CN109647367A - Large scale high photocatalysis activity titanium dioxide microballoon and preparation method thereof - Google Patents
Large scale high photocatalysis activity titanium dioxide microballoon and preparation method thereof Download PDFInfo
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- CN109647367A CN109647367A CN201910086149.9A CN201910086149A CN109647367A CN 109647367 A CN109647367 A CN 109647367A CN 201910086149 A CN201910086149 A CN 201910086149A CN 109647367 A CN109647367 A CN 109647367A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 48
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 33
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 26
- 230000000694 effects Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 25
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 21
- 239000002086 nanomaterial Substances 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 239000002070 nanowire Substances 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 238000004062 sedimentation Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 3
- 239000012071 phase Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000004887 air purification Methods 0.000 abstract description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 2
- 231100001261 hazardous Toxicity 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 231100000614 poison Toxicity 0.000 abstract description 2
- 230000007096 poisonous effect Effects 0.000 abstract description 2
- 239000004005 microsphere Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 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
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of large scale high photocatalysis activity titanium dioxide microballoons and preparation method thereof, belong to inorganic material photocatalysis technology field.The diameter of titanium dioxide microballoon sphere of the present invention is 0.1~10 millimeter, is made of the assembling of the titanium dioxide of one-dimensional nano structure and two-dimensional nanostructure；The unit of the one-dimensional nano structure is nano wire；The unit of the two-dimensional nanostructure is nanometer sheet；The titanium source of the titanium dioxide microballoon sphere is the titanium hydroxide powder of various crystal phase structures.Titanium dioxide microballoon sphere of the present invention is large scale, and macroscopic view is as it can be seen that have excellent photocatalytic activity；It is easy to sedimentation separation in liquid phase reactor, facilitates recycling and reuse；Preparation method is simple and convenient, is conducive to industrialized production；Have a wide range of application, the sufficiently catalytic poisonous and hazardous organic matter of degradation, can apply in the environmental areas such as wastewater treatment, indoor air purification, antibacterial and deodouring under ultraviolet light or natural light.
Description
Technical field
The present invention relates to a kind of large scale high photocatalysis activity titanium dioxide microballoons and preparation method thereof, belong to inorganic material
Photocatalysis technology field.
Background technique
With the fast development of industry and urban life level, the mankind are more than directly or indirectly its self-cleaning to environmental emission
The harmful substance or energy of ability, big weight organic compounds are discharged into the environment of our lives, not only lead to shortage of resources,
And polluted to environment, endanger the health and existence of the mankind.Therefore, environmental problem increasingly becomes various circles of society's concern
Focal issue, and develop the simple and effective method of one kind and have become the extremely urgent weight of various regions government department to curb environmental pollution
Appoint.
Photocatalysis technology has a wide range of applications in terms of organic pollutant degradation as a kind of Novel clean technology, is
The potential pollution-free technology for solving environmental problem at present, provides new approaches and new way for environmental improvement.Day in 1972 undergraduate course
Scholar Fujishima and Honda discovery titanium dioxide semiconductor electrode photochemical catalyzing under ultraviolet irradiation condition can produce
Hydrogen has pulled open the prelude of light-catalyzed reaction research since then.1976, John H.Carey etc. expanded photocatalysis technology application
This method is successfully applied to the degradation of organic pollutants by range.Photocatalysis technology is because it is with cheap, nontoxic, section
Energy, efficient advantage have become the hot spot that personages of various circles of society fall over each other research.
Titanium dioxide raw material is cheap, nontoxic corrosion-free, and performance is stablized, easy to operate, is therefore widely used in water
With the purification of air.Titanium dioxide mainly exists with powder and form of film at present.But powder cannot recycle, it may be to ring
Cause secondary pollution in border；And the photocatalysis efficiency of film is lower, and preparation cost is high, is not easy to be mass produced.
TiO2There are reports and publication for the synthesis of microballoon.Titanium dioxide microballoon sphere can by sol-gal process and
The group technology preparation of roasting heat treatment, Li X Z (Li X Z, Liu H, Cheng L F, et al.Photocatalytic
oxidation using a new catalyst--TiO2 microsphere--for water and wastewater
Treatment. [J] .Environmental Science&Technology, 2003,37 (17): 3989-94.) etc. report
A kind of TiO that colloidal sol-is sprayed-roasts2Microballoon synthetic method, the TiO of synthesis2There is microballoon porous structure and good light to urge
Change the performance of the degradation organic matters such as salicylic acid, but because of synthetic method complexity, higher cost and be not suitable for large-scale production and application.Two
Titania microsphere can also be by coating TiO on some organic carriers2Powder, which is realized, to be prepared, Chen Y H etc. (Chen Y H,
Liu Y Y,Lin R H,et al.Photocatalytic degradation of p-phenylenediamine with
TiO2-coated magnetic PMMA microspheres in an aqueous solution[J].Journal of
Hazardous Materials, 2009,163 (2): 973-981.) report it is a kind of by TiO2Powder coating is in methacrylate first
Ester surface forms TiO2The method of/mPMMA microballoon, the results showed that the microballoon has very strong visible light photocatalytic degradation p-phenylenediamine
Activity.But the material that this kind of coating method obtains is unstable, TiO2Powder is easy to fall off, and is unfavorable for reusing.
To the TiO with photocatalytic activity in domestic publication2There are also be related to for the preparation and application of microballoon.
CN201110305276.7 discloses a kind of flower-like titanium dioxide microsphere photocatalytic material and its preparation, and thus obtained microsphere diameter is 3
Microns；CN201710007236.1 discloses a kind of side for preparing Detitanium-ore-type micro-nano hierarchical structure titanium dioxide microballoon sphere
Method, thus obtained microsphere diameter are 3~6 microns.The method of these reports mainly uses titanium source hydro-thermal reaction in organic or aqueous solution
Method, but prepare TiO2Microsphere diameter is smaller (10 microns or less), and stability is poor, cannot be fast in water treatment applications
Speed sedimentation, is unfavorable for large-scale application into practical water process.
Summary of the invention
The object of the present invention is to provide a kind of large scale high photocatalysis activity titanium dioxide microballoons, and macroscopic view is as it can be seen that have
Efficient photocatalytic activity, and be easy to sedimentation separation, facilitate recycling and reuse；It is simple just that the present invention provides one kind simultaneously
Prompt preparation method.
Large scale high photocatalysis activity titanium dioxide microballoon of the present invention, the diameter of the titanium dioxide microballoon sphere are 0.1
It~10 millimeters, is made of the assembling of the titanium dioxide of one-dimensional nano structure and two-dimensional nanostructure；
The unit of the one-dimensional nano structure is nano wire；
The unit of the two-dimensional nanostructure is nanometer sheet；
The titanium source of the titanium dioxide microballoon sphere is the titanium hydroxide powder of various crystal phase structures.
The preparation method of the large scale high photocatalysis activity titanium dioxide microballoon, comprising the following steps:
(1) titanium hydroxide powder is added in aqueous slkali, stirs, obtains white dispersion liquid A；
(2) surfactant is added into dispersion liquid A and moves into the hydrothermal reaction kettle with agitating device, carries out hydro-thermal
Processing；
(3) precipitating for obtaining hydro-thermal process is filtered, and is then handled through acid, is washed and be dried to obtain white powder,
It is roasted again to get the large scale high photocatalysis activity titanium dioxide microballoon is arrived.
The partial size of the titanium hydroxide powder is 0.1-100 microns.
The aqueous slkali is one or both of sodium hydroxide, potassium hydroxide or ammonium hydroxide, the concentration of aqueous slkali is 0.2~
20 mol/Ls.
The mass volume ratio of the titanium hydroxide powder and aqueous slkali is 1~50 grams per liter.
The surfactant be neopelex, polyvinylpyrrolidone, cetyl trimethylammonium bromide,
One or both of polyvinyl alcohol or polyethylene glycol, concentration is 0.01~50 mM/l, with the volume metering of aqueous slkali.
The present invention joined surfactant in preparation method, for adjusting TiO2Surface phase interaction between nanometer sheet and nano wire
With facilitating nano-TiO2It is assembled into large-sized microspheroidal.
The temperature of the hydro-thermal process is 120~250 DEG C, and the reaction time is 1~48 hour.
The revolving speed for the agitating device that the hydrothermal reaction kettle has is 1~100 rev/min.Hydro-thermal in the prior art is anti-
It should be without stirring for the application is to increase the uniformity of mixing using the purpose that reaction kettle shears solution.
The acid used in step (3) acid treatment process is one or both of hydrochloric acid, sulfuric acid or nitric acid, concentration 0.1
~2 mol/Ls.
In step (3), drying temperature is 40~80 DEG C, and drying time is 4~24 hours；Maturing temperature is 250~550
DEG C, calcining time is 1~24 hour.
The large scale high photocatalysis activity titanium dioxide microballoon application field range is wide, can be under ultraviolet light or natural light
The sufficiently catalytic poisonous and hazardous organic matter of degradation.
The TiO of conventional method synthesis2Microballoon uses organic or inorganic titanium source, such as titanium tetrachloride, butyl titanate, preparation
TiO2Microspherulite diameter is at 10 microns hereinafter, these titanium source higher costs, environment are unfriendly.The present invention is directly with hydroxide titanium valve
End is titanium source, and titanium hydroxide and alkaline solution are stirred evenly, and surfactant is then added and carries out at hydro-thermal in a kettle
Reason synthesizes sodium titanate nano wire, is assembled into large-sized microballoon using the nanometer sheet that centre generates, the diameter dimension of microballoon all exists
Millimeter or more.The present invention passes through the control of reaction raw materials, response procedures and reaction condition, realizes the control to Microsphere Size.This
It is lower to invent the titanium source cost used, it is more environmentally friendly.
Compared with prior art, the invention has the following advantages:
(1) titanium dioxide microballoon sphere described in is large scale, and macroscopic view is as it can be seen that have excellent photocatalytic activity；
(2) titanium dioxide microballoon sphere described in is easy to sedimentation separation in liquid phase reactor, facilitates recycling and reuse；
(3) preparation method of the titanium dioxide microballoon sphere described in is simple and convenient, is not necessarily to expensive device, is conducive to industrialized production；
(4) titanium dioxide microballoon sphere described in has a wide range of application, and sufficiently catalytic degradation is toxic under ultraviolet light or natural light has
Harmful organic matter can apply in the environmental areas such as wastewater treatment, indoor air purification, antibacterial and deodouring.
Detailed description of the invention
Fig. 1 is the pattern picture of sample obtained by embodiment 1；
Fig. 2 is the degradation effect figure for the titanium dioxide microballoon sphere Pyrogentisinic Acid that under illumination prepared by embodiment 1.
Specific embodiment
In following embodiment, the Characterization of Its Photocatalytic Activity of the titanium dioxide microballoon sphere of each embodiment synthesis, using 0.1 mmoles
You/liter phenol be target contaminant, using 365nm ultraviolet light as light source (60W), be spaced 5~20 minutes and sample, instrument is
Shimadzu high performance liquid chromatography LC-2010AHT.
Embodiment 1
(1) titanium hydroxide powder is added in sodium hydroxide solution, wherein the ratio of titanium hydroxide quality and aqueous slkali volume
For 15 grams per liters, mixed liquor is stirred to react 2 hours synthesis dispersion liquid A at 25 DEG C；(2) above-mentioned dispersion liquid A is mixed into 0.01 mmoles
That/liter cetyl trimethylammonium bromide immigration is lined in the stainless steel cauldron of polytetrafluoroethylene (PTFE), is existed with 10 revs/min of revolving speeds
Hydro-thermal process 4 hours at 250 DEG C；(3) reaction kettle after hydro-thermal process is cooled to room temperature, and filtered precipitating is through 1 mol/L salt
Acid processing, washing are 12 hours dry at 60 DEG C；(4) sample after drying is roasted 24 hours at 250 DEG C, is can be obtained
Large scale self assembly titanium dioxide microballoon sphere.
Titanium dioxide microballoon sphere shape appearance figure made from the present embodiment is as shown in Figure 1, it is seen then that titanium dioxide microballoon sphere diameter is 0.5
~3 millimeters and compound with regular structure.
The degradation effect of titanium dioxide microballoon sphere Pyrogentisinic Acid made from the present embodiment is as shown in Figure 2.60 minutes phenol drops of illumination
Solution rate is up to 90%, TiO2Microballoon can be kept completely separate by natural subsidence 15 minutes.
Embodiment 2
(1) titanium hydroxide powder is added in potassium hydroxide solution, wherein titanium hydroxide powder quality and aqueous slkali volume
Ratio be 1 grams per liter, mixed liquor is stirred to react 2 hours synthesis dispersion liquid A at 25 DEG C；(2) above-mentioned dispersion liquid A is mixed into 5 mmoles
That/liter neopelex and 10 mM/ls of polyvinyl alcohol immigrations are lined in the stainless steel cauldron of polytetrafluoroethylene (PTFE),
With 1 rev/min of revolving speed at 120 DEG C hydro-thermal process 48 hours；(3) reaction kettle after hydro-thermal process is cooled to room temperature, after filtering
Precipitating through 0.1 mol/L HCl treatment, washing is 24 hours dry at 40 DEG C；(4) by the sample after drying at 350 DEG C
Roasting 6 hours, can be obtained large scale self assembly titanium dioxide microballoon sphere, and microsphere diameter is 0.1~1.5 millimeter.
Prepared TiO2Microballoon degradation of phenol the results show that 60 minutes phenol degrading rates 75% of illumination under ultraviolet light.
TiO2Microballoon can be kept completely separate by precipitating 30 minutes.
Embodiment 3
(1) titanium hydroxide powder is added in the mixed solution of sodium hydroxide and ammonium hydroxide, wherein titanium hydroxide powder quality
And the ratio of aqueous slkali volume is 50 grams per liters, and mixed liquor is stirred to react 4 hours synthesis dispersion liquid A at 35 DEG C；(2) by above-mentioned dispersion
Liquid A mixes 10 mM/ls of enuatrol immigrations and is lined in the stainless steel cauldron of polytetrafluoroethylene (PTFE), is existed with 100 revs/min of revolving speeds
Hydro-thermal process 1 hour at 180 DEG C；(3) reaction kettle after hydro-thermal process is cooled to room temperature, and filtered precipitating is through 2 mol/L nitre
Acid processing, washing are 4 hours dry at 80 DEG C；(4) sample after drying is roasted 1 hour at 550 DEG C, is can be obtained big
Size self assembly titanium dioxide microballoon sphere, microsphere diameter are 0.2~3 millimeter.
Prepared TiO2Microballoon degradation of phenol the results show that 60 minutes phenol degrading rates 82% of illumination under ultraviolet light.
TiO2Microballoon can be kept completely separate by precipitating 30 minutes.
Comparative example 1
(1) titanium hydroxide powder is added in sodium hydroxide solution, wherein the ratio of titanium hydroxide quality and aqueous slkali volume
For 15 grams per liters, mixed liquor is stirred to react 2 hours synthesis dispersion liquid A at 25 DEG C；(2) above-mentioned dispersion liquid A immigration is lined with polytetrafluoro
In the stainless steel cauldron of ethylene, with 10 revs/min of revolving speeds at 250 DEG C hydro-thermal process 4 hours；(3) anti-after hydro-thermal process
Kettle is answered to be cooled to room temperature, for filtered precipitating through 1 mol/L HCl treatment, washing is 12 hours dry at 60 DEG C；(4) it will do
Sample after dry roasts 24 hours at 250 DEG C, obtains TiO2Powder does not form large scale TiO2Microballoon.
Comparative example 2
(1) titanium hydroxide powder is added in sodium hydroxide solution, wherein the ratio of titanium hydroxide quality and aqueous slkali volume
For 15 grams per liters, mixed liquor is stirred to react 2 hours synthesis dispersion liquid A at 25 DEG C；(2) above-mentioned dispersion liquid A is mixed into 0.01 mmoles
That/liter cetyl trimethylammonium bromide immigration is lined in the stainless steel cauldron of polytetrafluoroethylene (PTFE), the case where not stirring
Under, hydro-thermal process 4 hours at 250 DEG C；(3) reaction kettle after hydro-thermal process is cooled to room temperature, and filtered precipitating is rubbed through 1
That/liter HCl treatment, washing are 12 hours dry at 60 DEG C；(4) sample after drying is roasted 24 hours at 250 DEG C, is obtained
To TiO2Powder does not form large scale TiO2Microballoon.
The above-mentioned description to embodiment is for ease of ordinary skill in the art to understand and use the invention.It is ripe
The personnel for knowing art technology obviously easily can make various modifications to these embodiments, and general original described herein
It ought to use in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, this field
Technical staff's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be in guarantors of the invention
Within the scope of shield.
Claims (10)
1. a kind of large scale high photocatalysis activity titanium dioxide microballoon, it is characterised in that: the diameter of the titanium dioxide microballoon sphere is
It 0.1~10 millimeter, is made of the assembling of the titanium dioxide of one-dimensional nano structure and two-dimensional nanostructure；
The unit of the one-dimensional nano structure is nano wire；
The unit of the two-dimensional nanostructure is nanometer sheet；
The titanium source of the titanium dioxide microballoon sphere is the titanium hydroxide powder of various crystal phase structures.
2. a kind of preparation method of large scale high photocatalysis activity titanium dioxide microballoon, it is characterised in that the following steps are included:
(1) titanium hydroxide powder is added in aqueous slkali, stirs, obtains white dispersion liquid A；
(2) surfactant is added into dispersion liquid A and moves into the hydrothermal reaction kettle with agitating device, carries out at hydro-thermal
Reason；
(3) precipitating for obtaining hydro-thermal process is filtered, then through acid processing, wash and be dried to obtain white powder, then into
Row roasts to arrive the large scale high photocatalysis activity titanium dioxide microballoon.
3. the preparation method of large scale high photocatalysis activity titanium dioxide microballoon according to claim 2, it is characterised in that:
The partial size of titanium hydroxide powder is 0.1-100 microns.
4. the preparation method of large scale high photocatalysis activity titanium dioxide microballoon according to claim 2, it is characterised in that:
Aqueous slkali is one or both of sodium hydroxide, potassium hydroxide or ammonium hydroxide, and the concentration of aqueous slkali is 0.2~20 mol/L.
5. the preparation method of large scale high photocatalysis activity titanium dioxide microballoon according to claim 2, it is characterised in that:
The mass volume ratio of titanium hydroxide powder and aqueous slkali is 1~50 grams per liter.
6. the preparation method of large scale high photocatalysis activity titanium dioxide microballoon according to claim 2, it is characterised in that:
Surfactant is neopelex, polyvinylpyrrolidone, cetyl trimethylammonium bromide, polyvinyl alcohol or poly-
One or both of ethylene glycol, concentration are 0.01~50 mM/l.
7. the preparation method of large scale high photocatalysis activity titanium dioxide microballoon according to claim 2, it is characterised in that:
The temperature of hydro-thermal process is 120~250 DEG C, and the reaction time is 1~48 hour.
8. the preparation method of large scale high photocatalysis activity titanium dioxide microballoon according to claim 2, it is characterised in that:
The revolving speed for the agitating device that hydrothermal reaction kettle has is 1~100 rev/min.
9. the preparation method of large scale high photocatalysis activity titanium dioxide microballoon according to claim 2, it is characterised in that:
The acid used is one or both of hydrochloric acid, sulfuric acid or nitric acid in step (3) acid treatment process, concentration is 0.1~2 mole/
It rises.
10. the preparation method of large scale high photocatalysis activity titanium dioxide microballoon according to claim 2, feature exist
In: the drying temperature in step (3) is 40~80 DEG C, and drying time is 4~24 hours；Maturing temperature is 250~550 DEG C, roasting
Burning the time is 1~24 hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111957305A (en) * | 2020-08-11 | 2020-11-20 | 上海锐朗光电材料有限公司 | Titanium dioxide microsphere photocatalyst and preparation method thereof |
| CN116212843A (en) * | 2023-02-14 | 2023-06-06 | 甘肃自然能源研究所 | Preparation method and application of self-template capable of realizing structural regulation and control of flower-like, hollow and solid titanium dioxide microspheres |
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2019
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111957305A (en) * | 2020-08-11 | 2020-11-20 | 上海锐朗光电材料有限公司 | Titanium dioxide microsphere photocatalyst and preparation method thereof |
| CN116212843A (en) * | 2023-02-14 | 2023-06-06 | 甘肃自然能源研究所 | Preparation method and application of self-template capable of realizing structural regulation and control of flower-like, hollow and solid titanium dioxide microspheres |
| CN116212843B (en) * | 2023-02-14 | 2024-01-19 | 甘肃自然能源研究所 | Preparation method and application of self-template capable of realizing structural regulation and control of flower-like, hollow and solid titanium dioxide microspheres |
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