CN103172030A - Oxide powder and preparation method thereof as well as catalyst and carrier thereof - Google Patents
Oxide powder and preparation method thereof as well as catalyst and carrier thereof Download PDFInfo
- Publication number
- CN103172030A CN103172030A CN2013100951093A CN201310095109A CN103172030A CN 103172030 A CN103172030 A CN 103172030A CN 2013100951093 A CN2013100951093 A CN 2013100951093A CN 201310095109 A CN201310095109 A CN 201310095109A CN 103172030 A CN103172030 A CN 103172030A
- Authority
- CN
- China
- Prior art keywords
- oxide
- salt
- preparation
- powder
- soluble
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses an oxide powder and a preparation method thereof as well as a catalyst and a carrier thereof. The powder comprises powder of hollow microballoon structure which is formed by converged nanocrystalline oxide, and the wall of the hollow microballoon is provided with a porous structure. The preparation method is the method for preparing the powder. Aqueous solution system slurry suitable for spray drying is prepared by a precipitation method, the target powder is obtained through roasting after spray drying, and the catalyst and the carrier thereof comprise the oxide powder. Compared with the prior art, the powder has the porous hollow microballoon structure, thus having high specific surface area and being beneficial to dispersing substances when being used as the catalyst or the carrier thereof; and the processes are simple, easy to operate and suitable for industrialized production.
Description
Technical field
The invention belongs to porous material preparation and environmental protection catalyst technical field, especially relate to a kind of oxide powder and preparation method thereof and a kind of catalyzer.
Background technology
TiO
2Have very high chemistry and biologically stable and advantages of environment protection, and itself have certain catalytic activity, be commonly used for the main ingredient (as the SCR material (SCR denitrating catalyst) of oxynitride) of environmental protection catalyst or environmental protection catalyst.
V
2O
5-WO
3-TiO
2Present main business SCR denitrating catalyst, the main dispersed activity component V that rises in catalyzer
2O
5With the effect that improves the catalyzer anti-sulfur poisonous performance.Due to WO
3-TiO
2Powder has accounted for more than 80% of catalyzer preparation cost, how to reduce WO
3-TiO
2The powder usage quantity is to reduce V
2O
5-WO
3-TiO
2The key of the whole preparation cost of catalyzer.In the stationary source denitrations such as thermal power plant, V
2O
5-WO
3-TiO
2Catalyzer mainly is prepared to cellular pottery and uses, and what play katalysis is mainly the surface of ceramic catalyst, and therefore preparation has the important goal that more catalyst surfaces that can effectively utilize are low-cost preparation high performance catalysts.
TiO
2Also be widely used in surrounding purifying material, as photocatalyst material (as adopting the organic pollutant in light-catalysed way degraded air and sewage).TiO
2Also exist two to limit to greatly as photocatalyst material, namely quantum yield hangs down and solar energy utilization ratio low (only can absorb the sunlight medium wavelength less than the UV-light of 380nm).In recent years, investigators are compound by metal ion mixing, semi-conductor, photosensitization etc. is to its modification, and obtained certain breakthrough.In all multi-methods, semi-conductor is compounded to form heterojunction structure can effectively be increased its electron hole separating power and not destroy its crystalline structure and natural characteristics, can also expand its light abstraction width and more additional other performances such as energy storage effect etc. simultaneously.
When preparation composite oxides hollow microsphere, investigators mainly utilize template, with superpolymer, carbon ball isocolloid particle as template, react or successively alternately adsorb by surface deposition and make the nucleocapsid structure composite particles, go to obtain hollow ball after template, the method is comparatively complicated, easily faces to fail to remove fully the problem of introducing impurity because of template molecule.In recent years, the Wei Yu of Hebei Normal University etc. take tetrabutyl titanate as the titanium source, sodium wolframate is as the tungsten source, synthesized WO by hydrothermal method without template
3/ TiO
2Hollow ball (documents 1:Y.Li, L Chen, Y.Guo, X.Sun, Y.Wei, " Preparation and characterization of WO
3/ TiO
2Hollow microsphere composites with catalytic activity in dark ", Chemical Engineering Journal.2012,181-182,734-739).Although it has solved the drawback that template is brought, the hydrothermal method in its preparation technology needs High Temperature High Pressure, and to having relatively high expectations of equipment, and the cycle of reaction is longer, is unfavorable for suitability for industrialized production.Therefore a kind of without template, low cost, production method is simple, and reaction time short preparation WO
3-TiO
2The method of composite oxides hollow microsphere will have prospects for commercial application.
The patent close with this patent has (according to time sequence): 1) patent JP59006945, and this patent is take titanyl sulfate as the titanium source, and the methylamine solution of tungsten or ammonia solution are the tungsten source, and combining by hydrolysis method and pickling process makes the WO that at high temperature has high catalytic activity
3-TiO
2Catalyzer; 2) patent JP57171440, this patent is with TiO
2Impregnated in the aqueous solution that contains ammonium tungstate phosphorus and Trimethylamine 99, obtain subsequently the WO of thermostable type 500 ℃ of lower roastings
3The TiO of doping
23) patent JP5309267, JP3592727, this patent makes WO take titanium/tungsten oxide colloidal sol as raw material by sol-gel method
3-TiO
24) patent EP812301, WO9626903, this patent makes WO take nonionic attitude Ti, tungsten source as raw material by hydrolysis method and pickling process
3-TiO
2, products obtained therefrom can reduce TiO
2Because absorb polluted matter reduces the active problem of bringing; 5) patent KR2001054342, KR330627, this patent replaces porous material to do template take titanium hydroxide, tungsten source as raw material with natural ore, makes WO by template
3-TiO
26) patent JP2001286733, JP3868705, this patent makes take titanium sulfate and ammonium paratungstate as raw material the WO that at low temperatures organic chloride is had high degradation rate by the pyrohydrolytic method
3-TiO
27) patent CN1425498, this patent obtains the loading type tungstic acid catalyst take titanium tetrachloride, ammonium tungstate/wolframic acid as raw material by homogeneous phase alcohol hydrothermal method, and its carrier is that size is 240m in 2-10 μ m, specific surface area
2The TiO of/g
2Microballoon, titanium dioxide particle diameter 20～50nm, the weight content of wolframic acid are 5～60%; 8) patent CN1772363, this patent is take the alkoxide of titanium and ammonium tungstate as raw material, and polystyrene is template, makes WO3-TiO2 composite oxides hollow microsphere by sol-gel method, and its size can be 10～10
4Regulate in the nm scope, its form is adjustable, and composition and thickness of shell are controlled; 9) patent CN1775349, this patent is take butyl (tetra) titanate and ammonium tungstate as raw material, by the precipitator method and hydrothermal method in conjunction with making WO
3The nano-TiO of modifying
2Semiconductor light-catalyst, its nano-TiO
2Grain-size is 5～6nm, WO
3The nanocrystalline TiO that is evenly distributed on
2Between nanocrystal; 10) patent CN101898139, this patent is with TiO
2With ammonium paratungstate or ammonium metawolframate be raw material, by the coating method and make the surface through the sulfate radical acidifying and coat different shape WO
xThe TiO of thin layer
2Photocatalyst; 11) patent CN102000561, this patent is take butyl (tetra) titanate and ammonium paratungstate as raw material, but makes the high-temperature selective Reduction of NO by sol-gel method
xWO
3-TiO
2Catalyzer, wherein active ingredient WO
3Account for 10～30% of integer catalyzer massfraction, TiO
2Take Anatase as main; 12) patent CN102284284, this patent is take the alkoxide of titanium and ammonium tungstate as raw material, and organic pollutant is template, makes by sol-gel method and template to have visible light-responded molecular imprinting TiO
2/ WO
3Composite photo-catalyst; 13) patent CN102294273, this patent makes specific surface area high (〉 90m take metatitanic acid and ammonium metawolframate as raw material by the precipitator method
2/ g) and the high WO3-TiO2 composite powder of chemical mobility of the surface; 14) patent CN102327783, this patent makes specific surface area high (〉 90m with take metatitanic acid and ammonium paratungstate as raw material by the precipitator method
2/ g) and the high WO of chemical mobility of the surface
3-TiO
2Composite powder.Gather and can learn by above patent, the patent of having announced often prepares WO by one of them of sol-gel, hydrolysis method, pickling process, hydrothermal method and template or combination between the two
3-TiO
2, it fails to make the porous hollow spheres body mostly, and its Patent CN1772363 characterizes out the composite oxides hollow microsphere, but adopting sol-gel method and need template, preparation section is complicated, and the problem that may exist template molecule to remove fully.。
The document close with this patent has (according to time sequence): 1) Fan Kangnian of Fudan University etc. take titanium tetrachloride and ammonium tungstate as raw material, first makes the Anatase TiO of core (hollow) shell structure by hydrothermal method
2Microballoon and as template, then made WO with nucleocapsid structure by traditional initial wet method pickling process
3-TiO
2Photocatalyst, WO
3Be evenly distributed in TiO
2(documents 2:X.Yanga, W.Daia, C.Guoa, H.Chena, Y.Caoa, H.Lib, H.Hea, K.Fana, " Synthesis of novel core-shell structured WO in the space of microballoon
3/ TiO
2Spheroids and its application in the catalytic oxidation of cyclopentene to glutaraldehyde by aqueous H
2O
2", Journal of Catalysis.2005,234 (2): 438-450); 2) Shangguan Wen Feng of Shanghai Communications University etc. is with commercial P25TiO
2With sodium wolframate be raw material, made WO by wet chemistry method
3-TiO
2Photocatalyst powder, WO
3Mainly there is TiO with foursquare macrobead form and some small-particles
2Particle is distributed in WO
3Interface link effect (documents 3:L.Cao is also played in the surface, J.Yuan, M.Chen, W.Shangguan, " Photocatalytic energy storage ability of WO3-TiO2composite prepared by wet-chemical technique ", Journal of Environmental Sciences.2010,22 (3): 454-459); 3) Zhang Jinlong of East China University of Science and Technology etc. take titanyl sulfate and ammonium tungstate as raw material, makes WO by hydrothermal method without template
3-TiO
2Complex body will form spheroid when the tungsten incorporation reaches 10.0wt%, otherwise will form nano particle (documents 4:S.A.K.Leghari, S.Sajjad, F.Chen, J.Zhang, " WO
3/ TiO
2Composite with morphology change via hydrothermal template-free route as an efficient visible light photocatalyst "; Chemical Engineering Journal.2011,166:906-915); 4) Li Jie of Central South University etc. is take tetrabutyl titanate and ammonium metawolframate as raw material, colloidal carbon sphere is template, by template synthesis the WO3-TiO2 hollow ball of mean sizes 320nm, its thickness of the shell is 50nm(documents 5:K.Lv, J.Li, X.Qin, W.Li, Q.Chen, " Synthesis and Photo-degradation Application of WO
3/ TiO
2Hollow Spheres ", Journal of Hazardous Materials, 2011,189:329-335); 5) Zhang Xintong of Northeast Normal University etc. is with commercial P25TiO
2With ammonium tungstate be raw material, prepared the WO3-TiO2 porous microsphere of heterojunction structure by the ullrasonic spraying high-temperature decomposition, its mean sizes is 500nm, wherein along with the increase WO of W content
3Become rhombic form (documents 6:J.Yang, X.Zhang., H.Liu, C.Wang, S.Liu, P.Sun, L.Wang, Y.Liu, " Heterostructured TiO from amorphous
2/ WO
3Porous microspheres:Preparation, characterization and photocatalytic properties ", CatalysisToday.2013,201:195-202).Gather and can learn by above document, the document of having delivered often has the spheroid of hollow structure by template or hydro-thermal without template synthesis, the lengthy and tedious complexity of the technique of preparation.
Summary of the invention
One of technical problem to be solved by this invention is: a kind of oxide powder is provided, and it has porous hollow microsphere structure.
Two of technical problem to be solved by this invention is: a kind of catalyzer and a kind of support of the catalyst are provided, and its tool porous hollow spheres shape structure is to improve its catalytic efficiency.
Three of technical problem to be solved by this invention is: provide a kind of preparation method of oxide powder, for the preparation of the oxide powder with porous hollow spheres shape structure.
Technical problem of the present invention is solved by following technique means:
A kind of oxide powder comprises the hollow microsphere structure of being reunited and being formed by nano-crystal oxide, and the particle diameter of described nano-crystal oxide is 10～20nm, and the diameter of described hollow microsphere is 1～10 μ m, has vesicular structure on the ball wall of described hollow microsphere.
Preferably: the specific surface area of described oxide powder is greater than 70m
2/ g.
Preferably: described oxide compound is the wherein a kind of or mixtures two or more compositions among them in Tungsten oxide 99.999, titanium oxide, zirconium white, zinc oxide, cerium oxide, silicon oxide, stannic oxide, nickel oxide, ferric oxide, Red copper oxide, molybdenum oxide.
A kind of catalyzer comprises aforesaid oxide powder.Preferably, described oxide compound is the mixture of Tungsten oxide 99.999 and titanium oxide, and wherein the weight percent of Tungsten oxide 99.999 is 0.1%～20%.
A kind of support of the catalyst comprises aforesaid oxide powder.
A kind of preparation method of oxide powder comprises the following steps:
S1: the water-soluble or CTAB(cetyl trimethylammonium bromide with soluble metallic salt) in the aqueous solution, stir the solution that 0.5～100h obtains metal ion under 0～90 ℃, the solution of this metal ion is filtered obtain settled solution A after removing impurity;
S2: the pH value to 3 of the described solution A of adjusting～12 make precipitation by metallic ion be precipitated thing B;
S3: the filter cake C that sediment B or water or CTAB solution washing sediment B are obtained is placed in water or the CTAB aqueous solution, add ammoniacal liquor to regulate pH value to 3～12, and adopt and stir or/and hyperacoustic method is uniformly dispersed it, place aging 0.1～100h and obtain slurry D;
S4: slurry D is carried out spraying drying obtain product E;
S5: product E is obtained described oxide powder at 300～900 ℃ of roasting 0.1～50h.
Soluble metallic salt described in described step S1 is soluble tungsten salt, solubility titanium salt, solubility zirconates, soluble zinc salt, solubility cerium salt, soluble silicon salt, solubility pink salt, soluble nickel salt, soluble ferric iron salt, soluble copper salt or soluble molybdenum salt.
Described oxide compound is Tungsten oxide 99.999-titanium oxide composite oxides, and the soluble metallic salt described in described step S1 is the solubility titanium salt, contains soluble tungsten salt in the water that in described step S3, sediment B or filter cake C add or the CTAB aqueous solution.
In described oxide powder, the weight percent of Tungsten oxide 99.999 is 0.1%～20%.
The mode of regulating the pH value of described solution A in described step S2 is that to add concentration be 1%～32.5% ammoniacal liquor.
In described step S4, spray-dired moisture eliminator inlet temperature is 120～300 ℃, and airshed is 0.01-5000m
3/ hour, input speed is 0.01-1000m
3/ hour, to guarantee that its thermo-efficiency is higher than 50%.
It is room temperature～120 ℃ that described step S3 places aging temperature.
In described step S1 and S3 in the CTAB aqueous solution concentration of CTAB greater than 0g/L less than 2g/L.
Compared with prior art, oxide powder of the present invention is owing to having the hollow microsphere structure, it has high-specific surface area, low-density advantage, and, owing to having vesicular structure on its ball wall, make powder of the present invention as catalyzer or material carrier (for example support of the catalyst) time, more be conducive to catalysant matter or by the diffusion of loading matter.
Catalyzer of the present invention and support of the catalyst, owing to having above-mentioned porous hollow microsphere structure, catalysant matter can diffuse to microballoon inside, microballoon inwall and outside surface can have katalysis simultaneously, have higher specific surface area and catalytic activity with respect to prior art, can reduce significantly catalyst levels.In preferred version, has the WO of porous hollow microsphere structure
3-TiO
2Catalyzer, in its composite oxides, WO
3(E
g≈ 2.8eV) have suitable energy band structure can and TiO
2Forming the structure of II type heterojunction, is 0.1%～20% WO
3Make TiO
2(E
g≈ 3.2eV) light induced electron on can move to WO
3On, and WO
3On the hole to TiO
2Upper migration, thus make material have very high photocatalytic activity, and the characteristic of above-mentioned composite oxides coordinates with porous hollow microsphere structure, is applied in industry, can reduce significantly the usage quantity of catalyzer.
The prepared product of oxidate powder preparation of the present invention has porous hollow microsphere structure (shown in Figure 1), and, method of the present invention utilizes the precipitator method and spraying drying to combine, and adopts water solution system to precipitate, and adopts suitable pH value, the slurry of aging rear acquisition can obtain to have by spraying drying the powder of porous hollow microsphere structure, working method is simple, and production cost is low, but continuous production, and preparation cycle is short, is convenient to suitability for industrialized production.Preferably, add CTAB and can make the crystal grain of oxide compound less in the precipitation water solution system, powder is thinner.
In preferred version, preparation WO
3-TiO
2During composite oxides, add soluble tungsten salt in the aqueous solution of step S3 or CTAB solution, experimental results show that to make particle diameter less than the WO that comprises of 13nm
3-TiO
2The powder of composite oxide porous hollow microsphere.
Description of drawings
Fig. 1 is the WO that adopts the inventive method to make
3-TiO
2The scanning electron microscope image of composite oxide porous hollow microsphere.
Embodiment
Preferred embodiment the invention will be further described for the below's contrast accompanying drawing and combination.
Present embodiment provides a kind of oxide powder, it comprises the powder with the hollow microsphere structure that is formed by the nano-crystal oxide reunion, the particle diameter of described nano-crystal oxide is 10～20nm, the diameter of described hollow microsphere is 1～10 μ m, have vesicular structure on the ball wall of described hollow microsphere, the specific surface area of oxide powder is greater than 70m
2/ g.Wherein, this oxide compound is the wherein a kind of or mixtures two or more compositions among them in Tungsten oxide 99.999, titanium oxide, zirconium white, zinc oxide, cerium oxide.If catalyzer or support of the catalyst are prepared into the oxide powder with above-mentioned feature, can make catalyzer obtain higher catalytic activity.
Present embodiment also provides a kind of method for preparing above-mentioned oxide powder, comprises the following steps:
S1) in soluble metallic salt is the water-soluble or CTAB aqueous solution, stir the solution that 0.5～100h obtains metal ion under 20～90 ℃, the solution of this metal ion is filtered obtain settled solution A after removing impurity.The concentration of this soluble metallic salt can obtain according to it in the cubage in target product.Method of the present invention can be used for preparing a kind of or composite oxide powders two or more compositions among them in Tungsten oxide 99.999, titanium oxide, zirconium white, zinc oxide, cerium oxide, silicon oxide, stannic oxide, nickel oxide, ferric oxide, Red copper oxide, molybdenum oxide, and above-mentioned soluble metal corresponds to the soluble metallic salt of metal target oxide compound.
S2) the pH value to 3 of the described solution A of adjusting～12, make precipitation by metallic ion be precipitated thing B.In this step, can adopt the alkaline liquids such as sal volatile, sodium hydroxide solution, ammoniacal liquor to regulate the pH value, preferably adopting concentration is that 1%～32.5% ammoniacal liquor is to avoid bringing impurity to target product.
S3) the filter cake C that sediment B or water or CTAB solution washing sediment B is obtained is placed in water or the CTAB aqueous solution, add ammoniacal liquor to regulate pH value to 3～12, and adopt and stir or/and ultrasonic method is uniformly dispersed it, place aging 0.1～100h and obtain slurry D, aging temperature is room temperature～120 ℃, digestion time 0.1～100h is more than preferred 0.5h.
At preparation WO
3-TiO
2During composite oxides, the soluble salt in step S1 is titanium salt, for example: titanyl sulfate, metatitanic acid, titanium tetrachloride, titanous chloride, tetrabutyl titanate or their two or more mixtures; And must add soluble tungstate salt in the aqueous solution of this step or CTAB solution, and for example ammonium paratungstate or ammonium tungstate, in solution, the content of tungsten mass ratio 0.1%～20% shared according to Tungsten oxide 99.999 in target product calculates and obtains.
S4) slurry D is carried out spraying drying and obtain product E; Spray-dired moisture eliminator inlet temperature is 120～300 ℃, and airshed is 0.01-5000m
3/ hour, input speed is 0.01-1000m
3/ hour, to guarantee that its thermo-efficiency is higher than 50%.
S5) product E is obtained described oxide powder at 300～900 ℃ of roasting 0.1～50h.
For further explaining technical scheme of the present invention, hereinafter provide more specific embodiments more:
Embodiment 1:
Under room temperature, a certain amount of titanyl sulfate is added that in the aqueous solution of CTAB, (0.4g/L) obtains titanyl sulfate solution (solid content 5wt%) through filtering after the stirring of 12h, add ammoniacal liquor (ammonia concn 28%) to obtain slip A1 to pH=5.5; After slip A1 uses the aqueous solution (0.4g/L) of CTAB to wash three times, gained solid phase filter cake adds in the aqueous solution (0.4g/L) of CTAB and adds ammoniacal liquor (ammonia concn 28%) to regulate pH to 5.5, aging 6h under 80 ℃ after ultrasonic 1h under 50kHZ is through 220 ℃ of lower spraying drying (input speeds: 0.3m
3/ hour), 550 ℃ of lower roasting 3h obtain white TiO
2Powder (being labeled as T-5.5).
Embodiment 2:
Preparation condition and preparation procedure are with example 1, and regulating pH is 9, makes white TiO2 powder (being labeled as T-9).
Embodiment 3:
Preparation condition and preparation procedure are with example 1, and the CTAB content of the CTAB aqueous solution changes 0g/L into, makes white TiO
2Powder (being labeled as T-5.5-C0).
Embodiment 4:
Preparation condition and preparation procedure are with example 1, and titanyl sulfate makes metatitanic acid into, make white TiO
2Powder.
Embodiment 5:
Under room temperature, a certain amount of titanyl sulfate is added that in the aqueous solution of CTAB, (0.4g/L) obtains titanyl sulfate solution (solid content 5wt%) through filtering after the stirring of 12h, add ammoniacal liquor (28%) to obtain slip A2 to pH=5.5; After slip A2 used the aqueous solution (0.4g/L) of CTAB to wash three times, gained solid phase filter cake added and contains ammonium paratungstate (WO
3: TiO
2In=9wt%) the aqueous solution (0.4g/L) of CTAB and add ammoniacal liquor (28%) to regulate pH to 5.5, aging 6h under 80 ℃ after ultrasonic 1h under 50kHZ is through 220 ℃ of lower spraying drying (input speeds: 0.3m
3/ hour), 550 ℃ of lower roasting 3h obtain faint yellow WO
3-TiO
2Powder (being labeled as WT9-5.5).
Embodiment 6
Preparation condition and preparation procedure are with example 3, and regulating pH is 9, makes faint yellow WO
3-TiO
2Powder (being labeled as WT9-9).
Embodiment 7
Preparation condition and preparation procedure are with example 3, and the titanyl sulfate solid content changes 25% into, make faint yellow WO
3-TiO
2Powder.
Embodiment 8
Preparation condition and preparation procedure remove by filter impurity after titanyl sulfate adds and obtain titanyl sulfate solution with example 3 after stirring 12h under 80 ℃, make faint yellow WO
3-TiO
2Powder.
Embodiment 9
Preparation condition and preparation procedure be with example 3, at room temperature stirs after titanyl sulfate adds to remove by filter impurity after 24h and obtain titanyl sulfate solution, makes faint yellow WO
3-TiO
2Powder.
Embodiment 10
Preparation condition and preparation procedure are with example 3, and precipitation temperature changes 80 ℃ into, make faint yellow WO
3-TiO
2Powder.
Embodiment 11
Preparation condition and preparation procedure be with example 3, changes the concentration of CTAB into 0g/L, makes faint yellow WO
3-TiO
2Powder.
Embodiment 12
Preparation condition and preparation procedure be with example 3, changes the concentration of CTAB into 0.7g/L, makes faint yellow WO
3-TiO
2Powder.
Embodiment 13
Preparation condition and preparation procedure change ammonia concn into 10% with example 3, make faint yellow WO
3-TiO
2Powder.
Embodiment 14
Preparation condition and preparation procedure are with example 3, and washing times changes into five times, makes faint yellow WO
3-TiO
2Powder.
Embodiment 15
Preparation condition and preparation procedure be with example 3, ultrasonicly changes 1h under 60kHz into, makes faint yellow WO
3-TiO
2Powder.
Embodiment 16
Preparation condition and preparation procedure without ultrasonic, make faint yellow WO with example 3
3-TiO
2Powder.
Embodiment 17
Preparation condition and preparation procedure be with example 3, ultrasonicly changes 3h under 50kHz into, makes faint yellow WO
3-TiO
2Powder.
Embodiment 18
Preparation condition and preparation procedure are with example 3, and aging temperature changes 90 ℃ into, make faint yellow WO
3-TiO
2Powder.
Embodiment 19
Preparation condition and preparation procedure are with example 3, and digestion time changes 3h into, make faint yellow WO
3-TiO
2Powder.Embodiment 20
Preparation condition and preparation procedure are with example 3, and the spraying drying temperature changes 200 ℃ into, make faint yellow WO
3-TiO
2Powder.
Embodiment 21
Preparation condition and preparation procedure are with example 3, and spray-dired input speed changes 60m into
3/ hour, make faint yellow WO
3-TiO
2Powder.
Embodiment 22
Preparation condition and preparation procedure are with example 3, and the titanyl sulfate raw material is replaced by titanium tetrachloride, make faint yellow WO
3-TiO
2Powder.
Embodiment 23
Preparation condition and preparation procedure are with example 3, and maturing temperature changes 600 ℃ into, make faint yellow WO
3-TiO
2Powder.
Embodiment 24
Preparation condition and preparation procedure are with example 3, and roasting time changes 5h into, make faint yellow WO
3-TiO
2Powder.Test case 1:
Take WT9-5.5(embodiment 5) be example, carry out scanning electron microscope test, test result shows (as shown in Figure 1), the gained sample is mainly a small-particle (10nm left and right) and is agglomerated into secondary spherical particle (1～10 μ m).Can find out from the spheroid of partial rupture, its inside is hollow form.
Test case 2:
Respectively take T-5.5(embodiment 1), T-9(embodiment 2), T-5.5-C0(embodiment 3), WT9-5.5(embodiment 5) and WT9-9(embodiment 6) be example, carry out XRD test.The sample peak position is all 25.2,37.8,47.9,53.8,54.0,62.6,68.8,70.4 and 75.0, and wherein there are a peak in T-5.5 and T-5.5-C0 at 30.8 places.
Test result shows: the TiO of the catalyzer of developing
2Mainly take Anatase as main, there is the part brookite in T-5.5, does not wherein find WO
3-TiO
2Mixed oxide or pure WO
3Corresponding reflection peak, this shows WO
3Not with TiO
2Surface Dispersed W O
3Air mass or amorphous layer occur, also or WO
3Concentration is too low and can't detect.So we suppose that tungsten ion enters TiO
2Substituting the Ti ion in lattice forms the W-O-Ti key or enters interstitial site.And utilize the Scherrer formula to calculate its particle diameter (seeing Table 1).
Test case 3:
Respectively take T-5.5(embodiment 1), T-9(embodiment 2), WT9-5.5(embodiment 5) and WT9-9(embodiment 6) be example, carry out N
2The adsorption desorption test, its result is as shown in table 1.
Hollow WO in table 1 embodiment
3-TiO
2The partial properties parameter of composite oxides microballoon
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that concrete enforcement of the present invention is confined to these explanations.For those skilled in the art, without departing from the inventive concept of the premise, can also make some being equal to substitute or obvious modification, and performance or purposes identical, all should be considered as belonging to protection scope of the present invention.
Claims (14)
1. oxide powder, it is characterized in that: comprise the powder with the hollow microsphere structure that is formed by the nano-crystal oxide reunion, the particle diameter of described nano-crystal oxide is 10～20nm, and the diameter of described hollow microsphere is 1～10 μ m, has vesicular structure on the ball wall of described hollow microsphere.
2. oxide powder according to claim 1, it is characterized in that: the specific surface area of described oxide powder is greater than 70m
2/ g.
3. oxide powder according to claim 1 and 2, it is characterized in that: described oxide compound is the wherein a kind of or mixtures two or more compositions among them of Tungsten oxide 99.999, titanium oxide, zirconium white, zinc oxide, cerium oxide, silicon oxide, stannic oxide, nickel oxide, ferric oxide, Red copper oxide, molybdenum oxide.
4. a catalyzer, is characterized in that: comprise the described oxide powder of claim 1 or 2.
5. catalyzer according to claim 4, it is characterized in that: described oxide compound is the mixture of Tungsten oxide 99.999 and titanium oxide, wherein the weight percent of Tungsten oxide 99.999 is 0.1%～20%.
6. a support of the catalyst, is characterized in that: comprise the described oxide powder of claim 1 or 2.
7. the preparation method of an oxide powder, is characterized in that, comprises the following steps:
S1: soluble metallic salt in the water-soluble or CTAB aqueous solution, is stirred the solution that 0.5～100h obtains metal ion under 0～90 ℃, the solution of this metal ion is filtered obtain settled solution A after removing impurity;
S2: the pH value to 3 of the described solution A of adjusting～12 make precipitation by metallic ion be precipitated thing B;
S3: the filter cake C that sediment B or water or CTAB solution washing sediment B are obtained is placed in water or the CTAB aqueous solution, add ammoniacal liquor to regulate pH value to 3～12, and adopt and stir or/and hyperacoustic method is uniformly dispersed it, place aging 0.1～100h and obtain slurry D;
S4: slurry D is carried out spraying drying obtain product E;
S5: product E is obtained described oxide powder at 300～900 ℃ of roasting 0.1～50h.
8. the preparation method of oxide powder according to claim 7, it is characterized in that: the soluble metallic salt described in described step S1 is soluble tungsten salt, solubility titanium salt, solubility zirconates, soluble zinc salt, solubility cerium salt, soluble silicon salt, solubility pink salt, soluble nickel salt, soluble ferric iron salt, soluble copper salt or soluble molybdenum salt.
9. the preparation method of oxide powder according to claim 7, it is characterized in that: described oxide compound is Tungsten oxide 99.999-titanium oxide composite oxides, soluble metallic salt described in described step S1 is the solubility titanium salt, contains soluble tungsten salt in the water that in described step S3, sediment B or filter cake C add or the CTAB aqueous solution.
10. the preparation method of oxide powder according to claim 9, it is characterized in that: in described oxide powder, the weight percent of Tungsten oxide 99.999 is 0.1%～20%.
11. require the preparation method of 7,8,9 or 10 described oxide powders according to power, it is characterized in that: the mode of regulating the pH value of described solution A in described step S2 is that to add concentration be 1%～32.5% ammoniacal liquor.
12. require the preparation method of 7,8,9 or 10 described oxide powders according to power, it is characterized in that: in described step S4, spray-dired moisture eliminator inlet temperature is 120～300 ℃, and airshed is 0.01-5000m
3/ hour, input speed is 0.01-1000m
3/ hour, to guarantee that its thermo-efficiency is higher than 50%.
13. require the preparation method of 7,8,9 or 10 described oxide powders according to power, it is characterized in that: it is room temperature～120 ℃ that described step S3 places aging temperature, and digestion time is 0.1～100h.
14. require the preparation method of 7,8,9 or 10 described oxide powders according to power, it is characterized in that: in described step S1 and S3 in the CTAB aqueous solution concentration of CTAB greater than 0g/L less than 2g/L.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310095109.3A CN103172030B (en) | 2013-03-22 | 2013-03-22 | Oxide powder and preparation method thereof as well as catalyst and carrier thereof |
| HK13109859.6A HK1182373A1 (en) | 2013-03-22 | 2013-08-22 | Oxide powder and its preparation method, catalyst, and catalyst carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310095109.3A CN103172030B (en) | 2013-03-22 | 2013-03-22 | Oxide powder and preparation method thereof as well as catalyst and carrier thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103172030A true CN103172030A (en) | 2013-06-26 |
| CN103172030B CN103172030B (en) | 2015-04-15 |
Family
ID=48632315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310095109.3A Expired - Fee Related CN103172030B (en) | 2013-03-22 | 2013-03-22 | Oxide powder and preparation method thereof as well as catalyst and carrier thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN103172030B (en) |
| HK (1) | HK1182373A1 (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104120508A (en) * | 2014-06-26 | 2014-10-29 | 浙江大学 | Metal oxide nanofiber with hierarchical structure as well as preparation method and application thereof |
| CN104607164A (en) * | 2015-01-16 | 2015-05-13 | 吉林化工学院 | Novel preparation method of photocatalytic material |
| CN104741112A (en) * | 2015-03-27 | 2015-07-01 | 陕西科技大学 | A kind of preparation method of TiO2/WO3 composite powder |
| CN105056923A (en) * | 2015-08-17 | 2015-11-18 | 成都金鑫天蓝科技有限公司 | Anti-water and anti-sulfur denitration catalyst, preparation method and application thereof |
| CN105788870A (en) * | 2016-04-01 | 2016-07-20 | 浙江工业大学 | Application of mesoporous hollow spherical titanium dioxide/tungsten trioxide composite material in preparation of thin film electrode |
| CN106668880A (en) * | 2014-10-31 | 2017-05-17 | 苏州大学 | Application of ultrasound/ magnetic resonance bimodal contrast medium |
| CN106925268A (en) * | 2015-12-30 | 2017-07-07 | 中国科学院过程工程研究所 | A kind of hollow-core construction cerium-based composite oxides catalyst and preparation method thereof |
| CN106925265A (en) * | 2015-12-30 | 2017-07-07 | 中国科学院过程工程研究所 | A kind of transition metal composite oxide catalytic agent |
| CN107281997A (en) * | 2017-08-03 | 2017-10-24 | 中国矿业大学 | A kind of porous oxide/titanium dioxide micrometer ball composite catalyzing material and preparation method thereof |
| CN107952427A (en) * | 2017-12-06 | 2018-04-24 | 南京威安新材料科技有限公司 | The production method and production equipment of SCR catalyst |
| CN108046217A (en) * | 2017-11-07 | 2018-05-18 | 深圳市大擎科技有限公司 | The preparation method of nano composite metal oxide |
| CN108722466A (en) * | 2018-06-05 | 2018-11-02 | 青岛科技大学 | A kind of g-C3N4The preparation method of/ZnO compound hollow microballoons |
| CN108726485A (en) * | 2018-06-29 | 2018-11-02 | 华中科技大学 | A kind of Porous hollow oxidate nano microballoon and the preparation method and application thereof |
| CN109354062A (en) * | 2018-11-26 | 2019-02-19 | 昆明冶金研究院 | Anatase type nano titanium dioxide and preparation method and application thereof |
| CN112138665A (en) * | 2020-10-21 | 2020-12-29 | 石河子大学 | CO-SCR low-temperature high-efficiency non-noble metal oxide catalyst and preparation method thereof |
| CN113145093A (en) * | 2021-05-07 | 2021-07-23 | 中国地质大学（北京） | Application of waste SCR catalyst in preparation of silicon dioxide-titanium dioxide composite photocatalyst |
| CN113908844A (en) * | 2021-10-28 | 2022-01-11 | 济南大学 | Iron-cerium-titanium composite oxide supported vanadium oxide catalyst, preparation method and application thereof |
| CN118136870A (en) * | 2024-05-07 | 2024-06-04 | 国家电投集团氢能科技发展有限公司 | Catalyst carrier, catalyst, preparation and application of catalyst and fuel cell |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093951A (en) * | 1992-12-08 | 1994-10-26 | 恩格尔哈德公司 | The composition and method of making the same that is used for the catalytic cracking passivating vanadium |
| US20090241496A1 (en) * | 2006-04-26 | 2009-10-01 | Bruno Pintault | Process for Producing a Nanoporous Layer of Nanoparticles and Layer Thus Obtained |
| CN101708853A (en) * | 2009-07-08 | 2010-05-19 | 济南大学 | Hollow silicon dioxide microsphere with different surface configurations and preparation method thereof |
| CN101905904A (en) * | 2010-07-22 | 2010-12-08 | 北京航空航天大学 | Preparation method of nickel oxide microspheres composed of lotus root-shaped nanosheets |
-
2013
- 2013-03-22 CN CN201310095109.3A patent/CN103172030B/en not_active Expired - Fee Related
- 2013-08-22 HK HK13109859.6A patent/HK1182373A1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093951A (en) * | 1992-12-08 | 1994-10-26 | 恩格尔哈德公司 | The composition and method of making the same that is used for the catalytic cracking passivating vanadium |
| US20090241496A1 (en) * | 2006-04-26 | 2009-10-01 | Bruno Pintault | Process for Producing a Nanoporous Layer of Nanoparticles and Layer Thus Obtained |
| CN101708853A (en) * | 2009-07-08 | 2010-05-19 | 济南大学 | Hollow silicon dioxide microsphere with different surface configurations and preparation method thereof |
| CN101905904A (en) * | 2010-07-22 | 2010-12-08 | 北京航空航天大学 | Preparation method of nickel oxide microspheres composed of lotus root-shaped nanosheets |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104120508B (en) * | 2014-06-26 | 2016-08-24 | 浙江大学 | A kind of metal oxide nanofibres with hierarchy and its preparation method and application |
| CN104120508A (en) * | 2014-06-26 | 2014-10-29 | 浙江大学 | Metal oxide nanofiber with hierarchical structure as well as preparation method and application thereof |
| CN106668880B (en) * | 2014-10-31 | 2019-11-22 | 苏州大学 | Application of Ultrasound/Magnetic Resonance Dual Mode Contrast Agent |
| CN106668880A (en) * | 2014-10-31 | 2017-05-17 | 苏州大学 | Application of ultrasound/ magnetic resonance bimodal contrast medium |
| CN104607164A (en) * | 2015-01-16 | 2015-05-13 | 吉林化工学院 | Novel preparation method of photocatalytic material |
| CN104741112A (en) * | 2015-03-27 | 2015-07-01 | 陕西科技大学 | A kind of preparation method of TiO2/WO3 composite powder |
| CN105056923B (en) * | 2015-08-17 | 2018-11-09 | 成都金鑫天蓝科技有限公司 | A kind of water resistant sulfur resistive type denitrating catalyst, preparation method and its usage |
| CN105056923A (en) * | 2015-08-17 | 2015-11-18 | 成都金鑫天蓝科技有限公司 | Anti-water and anti-sulfur denitration catalyst, preparation method and application thereof |
| CN106925268A (en) * | 2015-12-30 | 2017-07-07 | 中国科学院过程工程研究所 | A kind of hollow-core construction cerium-based composite oxides catalyst and preparation method thereof |
| CN106925265B (en) * | 2015-12-30 | 2019-09-24 | 中国科学院过程工程研究所 | A kind of transition metal composite oxide catalytic agent |
| CN106925268B (en) * | 2015-12-30 | 2019-10-18 | 中国科学院过程工程研究所 | A kind of hollow structure cerium-based composite oxide catalyst and preparation method thereof |
| CN106925265A (en) * | 2015-12-30 | 2017-07-07 | 中国科学院过程工程研究所 | A kind of transition metal composite oxide catalytic agent |
| CN105788870A (en) * | 2016-04-01 | 2016-07-20 | 浙江工业大学 | Application of mesoporous hollow spherical titanium dioxide/tungsten trioxide composite material in preparation of thin film electrode |
| CN107281997A (en) * | 2017-08-03 | 2017-10-24 | 中国矿业大学 | A kind of porous oxide/titanium dioxide micrometer ball composite catalyzing material and preparation method thereof |
| CN107281997B (en) * | 2017-08-03 | 2020-02-14 | 中国矿业大学 | Porous oxide/titanium dioxide microsphere composite catalytic material and preparation method thereof |
| CN108046217B (en) * | 2017-11-07 | 2020-12-01 | 深圳市大擎科技有限公司 | Method for preparing nano composite metal oxide |
| CN108046217A (en) * | 2017-11-07 | 2018-05-18 | 深圳市大擎科技有限公司 | The preparation method of nano composite metal oxide |
| CN107952427A (en) * | 2017-12-06 | 2018-04-24 | 南京威安新材料科技有限公司 | The production method and production equipment of SCR catalyst |
| CN107952427B (en) * | 2017-12-06 | 2022-12-20 | 南京威安新材料科技有限公司 | Production method and production equipment of SCR catalyst |
| CN108722466A (en) * | 2018-06-05 | 2018-11-02 | 青岛科技大学 | A kind of g-C3N4The preparation method of/ZnO compound hollow microballoons |
| CN108726485A (en) * | 2018-06-29 | 2018-11-02 | 华中科技大学 | A kind of Porous hollow oxidate nano microballoon and the preparation method and application thereof |
| CN108726485B (en) * | 2018-06-29 | 2020-07-10 | 华中科技大学 | Porous hollow oxide nano-microsphere and preparation method and application thereof |
| CN109354062A (en) * | 2018-11-26 | 2019-02-19 | 昆明冶金研究院 | Anatase type nano titanium dioxide and preparation method and application thereof |
| CN112138665A (en) * | 2020-10-21 | 2020-12-29 | 石河子大学 | CO-SCR low-temperature high-efficiency non-noble metal oxide catalyst and preparation method thereof |
| CN112138665B (en) * | 2020-10-21 | 2022-10-28 | 石河子大学 | CO-SCR low-temperature high-efficiency non-noble metal oxide catalyst and preparation method thereof |
| CN113145093A (en) * | 2021-05-07 | 2021-07-23 | 中国地质大学（北京） | Application of waste SCR catalyst in preparation of silicon dioxide-titanium dioxide composite photocatalyst |
| CN113908844A (en) * | 2021-10-28 | 2022-01-11 | 济南大学 | Iron-cerium-titanium composite oxide supported vanadium oxide catalyst, preparation method and application thereof |
| CN118136870A (en) * | 2024-05-07 | 2024-06-04 | 国家电投集团氢能科技发展有限公司 | Catalyst carrier, catalyst, preparation and application of catalyst and fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1182373A1 (en) | 2013-11-29 |
| CN103172030B (en) | 2015-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103172030B (en) | Oxide powder and preparation method thereof as well as catalyst and carrier thereof | |
| CN101318700B (en) | Bismuth vanadate powder and preparation method thereof | |
| CN106914264B (en) | Preparation method of composite visible light catalyst | |
| EP2519348B1 (en) | Method of production of photocatalytic powder comprising titanium dioxide and manganese dioxide active under ultraviolet and visible light | |
| CN106732524B (en) | Alpha/beta-bismuth oxide phase heterojunction photocatalyst and preparation method and application thereof | |
| CN101792117B (en) | Method for preparing tungsten-doped anatase type nano titanium dioxide composite powder | |
| CN101811040B (en) | Synthesis method of surface hydrophobicity bismuth orthovanadate with performance of catalyzing and degrading pollutant by visible light | |
| CN112371105B (en) | A kind of niobium pentoxide/titanium dioxide composite photocatalyst and its preparation method and application | |
| CN102698785A (en) | A kind of preparation method of diatomite-supported nitrogen-doped nano-TiO2 photocatalytic material | |
| CN106622318A (en) | Layered composite photocatalyst using bimetallic nanoparticles as heterojunctions and preparation method thereof | |
| CN109331817A (en) | It is a kind of for decomposing the catalysis material and preparation method of organic matter in air | |
| CN101559368A (en) | Visible light active boron-nickel co-doped titanium dioxide solid solution catalyst and preparation method thereof | |
| CN105797762A (en) | Photocatalytic ceramsite as well as preparation method and application thereof | |
| CN106140144A (en) | SCR denitration and preparation method thereof | |
| CN102974379B (en) | Method for preparing nitrogen-doped photo-catalytic material containing gallium oxide at low temperature | |
| Liu et al. | Biomimetic synthesis of C-doped g-C3N4 spinous hollow microspheres from sunflower pollen with enhanced visible-light photocatalytic performance | |
| CN102909009A (en) | A kind of preparation method of crystalline silver supported TiO2 nanoparticle | |
| CN111054419A (en) | A kind of semiconductor/g-C3N4 photocatalyst for CO2 reduction and preparation method thereof | |
| CN102553562A (en) | Multiple modified composite photocatalyst and preparation method thereof | |
| CN108014822B (en) | A kind of preparation method and application of silver iodide/bismuth selenate composite material | |
| CN105233821A (en) | Strontium-doped and silver-doped nanometer titanium dioxide visible light catalyst | |
| CN102786080B (en) | Indium tin oxide compound and preparation method thereof and photocatalytic applications | |
| Liu et al. | Fabrication of multilayer porous structured TiO2–ZrTiO4–SiO2 heterostructure towards enhanced photo-degradation activities | |
| CN105032471B (en) | A kind of visible light-responded nano-TiO2The preparation of/Zeolite composite materials | |
| CN110252375B (en) | A kind of iron, nitrogen, cobalt co-doped titanium dioxide/activated carbon composite, preparation method and application as photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1182373 Country of ref document: HK |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1182373 Country of ref document: HK |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150415 Termination date: 20180322 |