CN101391211A - Alumina substrate shaped titanium dioxide-nucleus/shell structure composite microsphere photocatalyst and preparation method thereof - Google Patents
Alumina substrate shaped titanium dioxide-nucleus/shell structure composite microsphere photocatalyst and preparation method thereof Download PDFInfo
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- CN101391211A CN101391211A CNA2008102264390A CN200810226439A CN101391211A CN 101391211 A CN101391211 A CN 101391211A CN A2008102264390 A CNA2008102264390 A CN A2008102264390A CN 200810226439 A CN200810226439 A CN 200810226439A CN 101391211 A CN101391211 A CN 101391211A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000004005 microsphere Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 20
- 239000010936 titanium Substances 0.000 title claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000000758 substrate Substances 0.000 title claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 25
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 13
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims description 25
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- -1 deionized water compound Chemical class 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000008187 granular material Substances 0.000 claims description 10
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 238000005216 hydrothermal crystallization Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 239000012528 membrane Substances 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 229910010413 TiO 2 Inorganic materials 0.000 description 19
- 230000001699 photocatalysis Effects 0.000 description 8
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000593 degrading effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 5
- 229940012189 methyl orange Drugs 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
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- 239000002351 wastewater Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
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- 239000000969 carrier Substances 0.000 description 3
- 239000003034 coal gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002894 chemical waste Substances 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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Abstract
The invention relates to a composite microsphere photocatalyst with an alumina base/flake titanium dioxide-nucleus/shell structure as well as a preparation method thereof. The form of the catalyst is a composite microsphere taking a spherical gamma-aluminum oxide powder with the particle diameter of between 10 and 30mu m as a core and having the surface wrapped with a layer of anatase phase flake titanium dioxide particle membrane, and is synthesized by adopting a heterogeneous phase precipitation coating-hydrothermal crystallization method: namely, a composite microsphere precursor is firstly formed after the heterogeneous phase precipitation coating reaction on the surface of the aluminum oxide microsphere through industrial titanium sulfate and a precipitator under the room temperature, then the precursor undergoes the hydrothermal crystallization treatment and then procedures such as washing and drying to get the finished product photocatalyst. The catalyst has rather high specific surface area and catalytic activity, can fully degrade organic pollutants, and can utilize the weight of the aluminum oxide microsphere to rapidly settle and recover catalyst in an aqueous solution. Meanwhile, the preparation process and equipment are simple and controllable, costs are low, and the scale production is easy.
Description
Technical field
A kind of alumina substrate shaped titanium dioxide titanium-nucleus/shell structure composite microballoons photochemical catalyst and preparation method thereof particularly relates to a kind of core/shell structure Al of degrading organic pollutant
2O
3Base/sheet TiO
2Composite microsphere photocatalyst and preparation method thereof.
Background technology
With nano-TiO
2For the photocatalysis technology of catalyst as a kind of emerging organic pollution treatment technology, it is fast to have processing speed, degraded does not have selectivity, equipment is simple, and is easy to operate, non-secondary pollution, characteristics such as treatment effect is good have caused the attention of countries in the world, competitively develop new and effective TiO
2Photochemical catalyst as the P-25 of Germany, the SSP-25 of Japan etc., has become the object of numerous photocatalysis researchers uses and comparative study, has obtained extensive use at aspects such as antifouling, antibiotic, deodorizing, air cleaning, water treatment and environmental pollution improvements.Yet, nano-TiO
2Be used for the organic sewage processing and still be in breadboard basic research at present, the reason that hinders its practicability application mainly contains 2 points: at first, photocatalysis efficiency is lower.When carrying out light-catalyzed reaction, redox reaction only occurs in TiO
2The particle outer surface, therefore, TiO
2The size of particle, specific area and dispersiveness are the key factors that influences its catalytic efficiency.Discover that particle is more little, dispersiveness is high more, and then response area is big more, and the light adsorption efficiency is just high more, and the simple composite probability in electronics and hole is also low more, and quantum yield then can improve rapidly, and existing result of study shows: the nano-TiO of high degree of dispersion
2Catalyst is than the powder TiO of big particle diameter
2Show unique more high activity.But nano-TiO
2The powder water imbibition is strong, particularly reclaims when the back secondary uses and reunites easily, and the electron-hole pair that optical excitation produces is easy to compound when moving to the surface, can't fully disperse to bring into play its catalytic activity in slurry.Simultaneously, the TiO that exists with interior kernel form
2Be actually a kind of waste of resource, the TiO of unit mass
2Utilization rate is low.Secondly, for more widely used water in suspension system, nano-TiO
2Also there is the sedimentation difficulty in powder, is difficult for the recycling problem.Though the existing supported method of various catalyst as photochemical catalyst is loaded on sheet glass, glass fabric or the carriers such as cement, wire netting, has solved the separation difficult problem of photochemical catalyst, the efficient of using is starkly lower than slurry attitude system.Therefore, design preparation high-specific surface area, large aperture, to the many and immobilized carrier little of catalyst supported quantity to its activity influence, make its immobilization, to reduce the loss of catalyst in wastewater treatment, the recovery and the recycling difficult problem that solve catalyst are one of key issues that faces at present.
Occur a kind of more welcome solid support method at present, be about to nano-TiO
2Be fixed on the bulky grain powder, both to nano-TiO
2Activity influence is little, can utilize again carrier preferably settleability reduce the loss of catalyst in wastewater treatment, solve the recovery and the recycling difficult problem of catalyst.Heller (J.Phys.Chem., 7996,96 (8): 3423-3428) make the fixed TiO that loads on the hollow glass ball
2Photochemical catalyst can float on the water surface water surface oil pollution of degrading, and carry out medium scale outdoor experiment.This work has obtained the high degree of attention and support of U.S. government.(the journal .2001 of Ningxia University, 22 (2): be carrier to float ball in the coal ash 219-220), butyl titanate is a raw material to Zhao Wenkuan etc., has prepared a kind of nano-TiO that is loaded with
2The float type photochemical catalyst of powder.Yang Yang (catalysis journal, 2001,22 (2): the supported titanium that 177-180) has been preparing carriers with the expanded perlite
2Photochemical catalyst.Qin Shulin (Zhejiang chemical industry, 2005,36 (6): 17-18) with polypropylene filler loaded with nano level TiO
2Photochemical catalyst.Chen Shifu (Applied Surface Science, 2007, the TiO that 253:3077-3082) adopted Prepared by Sol Gel Method
2-xN
xCoat the hollow glass microballoon powder.(Journal of Catalysis, 2007, the TiO that 246:235-240) utilized titanium alkoxide immersion process for preparing such as Masato
2/ ZSM-5 photochemical catalyst.(Materials Letters, 2007, the Detitanium-ore-type TiO that 61:4828-4831) utilized dipping-Hydrothermal Preparation such as Subramani
2/ active carbon compound particle.Youji Li (Applied SurfaceScience, 2007, the TiO that 253:9254-9258) adopted Prepared by Sol Gel Method
2Coating active charcoal composite granule.In these composite granules, nano-TiO
2Particle is evenly distributed on substrate surface, and particle diameter is below 50nm, and the catalytic activity of composite granule obviously improves than single-phase titanium dioxide, illustrates that this loaded catalyst powder has bigger advantage.But these researchs are at present mostly only considered to support problem, do not consider the carrier better effects if of which kind of structure or pattern, adopt light carriers such as commercially available glass microsphere, active carbon or coal ash floater, because the surface is more smooth, make TiO
2Supported quantity is limited, and bond strength is not high, repeatedly uses the active obviously reduction in back; And density is low, light weight, only is fit to swim in the photocatalysis system of the water surface, and range of application is narrow.Mo Shaofen etc. (the silicate circular, 1991,5:4-7) superfine alumina powder with 0.1～0.2 μ m is substrate, utilizes the facile hydrolysis of titanium tetrachloride, the parcel precipitation method have prepared Al
2O
3/ TiO
2Composite granule is mainly used in preparation low bulk Al
2TiO
5Material; And Chinese patent 99123760.9 has reported that a kind of metal alkoxide Hydrolyze method prepares the even monodisperse sphere type nano-TiO of particle diameter at 55～1400nm
2/ SiO
2Composite particles, this particle are at the single 50～1300nm of the dispersion SiO as kernel
2Particle surface coats the TiO of one deck 5～200nm thickness
2, form the complex microsphere particle, mainly be applicable to pigment.But these two kinds of composite granule particle diameters are all less, reclaim still difficulty when being applied to wastewater treatment, and the preparation method's complex process that is adopted is difficult for large-scale production.
In the report of preparation pure phase titanium dioxide nano-crystal, hydro-thermal method is widely adopted (M.C.Hidalgo etal., Catal.Today, 2007).Because this method has the equipment less investment, advantages such as temperature is low, easy control.The titanium dioxide of common this method preparation is the anatase phase, can be used for light-catalyzed reaction, and obtains fine-grain and high specific area, but rare with the report of Hydrothermal Preparation load shell/nuclear structure composite granule.
Goal of the invention
Purpose of the present invention is exactly the deficiency that exists at above-mentioned prior art, provide a kind of be used for degradable organic pollutant have highlight catalytic active, a bigger serface, and utilize the good settleability of alumina substrate to realize alumina base/flake nano titanium dioxide-nucleus/shell structure composite microballoons photochemical catalyst and novel preparation method thereof that catalyst reclaims fast in the aqueous solution.
Goal of the invention of the present invention is achieved through the following technical solutions.
A kind of alumina base/plate-like titanium dioxide-nucleus/shell structure composite microballoons photochemical catalyst, it is characterized in that: the ball-aluminium oxide substrate surface has wrapped up one deck flake nano titanium dioxide granule film, the nanostructured gama-alumina microsphere of described ball-aluminium oxide substrate for can commercially availablely obtaining, particle diameter is distributed in 10～30 μ m, nano titanium oxide in the form of sheets, particle thickness is below 100nm; Specific area is 138～160m
2/ g; Alumina substrate is 1:0.05～1:0.5 with the mass ratio of parcel titanium dioxide shell.
A kind of alumina base/plate-like titanium dioxide-nucleus/shell structure composite microballoons Preparation of catalysts method is characterized in that the step of its preparation process comprises:
(1) with the deionized water compound concentration is the spherical gama-alumina suspension of 50～200g/L, accounts for the technical grade titanium sulfate solution of aluminium oxide quality 5%～20%, stir to form and evenly mix suspension to wherein adding content of titanium dioxide; With the deionized water compound concentration is ammoniacal liquor or sodium carbonate or the carbonic hydroammonium alkaline sedimentation agent solution of 0.4～1.0M, and is added drop-wise to lentamente in the suspension continuously with the charging rate of 5～15mL/min, makes titanium ion precipitated crystal on suspended particulate, forms integument;
(2) treat that the pH value of solution value reaches at 6～7 o'clock and stop to drip precipitating reagent, at room temperature continue more than reaction half an hour, with suspension whole move into to have in heating and the churned mechanically reactor seal, 120～170 ℃ of following crystallization 2～5 hours, naturally cool to room temperature; Take out then, sediment is filtered, washs, in air,, promptly obtain flake nano titanium dioxide coated alumina nuclear/shell composite microsphere photocatalyst product in 60～80 ℃ of drying 10～12h.
Activity to photochemical catalyst provided by the invention can be tested with the following method:
The photocatalytic activity test that composite microsphere photocatalyst decomposes for oxidation operation in solution is carried out at normal temperatures.Accurately weighing 2 restrains catalyst, and then it being joined 300mL concentration is in the different organic pollution aqueous solution of 0.05～0.15 grams per liter, stirs not open close air (30 ml/min); Under uviol lamp (365 nanometers, 500 watts) irradiation, react, react 2～5 hours respectively after, natural subsidence 30 minutes.The organic concentration of surplus solution is analyzed on ultraviolet-visible spectrophotometer (Beijing is general analyses, TU-1901,190～900 nanometers).
Catalysts and its preparation method provided by the invention has following advantage:
1, the alumina base/plate-like titanium dioxide composite microsphere photocatalyst list that adopts the present invention to obtain disperses, the pattern and the size that are keeping the substrate aluminum oxide micro-sphere, contrast with the pure alumina microsphere surface, the complex microsphere surface is parcel one deck anatase phase sheet titanium dioxide granule film obviously, particle thickness is below 100nm, be evenly distributed, specific area reaches 138～160m
2/ g.
2, be light source with the ultraviolet light, need not outer adding assistant, degradable organic pollutant fully, the catalytic activity height has great industrial application value.
3, shell flake nano titanium dioxide can effectively be avoided reuniting by the high-ratio surface and the loose structure of alumina substrate microballoon, give full play to the catalytic activity of unit mass titanium dioxide, and can utilize weight rapid subsidence in the aqueous solution of aluminum oxide micro-sphere to reclaim titanium dioxide.
4, the non-homogeneous phase deposition parcel-hydrothermal crystallization method that adopts of the present invention is compared with existing composite construction powder body material preparation technology, technology, equipment simple controllable, and cost is low, be easy to large-scale production.
Description of drawings
Fig. 1 is the embodiment of the invention 1,2, the γ-Al that is adopted in 3
2O
3Microballoon macroscopic view stereoscan photograph;
Fig. 2 is the embodiment of the invention 1,2, the γ-Al that is adopted in 3
2O
3The microsphere surface stereoscan photograph;
The Al that Fig. 3 obtains for the embodiment of the invention 1
2O
3/ TiO
2Complex microsphere macroscopic view stereoscan photograph;
The Al that Fig. 4 obtains for the embodiment of the invention 1
2O
3/ TiO
2Complex microsphere surface scan electromicroscopic photograph;
Fig. 5 is the Al of the embodiment of the invention 1
2O
3/ TiO
2Complex microsphere surface energy spectrogram;
Fig. 6 is the Al of the embodiment of the invention 1
2O
3/ TiO
2The complex microsphere x-ray diffraction pattern;
Fig. 7 is the phenol organic wastewater degraded front and back ultraviolet-visible spectrophotometer spectral scan curve of the embodiment of the invention 1;
Fig. 8 is the methyl orange organic wastewater degraded front and back ultraviolet-visible spectrophotometer spectral scan curve of the embodiment of the invention 2;
Fig. 9 is the coal gas waste degraded front and back ultraviolet-visible spectrophotometer spectral scan curve of the embodiment of the invention 3.
The specific embodiment
A kind of alumina base/plate-like titanium dioxide-nucleus/shell structure composite microballoons photochemical catalyst, its spherical gamma-alumina base basal surface has wrapped up one deck anatase phase sheet titanium dioxide nanoparticle film, described spherical gamma-alumina substrate is for can commercially availablely obtaining, and particle diameter is distributed in 10～30 μ m; Flake nano TiO 2 particles thickness is evenly distributed below 100nm, and specific area reaches 138～160m
2/ g, alumina substrate is 1: 0.05～1: 0.5 with the mass ratio of parcel titanium dioxide shell.
The step of preparation process comprises:
(1) with the deionized water compound concentration is the spherical gama-alumina suspension of 50～200g/L, accounts for the technical grade titanium sulfate solution of aluminium oxide quality 5%～20%, stir to form and evenly mix suspension to wherein adding content of titanium dioxide; With the deionized water compound concentration is ammoniacal liquor or sodium carbonate or the carbonic hydroammonium alkaline sedimentation agent solution of 0.4～1.0M, and is added drop-wise to lentamente in the suspension continuously with the charging rate of 5～15mL/min, makes titanium ion precipitated crystal on suspended particulate, forms integument;
(2) treat that the pH value of solution value reaches at 6～7 o'clock and stop to drip precipitating reagent, at room temperature continue more than reaction half an hour, with suspension whole move into to have in heating and the churned mechanically reactor seal, 120～170 ℃ of following crystallization 2～5 hours, naturally cool to room temperature; Take out then, sediment is filtered, washs, in air,, promptly obtain flake nano titanium dioxide coated alumina nuclear/shell composite microsphere photocatalyst product in 60～80 ℃ of drying 10～12h.
Alumina base/plate-like titanium dioxide composite microsphere photocatalyst the list that adopts the present invention to obtain disperses, the pattern and the size that are keeping the substrate aluminum oxide micro-sphere, contrast with the pure alumina microsphere surface, the complex microsphere surface is parcel one deck anatase phase sheet titanium dioxide granule film obviously, particle thickness is below 100nm, be evenly distributed, specific area reaches 138～160m
2/ g sees accompanying drawing 1, Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6; Composite microsphere photocatalyst has advantages of high catalytic activity, and Pyrogentisinic Acid, methyl orange, coal gas waste can be degraded fully, see accompanying drawing 7, Fig. 8, Fig. 9.
The alumina base of nuclear/shell mass ratio 1:0.05/plate-like titanium dioxide composite microsphere photocatalyst
1, be 50g/L, particle diameter spherical gama-alumina suspension with the deionized water compound concentration at 10～50 μ m, to wherein adding 31.17g technical grade titanium sulfate solution, the titanium sulfate mass content is 19.26%, and mechanical agitation formed and evenly mixes suspension more than half an hour.With the deionized water compound concentration is the ammonia spirit of 0.4M, and is added drop-wise to lentamente in the suspension continuously with the charging rate of 10mL/min, makes titanium ion precipitated crystal on suspended particulate, forms integument;
2, treat that the pH value of solution value reaches at 6 o'clock and stop to drip precipitating reagent, at room temperature continue more than reaction half an hour, with suspension whole move into to have in heating and the churned mechanically reactor seal, 170 ℃ of following crystallization 2 hours, naturally cool to room temperature; Take out then, sediment is filtered, washs, in air,, promptly obtain flake nano titanium dioxide coated alumina nuclear/shell composite microsphere photocatalyst product in 80 ℃ of dry 10h.Below microsphere surface lamellar titanium oxide grain thickness 100 nanometers, specific area 138m
2/ g, the anatase phase is seen accompanying drawing 3, Fig. 4, Fig. 5, Fig. 6.
The photocatalytic activity test of 3, above-mentioned composite microsphere photocatalyst being decomposed for the phenol oxidation operation in solution is carried out at normal temperatures.Accurately weighing 2 restrains catalyst, and then it being joined 300mL concentration is in the phenol organic pollution aqueous solution of 0.15 grams per liter, stirs not open close air (30 ml/min); After reacting 3 hours under uviol lamp (365 nanometers, the 500 watts) irradiation, natural subsidence 30 minutes.The organic concentration of surplus solution is analyzed on ultraviolet-visible spectrophotometer (Beijing is general analyses, TU-1901,190～900 nanometers).By accompanying drawing 7 as seen, the complete obiteration after degrading of the characteristic absorption peak of phenolic waste water, degraded are fully.
The alumina base of nuclear/shell mass ratio 1:0.15/plate-like titanium dioxide composite microsphere photocatalyst
1, be 100g/L, particle diameter spherical gama-alumina suspension with the deionized water compound concentration at 10～50 μ m, to wherein adding 187.02g technical grade titanium sulfate solution, the titanium sulfate mass content is 19.26%, and mechanical agitation formed and evenly mixes suspension more than half an hour.With the deionized water compound concentration is the ammonium bicarbonate soln of 1.0M, and is added drop-wise to lentamente in the suspension continuously with the charging rate of 15mL/min, makes titanium ion precipitated crystal on suspended particulate, forms integument;
2, treat that the pH value of solution value reaches at 7 o'clock and stop to drip precipitating reagent, at room temperature continue more than reaction half an hour, with suspension whole move into to have in heating and the churned mechanically reactor seal, 150 ℃ of following crystallization 3 hours, naturally cool to room temperature; Take out then, sediment is filtered, washs, in air,, promptly obtain flake nano titanium dioxide coated alumina nuclear/shell composite microsphere photocatalyst product in 60 ℃ of dry 12h.Below microsphere surface lamellar titanium oxide grain thickness 100 nanometers, specific area 141m
2/ g, the anatase phase.
The photocatalytic activity test of 3, above-mentioned composite microsphere photocatalyst being decomposed for the methyl orange oxidation operation in solution is carried out at normal temperatures.Accurately weighing 2 restrains catalyst, and then it being joined 300mL concentration is in the methyl orange organic pollution aqueous solution of 0.05 grams per liter, stirs not open close air (30 ml/min); After reacting 2 hours under uviol lamp (365 nanometers, the 500 watts) irradiation, natural subsidence 30 minutes.The organic concentration of surplus solution is analyzed on ultraviolet-visible spectrophotometer (Beijing is general analyses, TU-1901,190～900 nanometers).By accompanying drawing 8 as seen, the complete obiteration after degrading of the characteristic absorption peak of methyl orange waste water, degraded are fully.
Nuclear/shell mass ratio is alumina base/plate-like titanium dioxide composite microsphere photocatalyst of 1:0.50
1, be 200g/L, particle diameter spherical gama-alumina suspension with the deionized water compound concentration at 10～50 μ m, to wherein adding 259.32g technical grade titanium sulfate solution, the titanium sulfate mass content is 19.26%, and mechanical agitation formed and evenly mixes suspension more than half an hour.With the deionized water compound concentration is the sodium carbonate liquor of 1.5M, and is added drop-wise to lentamente in the suspension continuously with the charging rate of 5mL/min, makes titanium ion precipitated crystal on suspended particulate, forms integument;
2, treat that the pH value of solution value reaches at 6 o'clock and stop to drip precipitating reagent, at room temperature continue more than reaction half an hour, with suspension whole move into to have in heating and the churned mechanically reactor seal, 120 ℃ of following crystallization 5 hours, naturally cool to room temperature; Take out then, sediment is filtered, washs, in air,, promptly obtain flake nano titanium dioxide coated alumina nuclear/shell composite microsphere photocatalyst product in 70 ℃ of dry 10h.Below microsphere surface lamellar titanium oxide grain thickness 100 nanometers, specific area 160m
2/ g, the anatase phase.
3, above-mentioned composite microsphere photocatalyst is carried out at normal temperatures for the photocatalytic activity test of coking chemical waste water oxidation Decomposition.Accurately weighing 2 gram catalyst join it in coal gas waste solution that 300mL COD concentration is 0.539 grams per liter then, stir not open close air (30 ml/min); React down in uviol lamp (365 nanometers, 500 watts) irradiation, react after 3 hours with after 5 hours the natural subsidence of taking a sample respectively 30 minutes.The organic concentration of surplus solution is analyzed on ultraviolet-visible spectrophotometer (Beijing is general analyses, TU-1901,190～900 nanometers) after the sedimentation.By accompanying drawing 9 as seen, the characteristic absorption peak of coking chemical waste water obviously decay after degrading 3 hours and 5 hours.
Claims (2)
1. alumina base/plate-like titanium dioxide-nucleus/shell structure composite microballoons photochemical catalyst, it is characterized in that: the ball-aluminium oxide substrate surface has wrapped up one deck flake nano titanium dioxide granule film, the nanostructured gama-alumina microsphere of described ball-aluminium oxide substrate for can commercially availablely obtaining, particle diameter is distributed in 10～30 μ m, nano titanium oxide in the form of sheets, anatase phase, particle thickness are below 100nm, and specific area is 138～160m
2/ g, alumina substrate is 1:0.05～1:0.5 with the mass ratio of parcel titanium dioxide shell.
2. alumina base/plate-like titanium dioxide-nucleus/shell structure composite microballoons Preparation of catalysts method is characterized in that the step of preparation process comprises:
(1) with the deionized water compound concentration is the spherical gama-alumina suspension of 50～200g/L, accounts for the technical grade titanium sulfate solution of aluminium oxide quality 5%～20%, stir to form and evenly mix suspension to wherein adding content of titanium dioxide; With the deionized water compound concentration is ammoniacal liquor or sodium carbonate or the carbonic hydroammonium alkaline sedimentation agent solution of 0.4～1.0M, and is added drop-wise to lentamente in the suspension continuously with the charging rate of 5～15mL/min, makes titanium ion precipitated crystal on suspended particulate, forms integument;
(2) treat that the pH value of solution value reaches at 6～7 o'clock and stop to drip precipitating reagent, at room temperature continue more than reaction half an hour, with suspension whole move into to have in heating and the churned mechanically reactor seal, 120～170 ℃ of following crystallization 2～5 hours, naturally cool to room temperature; Take out then, sediment is filtered, washs, in air,, promptly obtain flake nano titanium dioxide coated alumina nuclear/shell composite microsphere photocatalyst product in 60～80 ℃ of drying 10～12h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619177B (en) * | 2009-07-31 | 2012-08-08 | 孝感学院 | Preparation method of nano-titanium dioxide coated nano-aluminium oxide |
| CN103143362A (en) * | 2012-12-04 | 2013-06-12 | 江苏大学 | Magnetic photocatalyst used for gas waste water treatment and preparation method thereof |
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| CN106582592A (en) * | 2016-12-13 | 2017-04-26 | 湖北工业大学 | Spherical core-shell type TiO2/TiO2 material and preparation method thereof |
| CN109999774A (en) * | 2019-04-25 | 2019-07-12 | 河南科技大学 | Nano-titanium dioxide/gama-alumina composite powder preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101619177B (en) * | 2009-07-31 | 2012-08-08 | 孝感学院 | Preparation method of nano-titanium dioxide coated nano-aluminium oxide |
| CN103143362A (en) * | 2012-12-04 | 2013-06-12 | 江苏大学 | Magnetic photocatalyst used for gas waste water treatment and preparation method thereof |
| CN104307465A (en) * | 2014-09-11 | 2015-01-28 | 上海师范大学 | SiO2 and TiO2 adsorption-photocatalytic nanocomposite and preparation method thereof |
| CN104307465B (en) * | 2014-09-11 | 2017-01-04 | 上海师范大学 | A kind of SiO2@TiO2absorption-Photocatalytic nano composite material and preparation method thereof |
| CN105233787A (en) * | 2015-09-28 | 2016-01-13 | 辽宁石油化工大学 | Preparation method and applications of Al2O3/TiO2 core-shell nano material |
| CN106582592A (en) * | 2016-12-13 | 2017-04-26 | 湖北工业大学 | Spherical core-shell type TiO2/TiO2 material and preparation method thereof |
| CN106582592B (en) * | 2016-12-13 | 2019-07-09 | 湖北工业大学 | A kind of spherical nuclei shell mould TiO2/TiO2Material and preparation method thereof |
| CN109999774A (en) * | 2019-04-25 | 2019-07-12 | 河南科技大学 | Nano-titanium dioxide/gama-alumina composite powder preparation method |
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