost and simple preparation process; furthermore, the method does not need to update and transform the device and has no special production devices and low cost; the method has low cost of the titanium material and little environment pollution; the nano titanium dioxide is prepared by three steps.
Description
Technical field
The invention belongs to the nano-particle material preparing technical field, particularly adopt low cost titanium raw material---metatitanic acid (H
2TiO
3, TiO (OH)
2) adding does not have the inorganic impurity negatively charged ion or cationic combination organic surface active agent---the peptizing agent peptisation prepares the method for nano titanium oxide.
Background technology
Why nano material is subjected to the many-sided extensive concern in countries in the world in recent decades, particularly in recent years about the upsurge of nano material preparation and application especially a wave be higher than a wave, its basic reason is that people find under study for action, there are fundamental characteristics such as small-size effect, surface interface effect, quantum size effect and quantum tunneling effect in nano material, and these characteristics make nano material that incomparable special performance of traditional material and great potential using value be arranged.
Titanium dioxide (TiO
2Be commonly called as titanium white) be the present best a kind of white pigment of performance in the world, be widely used in industry such as coating, plastics, papermaking, printing-ink, chemical fibre, rubber, makeup.The industrial sulphuric acid method is produced the titanium dioxide Technology and is adopted the ilmenite of hot vitriol oil decomposition through selected pulverizing, is that reductive agent makes TiOSO with the iron powder
4, ferrous iron and other associated metal vitriol mixing solutions (being commonly called as titanium liquid).Titanium liquid is the inducing of nucleus under through concentrating the back at the titanic acid colloids, with dense titanium liquid pressurize, heating hydrolysis generation hydrated titanium dioxide (H
2TiO
3, TiO (OH)
2Be commonly called as metatitanic acid).Metatitanic acid after filtration, washing and bleaching, calcining, pulverize, packing promptly gets titanium dioxide powder (titanium dioxide).China is the big producing country of sulfate process titanium dioxide, family surplus the factory of national sulfuric acid process has 60, and about 600,000 t/a of overall throughput, output has occupied the 2nd in the world, is only second to the U.S..
Producing nano titanium oxide compares with titanium alkoxide, titanium tetrachloride, with the metatitanic acid is that raw materials cost can reduce several magnitude, at home raw material sources extensively and also raw material have nontoxic, not have danger, normal temperature liquid phase reaction, reaction process and reaction conditions loose, easily expand to industrial-scale production, " three wastes " pollution less, advantages such as the product purity height that obtains, steady quality.For sulfate process titanium dioxide production provides an economy, feasible approach in the deep processing of the enterprising interline product in original technology basis, be that the optimum feed stock of industrial production nano titanium oxide is selected.
The production method of nano titanium oxide mainly is divided into vapor phase process and liquid phase method.With the titanium alkoxide is that the main preparation technology of feedstock production nano titanium oxide is a sol-gel method; The main preparation technology who with the titanium tetrachloride is the feedstock production nano titanium oxide has liquid phase water solution (chemical precipitation method) and oxyhydrogen flame hydrolysis method; With TiOSO
4For the main method of feedstock production nano titanium oxide has chemical precipitation method, gel method and hydrothermal method, wherein chemical precipitation method is most widely used.Liquid-phase precipitation method has the advantages that apparatus and process is simple, technical requirements is not high and cost is low, therefore is highly suitable for the production of heavy industrialization.Adopting raw material cheapness, the simple preparation method of technology to obtain high performance nano titanium oxide, is the major objective pursued of industrial production nano titanium oxide technology now.
The titanium resource of China is very abundant, and standing stock occupy first place in the world.90 percent of titanium resource is to be used to make titanium dioxide, and the number of titanium dioxide consumption is that the economist is used for one of leading indicator of weighing a national people's living standard.Can predict, nano titanium oxide is used in the all-round popularization in each field, and people's life will be had a revolutionary change.
Liquid phase method prepares nano powder and has the common equipment of use, the ripe simple advantage of technical process, but a contradiction is arranged, if it is little to control sedimentary primary particle size, big, the high adsorption capacity of specific surface then, particle agglomeration is serious, stops up filter cloth, for filtering the matting operational difficulty; Because high adsorption capacity, foreign ion also is difficult for wash-out; Because high adsorption capacity, the particle of reuniting when seriously making the calcining powder change oxide compound into by oxyhydroxide is very easily grown up and is difficult to obtain nano particle.If it is bigger to control sedimentary primary particle size, to clean though easily filter, this moment, primary particle was not a nano level, so also can not get nano particle after the calcining.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, the object of the present invention is to provide that a kind of preparation technology is simple, low price, the combined surfactant that utilizes with actual application value prepare the method for nano titanium oxide as the peptizing agent peptisation.The present invention is with the intermediate product of sulfate process titanium dioxide---and metatitanic acid is the feedstock production nano-titanium dioxide powder, and it is extensive, cheap to have raw material sources, helps advantages such as suitability for industrialized production, is the important channel of mass preparation nano-titanium dioxide powder.
The present invention adopts the larger-size metatitanic acid of primary particle that hydrolysis obtains under the not too strict condition of titanium hydrolysis, after cleaning after filtration,, bleaching, utilize not combination compound surfactant with inorganic impurity ion (tensio-active agent can calcination process is burned fall) to carry out the peptization reaction for peptizing agent, nano level colloidal sol by control combination peptizing agent concentration and peptization temperature acquisition controlled dimensions easily obtains nano-oxide particles through calcining under the situation that does not increase operation and equipment.
Nano titanium dioxide (TiO of the present invention
2) powder can be at air, water body purification; And in makeup, paint, use.
Purpose of the present invention is achieved through the following technical solutions: a kind of method of utilizing the tensio-active agent peptisation to prepare nano titanium oxide comprises following processing step:
(1) in metatitanic acid, adds entry, being transferred to concentration is metatitanic acid powder-aqeous suspension of 0.125～1mol/L, add the peptizing agent that is combined into by tensio-active agent acetate, oxalic acid, citric acid, polysorbas20, span 40, Macrogol 2000 and polyvinyl alcohol 2000 then, under 20～90 ℃ of bath temperatures, carry out the peptization reaction, water-bath time 30～240min obtains nano level metatitanic acid colloidal solution.Described metatitanic acid: acetate: oxalic acid: citric acid: polysorbas20: span 40: Macrogol 2000: the mol ratio of polyvinyl alcohol 2000 is 1: 0.2～2: 0.2～2: 0.2～2: 0.01～0.1: 0.01～0.1: 0.01～0.1: 0.01～0.1.
(2) the nano level metatitanic acid colloidal solution drying that step (1) is obtained promptly makes precursor---the exsiccant metatitanic acid particle of nano titania grade particles.
(3) above-mentioned precursor is incubated 2～10h 150～550 ℃ of calcinings, prepares Nano titanium dioxide (TiO
2) powder.
In order to realize the present invention better, metatitanic acid is to adopt the metatitanic acid after cleaning, bleaching in the titanium dioxide factory Titanium White Production By Sulfuric Acid Process process in the described step (1); Water is distilled water or deionized water in the described step (1).
Drying is spraying drying or ultrasonic wave drying in the described step (2), described ultrasonic wave drying is the ultrasonic sound appratus that the nano level metatitanic acid colloidal solution that step (1) obtains is placed the band water-bath, under 40～80 ℃, every concussion in 10 minutes 5 minutes, after treating into pasty state, concussion is to doing continuously.Adopt spraying drying or ultrasonic wave drying to make the presoma of dried nano titania grade particles loose, be difficult for growing up at the calcination stage particle.
The present invention compared with prior art, have following advantage and beneficial effect: raw material sources of the present invention are extensive, with low cost, preparation technology simply, does not need equipment is renovated, no special producing equipment price is cheap, the titanium material cost is low, environmental pollution is few, only three steps promptly were prepared into Nano titanium dioxide, had actual application value.The present invention has walked around the nano material presoma has been filtered, and cleaning process easily produces obstruction, wear filter and be difficult to clean bottleneck step such as impurity, easily enlarges and produces, and has actual application value.
Description of drawings
Fig. 1 is a nano-titanium dioxide powder XRD figure of the present invention.
Fig. 2 is nano-titanium dioxide powder transmission electron microscope figure of the present invention.
Fig. 3 is a 0.25mol/L metatitanic acid colloidal sol grain-size graph.
Fig. 4 is nano titanium dioxide photocatalysis degraded tropeolin-D design sketch of the present invention.
Fig. 5 is nano titanium dioxide photocatalysis degraded benzene design sketch of the present invention.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
(1) adopt the intermediate product after cleaning, bleaching in the titanium dioxide factory Titanium White Production By Sulfuric Acid Process process---metatitanic acid adding distilled water, being transferred to concentration is metatitanic acid powder-aqeous suspension of 0.125mol/L, add the peptizing agent that acetate, oxalic acid, citric acid, polysorbas20, span 40, Macrogol 2000 and polyvinyl alcohol 2000 are combined into then, metatitanic acid: acetate: oxalic acid: citric acid: polysorbas20: span 40: Macrogol 2000: the mol ratio of polyvinyl alcohol 2000 is 1: 0.2: 0.4: 0.3: 0.01: 0.01: 0.01: 0.01.Carry out peptization reaction (stirring 1 minute every 5 minutes) under 50 ℃ of bath temperatures, water-bath time 60min obtains nano level metatitanic acid colloidal solution.Reaction formula is as follows:
TiO(OH)
2-(HO)
2OTi+nR
-＝TiO(OH)
2R
n/2+TiO(OH)
2R
n/2
R represents the organic carbon hydrogen group of tensio-active agent, interrupts the OH of strong reunion suction
-Key.
(2) the nano level metatitanic acid colloidal solution small-sized spray drier drying that step (1) is obtained enters the nano level metatitanic acid colloidal solution flow velocity 76ml/h of small-sized spray drier, 180 ℃ of hot blast temperatures, hot blast speed 18m
3/ h obtains precursor---the exsiccant metatitanic acid particle of loose nano titania grade particles.
(3) above-mentioned precursor is incubated 6h 400 ℃ of calcinings, prepares Nano titanium dioxide (TiO
2) powder.Show that by the X diffracting spectrum crystalline phase is the Detitanium-ore-type of titanium dioxide, as shown in Figure 1; Is 16.65nm according to the Scherrer formula by the peak width calculating grain-size of X diffracting spectrum, as shown in Figure 1.Transmission electron microscope observation also has analog result.As shown in Figure 2.
Embodiment 2
(1) adopt the intermediate product after cleaning, bleaching in the titanium dioxide factory Titanium White Production By Sulfuric Acid Process process---metatitanic acid adding deionized water, being transferred to concentration is metatitanic acid powder-aqeous suspension of 0.25mol/L, add the peptizing agent that acetate, oxalic acid, citric acid, polysorbas20, span 40, Macrogol 2000 and polyvinyl alcohol 2000 are combined into then, metatitanic acid: acetate: oxalic acid: citric acid: polysorbas20: span 40: Macrogol 2000: the mol ratio of polyvinyl alcohol 2000 is 1: 0.2: 0.2: 0.2: 0.01: 0.01: 0.01: 0.01.Carry out peptization reaction (stirring 1 minute every 5 minutes) under 90 ℃ of bath temperatures, water-bath time 30min obtains nano level metatitanic acid colloidal solution.Adopting the Malvern laser light scattering instrument to measure the colloidal particle diameter is 28.1nm.As Fig. 3.
(2) the nano level metatitanic acid colloidal solution that step (1) is obtained places the ultrasonic sound appratus of band water-bath, under 80 ℃, every 10 minutes the concussion 5 minutes, treat into pasty state after, concussion promptly makes precursor---the exsiccant metatitanic acid particle of nano titania grade particles to doing continuously.
(3) above-mentioned precursor is incubated 10h 150 ℃ of calcinings, prepares Nano titanium dioxide (TiO
2) powder, be 34.41nm according to the Scherrer formula by the peak width calculating grain-size of X diffracting spectrum.
Embodiment 3
(1) adopt the intermediate product after cleaning, bleaching in the titanium dioxide factory Titanium White Production By Sulfuric Acid Process process---metatitanic acid adding distilled water, being transferred to concentration is metatitanic acid powder-aqeous suspension of 0.5mol/L, add the peptizing agent that acetate, oxalic acid, citric acid, polysorbas20, span 40, Macrogol 2000 and polyvinyl alcohol 2000 are combined into then, metatitanic acid: acetate: oxalic acid: citric acid: polysorbas20: span 40: Macrogol 2000: the mol ratio of polyvinyl alcohol 2000 is 1: 1.5: 1.6: 0.5: 0.05: 0.05: 0.05: 0.02.Carry out peptization reaction (stirring 1 minute every 5 minutes) under 70 ℃ of bath temperatures, water-bath time 60min obtains nano level metatitanic acid colloidal solution.
(2) the nano level metatitanic acid colloidal solution that step (1) is obtained places the ultrasonic sound appratus of band water-bath, under 60 ℃, every 10 minutes the concussion 5 minutes, treat into pasty state after, concussion promptly makes precursor---the exsiccant metatitanic acid particle of nano titania grade particles to doing continuously.
(3) above-mentioned precursor is incubated 3h 500 ℃ of calcinings, prepares Nano titanium dioxide (TiO
2) powder, be 46.98nm according to the Scherrer formula by the peak width calculating grain-size of X diffracting spectrum.
Embodiment 4
(1) adopt the intermediate product after cleaning, bleaching in the titanium dioxide factory Titanium White Production By Sulfuric Acid Process process---metatitanic acid adding deionized water, being transferred to concentration is metatitanic acid powder-aqeous suspension of 0.75mol/L, add the peptizing agent that acetate, oxalic acid, citric acid, polysorbas20, span 40, Macrogol 2000 and polyvinyl alcohol 2000 are combined into then, metatitanic acid: acetate: oxalic acid: citric acid: polysorbas20: span 40: Macrogol 2000: the mol ratio of polyvinyl alcohol 2000 is 1: 2: 2: 2: 0.1: 0.1: 0.1: 0.1.Carry out peptization reaction (stirring 1 minute every 5 minutes) under 20 ℃ of bath temperatures, water-bath time 240min obtains nano level metatitanic acid colloidal solution.
(2) the nano level metatitanic acid colloidal solution that step (1) is obtained places the ultrasonic sound appratus of band water-bath, under 40 ℃, every 10 minutes the concussion 5 minutes, treat into pasty state after, concussion promptly makes precursor---the exsiccant metatitanic acid particle of nano titania grade particles to doing continuously.
(3) above-mentioned precursor is incubated 4h 550 ℃ of calcinings, prepares Nano titanium dioxide (TiO
2) powder, be 53.77nm according to the Scherrer formula by the peak width calculating grain-size of X diffracting spectrum.
The comparative example 1
(1) nano-titanium dioxide powder that the present invention is made carries out the photocatalytic degradation experiment, the Pyrex glass reactor of a capacity 150ml, ultraviolet high-pressure mercury lamps (the 150w of a built-in band silica tube sheath, predominant wavelength 368nm), the outer tube chuck feeds recirculated cooling water and keeps the temperature of reaction unanimity, adding concentration is the methyl orange aqueous solution 100ml of 40mg/L, and used tropeolin-D is analytical pure in the experiment, directly is mixed with solution and uses.The nano-titanium dioxide powder (as photocatalyst) that adds 0.020g again, ultra-sonic dispersion 10min on ultrasonic washing instrument, the dark place magnetic stirrer stirred 30 minutes, it is fully disperseed, and make absorption reach balance, under the ultraviolet high-pressure mercury lamps irradiation, carry out the photodegradation reaction then, every illumination 4min, the 2ml methyl orange aqueous solution sample that takes out, centrifugation under 9000 rev/mins rotating speed, supernatant liquid filters with the needle-based strainer again, with the absorbancy (the mensuration wavelength is decided to be 464nm during analysis) of 722s type spectrophotometric determination filtrate, thereby calculates the degradation rate of tropeolin-D.Experiment is model reaction with the methyl orange degradation, reflects the active size of photocatalyst with the degradation rate of tropeolin-D.Along with the prolongation of light application time, the color of methyl orange solution is shoaled gradually by orange, until colourless.Degradation rate calculates with following formula:
D＝1-Ct/C0
In the formula: C0 is that solution is in 464nm place absorbancy before the illumination, and Ct is the absorbancy of getting solution example behind every illumination 4min.Calculate the degradation rate D of different time in view of the above.Other gets P25 type titanium dioxide that German Degussa company produces and carries out photochemical catalysis similarity condition under and test and compare.By Fig. 4 be the degradation rate D that obtains of the prepared titanium dioxide of the present invention and P25 type optically catalytic TiO 2 experiment with the time relation curve as can be known, the nano-titanium dioxide powder photocatalysis performance that the present invention prepares is better.
The comparative example 2
Be degraded to model reaction with benzene, reflect the active size of nano-titanium dioxide powder photocatalyst of the present invention with the degradation rate of benzene.Used benzene is analytical pure in the experiment, is not further purified and directly use.Photocatalyst is contained in the quartz glass tube, reaction bed is respectively adorned a ultraviolet lamp up and down, the parallel placement with reactor of ultraviolet high-pressure mercury lamps is also fixing, benzene vapour passes through from right to left, to be adsorbed during by reaction bed and a degraded part arranged under the ultra violet lamp, residual gas by measuring the variation of benzene content, draws the degradation rate of benzene in sometime by gas chromatograph.
Degradation rate calculates with following formula:
D＝1-Ct/C
0
In the formula: C
0Be the benzene peak value of gas chromatograph for determination before the illumination, the benzene peak value of the gas chromatograph for determination when Ct is the every 20min of illumination.
Be illustrated in figure 5 as the degradation rate D and the time relation curve of benzene vapour, reach more than 80% through the 120min degradation rate.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (5)
1. method of utilizing the tensio-active agent peptisation to prepare nano titanium oxide is characterized in that comprising following processing step:
(1) in metatitanic acid, adds entry, being transferred to concentration is metatitanic acid powder-aqeous suspension of 0.125～1mol/L, add the peptizing agent that is combined into by tensio-active agent acetate, oxalic acid, citric acid, polysorbas20, span 40, Macrogol 2000 and polyvinyl alcohol 2000 then, under 20～90 ℃ of bath temperatures, carry out the peptization reaction, water-bath time 30～240min obtains nano level metatitanic acid colloidal solution; Described metatitanic acid: acetate: oxalic acid: citric acid: polysorbas20: span 40: Macrogol 2000: the mol ratio of polyvinyl alcohol 2000 is 1: 0.2～2: 0.2～2: 0.2～2: 0.01～0.1: 0.01～0.1: 0.01～0.1: 0.01～0.1;
(2) the nano level metatitanic acid colloidal solution drying that step (1) is obtained promptly makes precursor---the exsiccant metatitanic acid particle of nano titania grade particles;
(3) above-mentioned precursor is incubated 2～10h 150～550 ℃ of calcinings, prepares nanometer level titanium dioxide powder.
2. the method for utilizing the tensio-active agent peptisation to prepare nano titanium oxide according to claim 1 is characterized in that: metatitanic acid is to adopt the metatitanic acid after cleaning, bleaching in the titanium dioxide factory Titanium White Production By Sulfuric Acid Process process in the described step (1).
3. the method for utilizing the tensio-active agent peptisation to prepare nano titanium oxide according to claim 1 is characterized in that: water is distilled water or deionized water in the described step (1).
4. the method for utilizing the tensio-active agent peptisation to prepare nano titanium oxide according to claim 1 is characterized in that: dry in the described step (2) is spraying drying or ultrasonic wave drying.
5. the method for utilizing the tensio-active agent peptisation to prepare nano titanium oxide according to claim 4, it is characterized in that: described ultrasonic wave drying is the ultrasonic sound appratus that the nano level metatitanic acid colloidal solution that step (1) obtains is placed the band water-bath, under 40～80 ℃, every concussion in 10 minutes 5 minutes, after treating into pasty state, concussion is to doing continuously.
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| CN102616841B (en) * | 2012-02-22 | 2014-06-18 | 山东东佳集团股份有限公司 | Method for producing titanium dioxide for denitration catalyst |
| CN103523821B (en) * | 2013-05-04 | 2015-07-15 | 陕西华龙敏感电子元件有限责任公司 | Preparation method of titanium dioxide |
| CN103531363B (en) * | 2013-10-24 | 2017-05-31 | 攀枝花学院 | The preparation method of dye sensibilization solar cell nanometer TiO2 film light anode slurries |
| CN103913497A (en) * | 2014-04-17 | 2014-07-09 | 常州联德电子有限公司 | Lead-poisoning-resistant protective coating of automotive oxygen sensor and preparation method of coating |
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