CN109675540A - A kind of preparation method of amorphous nano titanium dioxide optical catalyst - Google Patents
A kind of preparation method of amorphous nano titanium dioxide optical catalyst Download PDFInfo
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- CN109675540A CN109675540A CN201811555134.4A CN201811555134A CN109675540A CN 109675540 A CN109675540 A CN 109675540A CN 201811555134 A CN201811555134 A CN 201811555134A CN 109675540 A CN109675540 A CN 109675540A
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- titanium dioxide
- metatitanic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 230000003287 optical effect Effects 0.000 title claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 129
- 239000002253 acid Substances 0.000 claims abstract description 83
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 239000012065 filter cake Substances 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000003825 pressing Methods 0.000 claims abstract description 11
- 238000001238 wet grinding Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 239000004576 sand Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 238000004061 bleaching Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000013067 intermediate product Substances 0.000 claims description 9
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical group [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 239000000356 contaminant Substances 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 3
- 206010013786 Dry skin Diseases 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 7
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 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 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001048 orange dye Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000593 microemulsion method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000007144 microwave assisted synthesis reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The present invention relates to a kind of preparation method of amorphous nano titanium dioxide optical catalyst, steps are as follows: metatitanic acid is configured to the suspension of 600~800g/L by A., and adjusting pH value with 10% NaOH solution is 7~8, is dispersed with stirring obtained metatitanic acid slurry；B. metatitanic acid slurry carries out 2~3h of wet grinding with sand mill；C. the metatitanic acid slurry after filters pressing grinding, then wash to filtrate conductivity less than 10 μ s/cm, filter cake is made；D. amorphous titanium dioxide is made in 200~250 DEG C of dryings in filter cake；E. air-flow crushing is carried out in airslide disintegrating mill, and amorphous nano titanium dioxide optical catalyst is made.Amorphous nano titanium dioxide optical catalyst prepared by the present invention has biggish specific surface area and preferable water dispersible and lower forbidden bandwidth, is used for degradation of contaminant, has good photocatalysis performance under the conditions of radiation of visible light.
Description
Technical field
The invention belongs to nanometer technical field of new material preparation, and in particular to a kind of amorphous nano optically catalytic TiO 2
The preparation method of agent.
Background technique
Titanium dioxide has many advantages, such as that chemical property is stable, nontoxic, UV absorbance is strong as photochemical catalyst, in light
Many necks such as catalysis, photoelectric conversion and self-cleaning material have a wide range of applications.Due to crystalline state TiO2With biggish band gap
Energy (3.2eV) cannot utilize visible absorption, carry out light-catalyzed reaction, therefore, it is seen that the low defect of light utilization efficiency is puzzlement
TiO2One of the emphasis of photocatalysis technology development.
Due to amorphous state TiO2Frame mode with " shortrange order " and " longrange disorder ", so in amorphous state TiO2Knot
Exist and crystalline state TiO in structure2The basic band structure of similar valence band and conduction band.Amorphous state TiO2In the presence of different with crystalline state
There is localized state magnetic tape trailer in the valence band and conduction band of sample, and due to amorphous state TiO2With the presence of a large amount of dangling bonds in semiconductor,
In band structure again between valence band and conduction band there are gap band, the difference of the two band structure is depositing for localized state magnetic tape trailer and gap band
In amorphous state TiO2In electron transition can occur between the electronic state between valence band and conduction band and valence band and conduction band,
A possibility that electron transition, increases considerably.Therefore, amorphous state TiO2With some and crystalline state TiO2Different optical properties.
Adan Luna~Flores etc. reports the amorphous state TiO to about 300nm2Carbon doping is carried out, in radiation of visible light
Under, it degrades to rhodamine B solution, 100min degradation rate about 90% has embodied photocatalytic activity under preferable visible light
(Economical and Efficient Carbon~Doped Amorphous TiO2Photocatalyst Obtained
by Microwave Assisted Synthesis for the Degradation ofRhodamine B[J].Mater.,
2017,10(12):1447).But the amorphous nano TiO about the low forbidden bandwidth for preparing large specific surface area2, to mention
The research of its high photocatalysis performance, then there is not been reported at present.
The prior art is by dichloride in anatase type TiO2Be doped modification, noble metal loading, semiconductors coupling etc. compared with
It is active to improve its ultraviolet light photocatalysis for complicated preparation method.For titanium dioxide amorphous nano particle, researcher also tastes
A variety of methods are tried, for example, colloidal sol~gel method, direct precipitation method, microemulsion method etc., finally require at 300 DEG C or so
At a temperature of, amorphous nano-titanium dioxide is made after carrying out calcination processing, in addition, microemulsion method and hydro-thermal method, although can be with
Accurate control amorphous nano TiO2Partial size, but exist very serious agglomeration.Therefore, generally existing in existing preparation method
The product particle size of preparation greatly and reunite and more serious problem and environmental pollution problem calcined to product.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of amorphous nano titanium dioxide optical catalyst, optimize titanium dioxide
The microstructure of titanium photochemical catalyst makes it have large specific surface area and lower forbidden bandwidth, improves optically catalytic TiO 2
The water dispersible of agent makes up the nano-titanium dioxide performance deficiency weaker to visible absorption.
The technical scheme is that a kind of preparation method of amorphous nano titanium dioxide optical catalyst, including it is following
Step:
A. metatitanic acid is configured to the suspension that concentration is 600~800g/L with deionized water, is 10% with mass concentration
NaOH aqueous solution to adjust the pH value of suspension be 7~8, add dispersing agent, then stirred with the revolving speed of 500~600r/min
Disperse 20~30min, metatitanic acid slurry is made；
B. the metatitanic acid slurry of step A is subjected to 2~3h of wet grinding with sand mill；
C. filters pressing is carried out with plate and frame filter press to the metatitanic acid slurry after step B grinding, be washed with deionized to filtrate
Filter cake is made less than 10 μ s/cm in conductivity；
D. the filtered filter cake of step C is put into box type drying equipment, is dried at a temperature of 200~250 DEG C, made
Obtain amorphous titanium dioxide；
E. amorphous titanium dioxide prepared by step D is subjected in airslide disintegrating mill air-flow crushing, amorphous state is made
Nano titanium dioxide photocatalyst.
Metatitanic acid used is the intermediate product that sulfuric acid process by bleaching prepares titanium dioxide in step A, metatitanic acid it is flat
Equal partial size≤5.0 μm, metatitanic acid mass percentage >=98%.The additive amount of dispersing agent is metatitanic acid with TiO in step A2Meter
The 0.1~0.3% of quality, dispersing agent are calgon.Average grain diameter≤0.35 μm that metatitanic acid is made is sanded in step B.
Drying time is 3~4h in step D.
A kind of preparation method of amorphous nano titanium dioxide optical catalyst of the present invention prepares crystalline silica with sulfuric acid process
The intermediate product metatitanic acid of titanium is basic raw material, by techniques such as wet grinding, filtering, drying, air-flow crushings, obtained amorphous state
Nano-titanium dioxide solves the dichloride in anatase type TiO of existing sulfuric acid process preparation2Photochemical catalyst does not absorb sunlight visible light
Defect.Amorphous nano titanium dioxide optical catalyst prepared by the present invention has biggish specific surface area and good moisture
Property and lower forbidden bandwidth are dissipated, degradation of contaminant is used for, there is good photocatalysis performance under the conditions of radiation of visible light,
The microstructure for optimizing titanium dioxide optical catalyst, solves nano-TiO2To the responsiveness of visible light, catalyst is improved
Performance.Preparation method technical process of the present invention is simple, equipment investment and operating cost are low, easy to operate, energy conservation and environmental protection.
Specific embodiment
The following describes the present invention in detail with reference to examples.The scope of protection of the present invention is not limited to the embodiment, this field
Technical staff makes any change within the scope of the claims and also belongs to the scope of protection of the invention.
Embodiment 1
Preparation 1#Amorphous nano titanium dioxide optical catalyst, step are as follows:
A, metatitanic acid is configured to the suspension that concentration is 600g/L with deionized water, the NaOH for being 10% with mass concentration
The pH value that aqueous solution adjusts suspension is 7.0, adds sodium hexametaphosphate dispersant, and additive amount is metatitanic acid with TiO2Count quality
0.1%, 20min is then dispersed with stirring with the revolving speed of 500r/min, be made metatitanic acid slurry；Metatitanic acid is the sulphur by bleaching
Acid system prepares the intermediate product of titanium dioxide, average grain diameter≤5.0 μm, metatitanic acid mass percentage >=98%；
B, the metatitanic acid slurry of step A is subjected to wet grinding 2.0h with sand mill, be made metatitanic acid average grain diameter≤
0.35μm；
C, filters pressing is carried out to the metatitanic acid slurry after step B grinding, be washed with deionized to filtrate conductivity less than 10 μ
Filter cake is made in s/cm；
D, the step C filter cake prepared is put into box type drying equipment, dry 3.0h, is made amorphous at a temperature of 200 DEG C
State titanium dioxide；
E, by amorphous titanium dioxide prepared by step D in airslide disintegrating mill, air-flow crushing is carried out, is made 1#Amorphous
State nano titanium dioxide photocatalyst.
Embodiment 2
Preparation 2#Amorphous nano titanium dioxide optical catalyst, step are as follows:
A, metatitanic acid is configured to the suspension that concentration is 700g/L with deionized water, the NaOH for being 10% with mass concentration
The pH value that aqueous solution adjusts suspension is 7.5, adds sodium hexametaphosphate dispersant, and additive amount is metatitanic acid with TiO2Count quality
0.2%, 25min is then dispersed with stirring with the revolving speed of 550r/min, be made metatitanic acid slurry；Metatitanic acid is the sulphur by bleaching
Acid system prepares the intermediate product of titanium dioxide, average grain diameter≤5.0 μm, metatitanic acid mass percentage >=98%；
B, the metatitanic acid slurry of step A is subjected to wet grinding 2.5h with sand mill, be made metatitanic acid average grain diameter≤
0.35μm；
C, filters pressing is carried out to the metatitanic acid slurry after step B grinding, be washed with deionized to filtrate conductivity less than 10 μ
Filter cake is made in s/cm；
D, the step C filter cake prepared is put into box type drying equipment, dry 3.5h, is made amorphous at a temperature of 220 DEG C
State titanium dioxide；
E, by amorphous titanium dioxide prepared by step D in airslide disintegrating mill, air-flow crushing is carried out, is made 2#Amorphous
State nano titanium dioxide photocatalyst.
Embodiment 3
Preparation 3#Amorphous nano titanium dioxide optical catalyst, step are as follows:
A, metatitanic acid is configured to the suspension that concentration is 800g/L with deionized water, the NaOH for being 10% with mass concentration
The pH value that aqueous solution adjusts suspension is 8.0, adds sodium hexametaphosphate dispersant, and additive amount is metatitanic acid with TiO2Count quality
0.3%, 30min is then dispersed with stirring with the revolving speed of 600r/min, be made metatitanic acid slurry；Metatitanic acid is the sulphur by bleaching
Acid system prepares the intermediate product of titanium dioxide, average grain diameter≤5.0 μm, metatitanic acid mass percentage >=98%；
B, the metatitanic acid slurry of step A is subjected to wet grinding 3.0h with sand mill, be made metatitanic acid average grain diameter≤
0.35μm；
C, filters pressing is carried out to the metatitanic acid slurry after step B grinding, be washed with deionized to filtrate conductivity less than 10 μ
Filter cake is made in s/cm；
D, the step C filter cake prepared is put into box type drying equipment, dry 3.0h, is made amorphous at a temperature of 250 DEG C
State titanium dioxide；
E, by amorphous titanium dioxide prepared by step D in airslide disintegrating mill, air-flow crushing is carried out, is made 3#Amorphous
State nano titanium dioxide photocatalyst.
Embodiment 4
Preparation 4#Amorphous nano titanium dioxide optical catalyst, step are as follows:
A, metatitanic acid is configured to the suspension that concentration is 650g/L with deionized water, the NaOH for being 10% with mass concentration
The pH value that aqueous solution adjusts suspension is 7.8, adds sodium hexametaphosphate dispersant, and additive amount is metatitanic acid with TiO2Count quality
0.25%, 27min is then dispersed with stirring with the revolving speed of 580r/min, be made metatitanic acid slurry；Metatitanic acid is by bleaching
Sulfuric acid process prepares the intermediate product of titanium dioxide, average grain diameter≤5.0 μm, metatitanic acid mass percentage >=98%；
B, the metatitanic acid slurry of step A is subjected to wet grinding 2.8h with sand mill, be made metatitanic acid average grain diameter≤
0.35μm；
C, filters pressing is carried out to the metatitanic acid slurry after step B grinding, be washed with deionized to filtrate conductivity less than 10 μ
Filter cake is made in s/cm；
D, the step C filter cake prepared is put into box type drying equipment, dry 4.0h, is made amorphous at a temperature of 230 DEG C
State titanium dioxide；
E, by amorphous titanium dioxide prepared by step D in airslide disintegrating mill, air-flow crushing is carried out, is made 4#Amorphous
State nano titanium dioxide photocatalyst.
Embodiment 5
Preparation 5#Amorphous nano titanium dioxide optical catalyst, step are as follows:
A, metatitanic acid is configured to the suspension that concentration is 750g/L with deionized water, the NaOH for being 10% with mass concentration
The pH value that aqueous solution adjusts suspension is 7.3, adds sodium hexametaphosphate dispersant, and additive amount is metatitanic acid with TiO2Count quality
0.15%, 22min is then dispersed with stirring with the revolving speed of 530r/min, be made metatitanic acid slurry；Metatitanic acid is by bleaching
Sulfuric acid process prepares the intermediate product of titanium dioxide, average grain diameter≤5.0 μm, metatitanic acid mass percentage >=98%.
B, the metatitanic acid slurry of step A is subjected to wet grinding 2.2h with sand mill, be made metatitanic acid average grain diameter≤
0.35μm；
C, filters pressing is carried out to the metatitanic acid slurry after step B grinding, be washed with deionized to filtrate conductivity less than 10 μ
Filter cake is made in s/cm；
D, the step C filter cake prepared is put into box type drying equipment, dry 3.8h, is made amorphous at a temperature of 210 DEG C
State titanium dioxide；
E, by amorphous titanium dioxide prepared by step D in airslide disintegrating mill, air-flow crushing is carried out, amorphous state is made
Nano titanium dioxide photocatalyst.
Comparative example 1
Preparation 1#Nanometer anatase titania photochemical catalyst:
(1) metatitanic acid is configured to the suspension that concentration is 700g/L, the NaOH for being 10% with mass concentration by deionized water
The pH value that aqueous solution adjusts suspension is 7.5, adds sodium hexametaphosphate dispersant, and additive amount is metatitanic acid with TiO2Count quality
0.2%, 25min is then dispersed with stirring with the revolving speed of 550r/min, be made metatitanic acid slurry；Metatitanic acid is the sulphur by bleaching
Acid system prepares the intermediate product of titanium dioxide, average grain diameter≤5.0 μm, metatitanic acid mass percentage >=98%；
(2) the metatitanic acid slurry of step (1) is subjected to wet grinding 2.5h with sand mill, the average grain diameter of metatitanic acid is made
≤0.35μm；
(3) filters pressing is carried out to the metatitanic acid slurry after step (2) grinding, is washed with deionized to filtrate conductivity and is less than
Filter cake is made in 10 μ s/cm；
(4) filter cake for preparing step (3), carries out calcining 3.5h in Muffle furnace at a temperature of 500 DEG C, anatase titanium dioxide two is made
Titanium oxide；
(5) by anatase titanium dioxide prepared by step (4) in airslide disintegrating mill, air-flow crushing is carried out, is made 1#
Nanometer anatase titania photochemical catalyst.
Comparative example 2
2#Nanometer anatase titania photochemical catalyst
The universal nanometer anatase titania (NA-100) of Hebei Mai Sen titanium dioxide Co., Ltd production, through superfine
Crush, particle size range be 0.2~0.4 μm, as 2#Nanometer anatase titania photochemical catalyst.NA-100 photochemical catalyst granularity
It is distributed that relatively uniform, with high purity, whiteness is good, good luster, the Optimality with stronger reducing power, covering power and water dispersible
Energy.Its performance indicator is shown in Table 1.
Table 12#Anatase titanium dioxide (NA-100) performance indicator
| Project | Index |
| TiO2Content (%) | ≥98.0 |
| Reducing power (Reynolds number) | ≥1300 |
| Whiteness (%) | ≥96.0 |
| Oil absorption (g/100g) | ≤25 |
| PH value | 6.5~8.5 |
| Resistivity (Ω m) | ≥20 |
| Sieve residue (45 μm, %) | ≤0.06 |
| Water content (%) | ≤0.5 |
| ISO591 classification | A1 |
| ASTMD476 classification | Ⅰ |
(1) performance test
5 groups of amorphous nano titanium dioxide optical catalysts are tested for the property, wherein band-gap energy is inhaled using ultraviolet-visible
Spectrum (UV-vis) method of receipts is tested, and the band-gap energy of sample is then calculated using the method for tangent line, and test result such as will
Shown in table 2, as a comparison, two kinds of dichloride in anatase type TiO of prior art sulfuric acid process preparation2The test result of photochemical catalyst also arranges
Enter in table 2.
2 titanium dioxide testing performance index result of table
It is biggish to show that amorphous nano titanium dioxide optical catalyst prepared by the present invention has by the test result of table 2
Specific surface area, preferable water dispersible and lesser band-gap energy, specific surface area, average grain diameter, water dispersible and band-gap energy are bright
It is aobvious to be better than comparative example dichloride in anatase type TiO2The performance of photochemical catalyst.Preparation method and 1 preparation process ratio of comparative example of the invention
It compared with it is found that in drying stage, is calcined using Muffle furnace at 500 DEG C of high temperature, can be converted into anatase titanium dioxide, 1#Comparison is urged
Due to forming anatase crystal structure, reduce its specific surface area can increase agent with band gap.Present invention process is created
Property instead of Muffle furnace high-temperature calcination amorphous titanium dioxide has been made using 200~250 DEG C of dryings of low temperature.
(2) application test
For the catalytic effect for verifying amorphous nano titanium dioxide optical catalyst prepared by the present invention, with Examples 1 to 5 system
1 obtained#~5#Photochemical catalyst carries out photocatalysis test, and test selects common methyl orange dye to be used as light-catalyzed reaction
Target contaminant, for characterizing the photocatalysis performance of titanium dioxide prepared by embodiment and comparative example under visible light illumination.Institute
It is 10mg/L with methyl orange solution initial concentration, the additive amount of titanium dioxide test specimen is 0.4g/L, using the xenon lamp of 300W,
Irradiation condition of the filter plate of additional 400nm as visible light.Before photocatalytic degradation, the methyl orange solution of 100mL is taken, by two
Titanium oxide test specimen is added in dye solution, stirs 30min in the dark state to reach absorption-desorption balance, then carries out again
Photocatalytic degradation test after light-catalyzed reaction starts, takes out 2mL reaction solution every 30min, is centrifuged, isolates molten
Remaining catalyst in liquid.Then using the absorbance of ultraviolet-visible spectrophotometer measurement supernatant.It is inhaled by measuring solution
Concentration variation of the variation of luminosity for methyl orange dye in analytical solution, and then it is living to characterize the catalysis of catalyst under visible light
Property, test result is shown in Table 3.As a comparison, with same test conditions to 1#、2#Nanometer anatase titania photochemical catalyst carries out
Photocatalysis test, test result are included in table 3 together.
3 optically catalytic TiO 2 of table degradation methyl orange test result
Amorphous nano two prepared by the present invention is shown by the photo-catalytic degradation of methyl-orange dye solution test result of table 3
Titania photocatalyst passes through the visible light photocatalytic degradation of 240min, and degradation rate has reached 50% or more, the two of comparative example 1 and 2
Kind anatase titanium dioxide sample visible light catalytic effect is obviously poor.Amorphous nano titanium dioxide optical catalyst prepared by the present invention,
Photocatalytic Degradation effect is substantially better than comparative example dichloride in anatase type TiO2Photocatalytic degradation effect.
Compared with prior art, the light of the preparation method preparation of a kind of amorphous nano titanium dioxide optical catalyst of the present invention
Catalyst has the advantages that
1. preparing the intermediate metatitanic acid of titanium dioxide as raw material, by simple work using the sulfuric acid process by bleaching
Skill transformation, carries out the preparation of amorphous nano titanium dioxide, the operative employee of nano-titanium dioxide complexity is prepared instead of sulfuric acid process
Skill and calcining etc. have the technique of environmental pollution, and the amorphous nano titanium dioxide of preparation has preferable visible absorption
Effect compensates for the nano-titanium dioxide defect weak to visible absorption performance.
2. being neutralized using sodium hydroxide in preparing slurry containing a small amount of acid in metatitanic acid, adjusting pH is meta-alkalescence,
Sodium hexametaphosphate dispersant is added, uniform particle sizes and sub-nanometer metatitanic acid is obtained for next step wet grinding and prepares larger
The titanium dioxide of specific surface area provides the foundation condition.
3. filters pressing after grinding, sufficiently washs filter cake with deionized water, wash off the inorganic sodium contained in metatitanic acid, on the one hand
Reduce the presence due to inorganic sodium, metatitanic acid is made to reunite, on the other hand fully ensures that prepared amorphous titanium dioxide
With preferable water dispersion.
4. the filter cake after washing, is dried at a temperature of 200~250 DEG C, in the drying process, on the one hand eliminate partially
On the other hand the moisture of metatitanic acid adsorption loses its constitution water, forms amorphous titanium dioxide by metatitanic acid.Then
Using air-flow crushing, amorphous nano titanium dioxide is formed.
Claims (5)
1. a kind of preparation method of amorphous nano titanium dioxide optical catalyst, it is characterized in that: the following steps are included:
A. metatitanic acid is configured to the suspension that concentration is 600~800g/L with deionized water, is 10% with mass concentration
The pH value that NaOH aqueous solution adjusts suspension is 7~8, adds dispersing agent, then with the revolving speed stirring point of 500~600r/min
20~30min is dissipated, metatitanic acid slurry is made；
B. the metatitanic acid slurry of step A is subjected to 2~3h of wet grinding with sand mill；
C. filters pressing is carried out with plate and frame filter press to the metatitanic acid slurry after step B grinding, then be washed with deionized to filtrate electricity
Filter cake is made less than 10 μ s/cm in conductance；
D. the filter cake after step C filters pressing is put into box type drying equipment, is dried at a temperature of 200~250 DEG C, is made non-
Crystalline titania；
E. amorphous titanium dioxide prepared by step D is subjected in airslide disintegrating mill air-flow crushing, amorphous nano is made
Titanium dioxide optical catalyst.
2. a kind of preparation method of amorphous nano titanium dioxide optical catalyst according to claim 1, it is characterized in that: described
Metatitanic acid used is the intermediate product that sulfuric acid process by bleaching prepares titanium dioxide, the average grain of the metatitanic acid in step A
Diameter≤5.0 μm, metatitanic acid mass percentage >=98%.
3. a kind of preparation method of amorphous nano titanium dioxide optical catalyst according to claim 1, it is characterized in that: step
The additive amount of dispersing agent described in A is metatitanic acid with TiO2The 0.1~0.3% of quality is counted, the dispersing agent is calgon.
4. a kind of preparation method of amorphous nano titanium dioxide optical catalyst according to claim 1, it is characterized in that: described
Average grain diameter≤0.35 μm that metatitanic acid is made is sanded in step B.
5. a kind of preparation method of amorphous nano titanium dioxide optical catalyst according to claim 1, it is characterized in that: described
Drying time is 3~4h in step D.
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