CN101062475A - Metasilicate hole material assembled nano titanium oxide composite material and preparation method thereof - Google Patents
Metasilicate hole material assembled nano titanium oxide composite material and preparation method thereof Download PDFInfo
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- CN101062475A CN101062475A CN 200610026268 CN200610026268A CN101062475A CN 101062475 A CN101062475 A CN 101062475A CN 200610026268 CN200610026268 CN 200610026268 CN 200610026268 A CN200610026268 A CN 200610026268A CN 101062475 A CN101062475 A CN 101062475A
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Abstract
The invention relates to the making of nanometer titanic anhydride compound material using silicate porous material, with weight percentage of phyllosilicate being 92. 2-95. 9%, and anatase Ti being O27. 8-4. 1%. It is low in processing cost, extended in stone ore application, being able to produce high value-added product with simple process, easy material access, undemanding processing conditions, difficult to pollute, better distribution, effective control of the crystalline dimension, greatly improved in TiO2 compound material feature.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material, particularly metasilicate hole material assembled nano titanium oxide composite material and preparation method thereof.
Background technology
Pure TiO
2Semi-conductive photoresponse scope is narrower, and the recombination probability that semiconductor photoproduction electrons/is right is higher, and excitation state valence band hole and conduction band electron be inactivation very easily, and is therefore limited to the degradation effect of organic pollution (as the dioxin persistence organic pollutant).TiO
2Composite can improve TiO to a certain extent
2Activity, however the reunion easily in the preparation of grained catalyst particle is dispersed bad in application, can not fully contact with pollutant.
Early 1990s, the compound system of nano particle/mesoporous solid is noticeable in the nanometer material science.The hole that the method for utilizing physics or chemistry is put into micro/meso porous solid with nano particle constitutes the assembly system of the two, the numerous characteristics that not only has nanoparticle, and produced nanoparticle and the not available special nature of mesoporous solid itself again.Simultaneously, also be expected to make people to realize modulation to some character according to oneself wish.This assembly system and metallic/glass composite material, particle mosaic coat, nano composite material etc. are structurally completely different.Because the hole in the mesoporous solid is open; and interconnect; therefore; not only there is the interface between heterogeneous nano particle and the hole wall in assembly system; and also there is Free Surface in the hole endoparticle; and contact with surrounding medium (atmosphere or liquid phase medium); so this assembly system certainly exists the restriction in hole; the interface coupling; with since the high activity of nano grain surface and to around atmosphere; liquid phase; temperature; environmental condition sensitivities such as relative humidity (the especially assembly system of metallic particles); thereby make the mesoporous micropore reactor that constituted, form a series of particular performances.
Nano pore with micro/meso porous material is that the method that template agent assembling function particle adopts usually has ion-exchange, chemical deposition, absorption object method and hydrothermal synthesis method etc., and assembly object mainly contains simple substance, sulfide, oxide and composite nanometer particle.Katovic has been assembled into metal simple-substance Al, Fe and Zn in the pore structure.Found that, the existence of Al, Fe and Zn has changed the acidity of former mesopore molecular sieve, makes it might be applied to acidity, oxidative catalyst field (Microporous andMesoporous Materials, 2001,44～45:275～281), people such as Li adopt mechanical mixture with SnO
2Be assembled in the MCM-41 mesopore molecular sieve.Because mesopore molecular sieve duct itself is to the limitation effect of particle, the SnO after the assembling
2Particle evenly distributes in the duct, and agglomeration obviously reduces, and the corresponding increase of its specific area impels its selectivity and sensitiveness to gas all to increase, especially at 250～600 ℃ to H
2Susceptibility than pure SnO
2Significant raising (Sensors and Actuators1999, B 59:1～8) has been arranged.
At present also relevant for nanometer Zn FeO
4Successfully be assembled into the report in the mesoporous silicon based body, but its heat endurance of prepared product is not ideal.People such as Zhou are successfully with ZnFeO
4Be assembled in the silicon mesoporous material, products therefrom not only has the good magnetic performance of being expected, and shows the transparency (Materials Chemistry and Physics, 2002,75:181～185) in visible wavelength range.These researchs are to adopt M41S series molecular sieve to be the assembling main body mostly, and the raw material for preparing this molecular sieve analog mostly is organic matter greatly, and cost is higher, and the easy contaminated environment of product.
Hole assembling TiO
2Can make TiO
2Be evenly distributed in the duct, fully contact, thereby improve active effectively with pollutant.In addition because the hole in the mesoporous solid is open; and interconnect; therefore; not only there is the interface between heterogeneous nano particle and the hole wall in assembly system; and also there is Free Surface in the hole endoparticle; and contact with surrounding medium (atmosphere or liquid phase medium); so this assembly system certainly exists the restriction in hole; the interface coupling; with since the high activity of nano grain surface and to around atmosphere; liquid phase; temperature; environmental condition sensitivities such as relative humidity (the especially assembly system of metallic particles); thereby make the mesoporous micropore reactor that constituted, form a series of particular performances.
But, existing hole assembling TiO
2All be to utilize MCM41, must be synthetic by certain chemical technology, more time-consuming.
Summary of the invention
The object of the present invention is to provide metasilicate hole material assembled nano titanium oxide composite material and preparation method thereof, processing cost is low, widens the range of application in talcum ore deposit simultaneously, produces high value-added product; Technology is simple, and raw material is easy to get, and condition is comparatively loose, is difficult for contaminated environment; Assembled titania is well disperseed, and crystallite dimension is controlled, and prepared hole assembling TiO2 performance of composites improves a lot before the assembling.
Technical scheme of the present invention is, metasilicate hole material assembled nano titanium oxide composite material, and its composition quality percentage is:
Layered phyllosilicate porous material 92.2～95.9
Detitanium-ore-type TiO
27.8～4.1.
The pore volume of phyllosilicate mesoporous material is 0.22ml/g, and pore size distribution range is 1.2～5.5nm, and specific area is 133m
2/ g.The TiO that is assembled
2Particle size range be 3.5～6.2nm.
The preparation method of metasilicate hole material assembled nano titanium oxide composite material of the present invention, it comprises the steps:
1) preparation of layered phyllosilicate porous material: take by weighing granularity according to Si/Ti mol ratio in product and be the phyllosilicate less than 3mm, the Si/Ti mol ratio was got any one value from 10: 1～20: 1, as 10: 1; Pulverize, leach under stirring condition with acid solution then, with leachate cooling, filtration, washing, oven dry obtains the micro/meso porous material of layered phyllosilicate (as the micro/meso porous material of talcum matter);
2) preparation of titanium salt solution: according to volume ratio is to measure titanium salt and solvent in 1: 3～1: 8 respectively, and these two kinds of solution are mixed, and fully is uniformly dispersed with ultrasonic wave or magnetic agitation, obtains the solution (as the ethanolic solution of butyl titanate) of titanium salt; The purpose that adds solvent in this operation is for reaction is relaxed;
3) colloidal sol is produced in the mixing of titanium salt solution and layered phyllosilicate porous material: the beaker that titanium salt solution (as the ethanolic solution of butyl titanate) will be housed places on the magnetic agitation instrument and stirs, by the Si/Ti ratio is to take by weighing above-mentioned steps 1 in 10: 1～20: 1) layered phyllosilicate porous material (as the micro/meso porous material of talcum matter) that makes, and this hole material is added in the titanium salt solution; After stirring, in molar ratio: water/titanium salt＞1 dropwise adds a certain amount of deionized water, makes the butyl titanate hydrolysis.The pH value of controlling reaction system with acid solution in the hydrolytic process is acid (being pH value＜7), fully after the reaction, stops stirring, promptly obtains colloidal sol;
4) producing of layered phyllosilicate porous material assembled nano titanium oxide composite: the utilize above-mentioned steps 3) colloidal sol that obtains, ageing at room temperature, (ageing, promptly, colloidal sol is the colloidal dispersion with fluid characteristics, and the particle of dispersion is solid or big molecule, and gel is the colloidal dispersion with solid features, dispersed material forms continuous mesh skeleton, is filled with liquid or gas in the skeleton space.Colloidal sol is slowly polymerization through between the ageing micelle, forms the gel of three-dimensional space network structure, has been full of the solvent that loses flowability between gel network, forms gel; Gel is prepared the material of molecule and even nanostructured through super-dry, sintering curing.) become gel; With distilled water washing, filtration at least twice, with absolute ethanol washing, filtration at least once, remove remaining organic matter and other impurity again; To can make the presoma of layered phyllosilicate porous material assembled nano titanium oxide composite after the oven dry of the powder after the washing, presoma obtains layered phyllosilicate porous material assembled nano titanium oxide composite through grinding the back at 350～500 ℃ of following roasting 4～8h.
Wherein, described titanium salt is butyl titanate, isopropyl titanate, titanium tetrachloride, titanyl sulfate or titanium sulfate; Described phyllosilicate is talcum, kaolinite, pyrophillite, montmorillonite, illite or muscovite;
Described solvent comprises absolute ethyl alcohol, acetylacetone,2,4-pentanedione etc.; Described acid solution is hydrochloric acid, glacial acetic acid.
With planetary mills ball milling 4～6h, ball material weight ratio is 10: 1.
The catalyst that technology of the present invention closes and be to seek that performance is good, cost is low, environment is had no side effect.This be because dioxin to be a kind of environmental pollution serious and the organic pollution of utmost point difficult degradation, present other common catalyst degradation efficient are not high or to the environment toxigenicity, selecting a kind of catalytic activity height, cheap catalyst is the pass of realizing dioxin catalytic decomposition in the waste gas.
The present invention designs the catalyst of different hole material/titanium proportionings on the basis of existing research work, adopt different process schemes, and the resulting finished product of different tests is carried out catalytic test to dioxin.Process is to the adjustment and the optimization of hole material/titanium proportioning and technological parameter, and the improvement of catalytic condition nearly 100 times, has obtained to satisfy the hole material composite catalyst of dioxin in the resolution process waste gas.
Beneficial effect of the present invention
The present invention compares with existing technology and has the following advantages:
(1) all to adopt organosilicon and Ludox be raw material to prior art, and through the method preparation assembling main body of hydro-thermal reaction or colloidal sol-glue, raw material are expensive and time-consuming; The present invention is to be that raw material prepares micro/meso porous material through chemical treatment with the phyllosilicate, can cut down finished cost, and widens the range of application in talcum ore deposit simultaneously, produces high value-added product.
(2) technology of the present invention is simple, and raw material is easy to get, and condition is comparatively loose, is difficult for contaminated environment.
(3) because prepared micro/meso porous material contains uniform sequential duct and empty cage makes that assembled titania is well disperseed, and crystallite dimension is controlled, prepared hole assembling TiO2 performance of composites improves a lot before the assembling.
Description of drawings
Fig. 1 prepares the process flow diagram of stratiform metasilicate hole material assembled nano titanium oxide composite material for the present invention;
Fig. 2 is the XRD figure of the layered phyllosilicate porous material assembled nano titanium oxide composite before and after the assembling;
Fig. 3 is the N of layered phyllosilicate porous material assembled nano titanium oxide composite of the present invention
2The adsorption-desorption isothermal curve;
Fig. 4 is the BJH pore size distribution curve of layered phyllosilicate porous material assembled nano titanium oxide composite of the present invention;
Fig. 5 is the HK pore size distribution curve of layered phyllosilicate porous material assembled nano titanium oxide composite of the present invention.
The specific embodiment
The technological process of producing layered phyllosilicate porous material assembled nano titanium oxide composite is as shown in Figure 1:
With-80 orders (0.20mm) granularity (also can for-1mm ,-2mm ,-the 3mm granularity) the talcum raw material with planetary mills ball milling 6h, ball material weight ratio is 10: 1, leach under 80 ℃ of stirring conditions with hydrochloric acid behind the ball milling, acid concentration is 4mol/L, extraction time is 2h, with leachate cooling, filtration, washing, oven dry gets the micro/meso porous material of talcum matter (S101).Get 10ml butyl titanate (analyzing pure) and 30ml absolute ethyl alcohol and mix, disperse 10min (S102) with ultrasonic wave.Mixed liquor is used in the heat collecting type constant temperature blender with magnetic force stirs (S103), according to Si/Ti=10: 1 (mol ratio), in the ethanolic solution of butyl titanate, add talcum matter hole material, in 60 ℃ of water-baths behind the magnetic agitation 30min, dropwise drip the 10ml deionized water, and with HCl or glacial acetic acid solution control pH value about 3.0, and then stirring 1h (S104), still aging 24h (S105) under the room temperature, xerogel with ageing filters respectively with deionized water and absolute ethyl alcohol in circulation ability of swimming vavuum pump then, washed twice, 100 ℃ obtain layered phyllosilicate porous material assembled nano titanium oxide composite material precursor (S106) after the oven dry down in the electric heating constant temperature air dry oven.Respectively at 350 ℃, 400 ℃, 500 ℃ of following roasting 4h (S107), can obtain the Si/Ti mol ratio and be 10: 1 layered phyllosilicate porous material assembled nano titanium oxide composite (S108) with the box-shaped resistance furnace.
The XRD figure that makes product as shown in Figure 2, the XRD figure of the layered phyllosilicate porous material assembled nano titanium oxide composite that Fig. 2 obtains for presoma and 350 ℃ of following roastings.(a-talcum matter hole material; B-hole assembling TiO
2Composite).
As seen from the figure, 350 ℃ of following roastings, Detitanium-ore-type TiO has appearred
2, also have some amorphous substances.The component content of the layered phyllosilicate porous material assembled nano titanium oxide composite that makes is as shown in table 1 below.
The content (%) of each phase in the material assembled nano titanium oxide composite of the different embodiment of table 1 hole
N
2The adsorption-desorption isothermal curve, as shown in Figure 3, successful as can be seen prepared TiO
2The specific area of/hole material powder is by the preceding 260.20m of assembling
2/ g drops to 189.50m
2/ g, pore volume drops to 0.40ml/g by 0.51ml/g, and the micropore quantity minimizing of assembling back, and this proves absolutely TiO
2Successfully be assembled into little mesoporous in.
The BJH pore size distribution curve, as shown in Figure 4, the HK pore size distribution curve as shown in Figure 5, pore size distribution range is 1.2～5.5nm.
TiO
2It itself is a kind of semiconductor nano catalyst, to greatly improve its catalytic activity after being assembled into layered phyllosilicate porous material, can be used as the efficient decomposition catalyst of dioxin persistence organic pollutant, be applied to the reduction of discharging process field of dioxin in the waste gas of steel industry, waste incineration industry etc.Advantages such as the Yttria/titanium dioxide nano composite material oxidability of the present invention's preparation is strong, and the catalytic activity height is nontoxic, and is biological, chemical, that photochemical stability is good can be used for fields such as sewage disposal, air cleaning, sterilization, energy and material.
The present invention can be applied to the reduction of discharging of the dioxin persistence organic pollutant in sintering and the electric furnace production discharging waste gas and handle, and can be applied to the exhaust-gas treatment of domestic iron and steel enterprise, waste incineration industry.In steel industry worldwide and the incineration treatment of garbage industry wide promotional value and application prospect are arranged all.
Claims (11)
1. metasilicate hole material assembled nano titanium oxide composite material, its composition quality percentage is:
Layered phyllosilicate porous material 92.2～95.9
Detitanium-ore-type TiO
27.8～4.1.
2. metasilicate hole material assembled nano titanium oxide composite material as claimed in claim 1 is characterized in that phyllosilicate comprises talcum, kaolinite, pyrophillite, montmorillonite, illite or muscovite.
3. metasilicate hole material assembled nano titanium oxide composite material as claimed in claim 1 is characterized in that, described titanium salt is butyl titanate, isopropyl titanate, titanium tetrachloride, titanyl sulfate or titanium sulfate.
4. metasilicate hole material assembled nano titanium oxide composite material as claimed in claim 1 is characterized in that TiO
2Particle size range be 3.5～6.2nm.
5. metasilicate hole material assembled nano titanium oxide composite material as claimed in claim 1 is characterized in that, the pore volume of composite titania material is 0.22～0.40ml/g, and pore size distribution range is 1.2～5.5nm, and specific area is 133～189m
2/ g.
6. the preparation method of metasilicate hole material assembled nano titanium oxide composite material as claimed in claim 1, it comprises the steps:
1) preparation of layered phyllosilicate porous material: take by weighing granularity according to Si/Ti mol ratio in product and be phyllosilicate less than 3mm, the Si/Ti mol ratio is got any one value from 10: 1～20: 1, pulverize, leach under stirring condition with acid solution then, with leachate cooling, filtration, washing, oven dry obtains the micro/meso porous material of layered phyllosilicate;
2) preparation of titanium salt solution: according to volume ratio is to measure titanium salt and solvent in 1: 3～1: 8 respectively, and these two kinds of solution are mixed, and fully is uniformly dispersed with ultrasonic wave or magnetic agitation, obtains titanium salt solution;
3) colloidal sol is produced in the mixing of titanium salt solution and layered phyllosilicate porous material: the beaker that titanium salt solution will be housed places to stir on the instrument and stirs, by the Si/Ti ratio is to take by weighing above-mentioned steps 1 in 10: 1～20: 1) layered phyllosilicate porous material that makes, and this hole material is added in the titanium salt solution; After stirring, in molar ratio: water/titanium salt＞1 dropwise adds deionized water, makes the butyl titanate hydrolysis, and the pH value of controlling reaction system with acid solution in the hydrolytic process is acid; Fully after the reaction, stop to stir, promptly obtain colloidal sol;
4) producing of layered phyllosilicate porous material assembled nano titanium oxide composite: the utilize above-mentioned steps 3) colloidal sol that obtains, ageing at room temperature becomes gel; With distilled water washing, filtration at least twice, with absolute ethanol washing, filtration at least once, remove remaining organic matter and other impurity again; The presoma of layered phyllosilicate porous material assembled nano titanium oxide composite will can be made after the oven dry of the powder after the washing; Presoma obtains layered phyllosilicate porous material assembled nano titanium oxide composite through grinding the back at 350～500 ℃ of following roasting 4～8h.
7. the preparation method of metasilicate hole material assembled nano titanium oxide composite material as claimed in claim 6 is characterized in that, phyllosilicate comprises talcum, kaolinite, pyrophillite, montmorillonite, illite or muscovite.
8. the preparation method of metasilicate hole material assembled nano titanium oxide composite material as claimed in claim 6 is characterized in that, described titanium salt is butyl titanate, isopropyl titanate, titanium tetrachloride, titanyl sulfate or titanium sulfate.
9. the preparation method of metasilicate hole material assembled nano titanium oxide composite material as claimed in claim 6 is characterized in that, described acid solution is hydrochloric acid, glacial acetic acid.
10. the preparation method of metasilicate hole material assembled nano titanium oxide composite material as claimed in claim 6 is characterized in that, described solvent is absolute ethyl alcohol, acetylacetone,2,4-pentanedione.
11. the preparation method of metasilicate hole material assembled nano titanium oxide composite material as claimed in claim 6 is characterized in that, stirs and adopts ultrasonic wave or magnetic agitation instrument to stir.
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