CN104261465B - A kind of preparation method of titanate, metatitanic acid and titanium dioxide - Google Patents
A kind of preparation method of titanate, metatitanic acid and titanium dioxide Download PDFInfo
- Publication number
- CN104261465B CN104261465B CN201410581104.6A CN201410581104A CN104261465B CN 104261465 B CN104261465 B CN 104261465B CN 201410581104 A CN201410581104 A CN 201410581104A CN 104261465 B CN104261465 B CN 104261465B
- Authority
- CN
- China
- Prior art keywords
- titanium
- acid
- hemicentrotus seu
- seu strongylocentrotus
- titanate
- 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.)
- Active
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 101
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000002253 acid Substances 0.000 title claims abstract description 78
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 241000258149 Hemicentrotus Species 0.000 claims abstract description 110
- 241000258125 Strongylocentrotus Species 0.000 claims abstract description 110
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 58
- 239000010936 titanium Substances 0.000 claims abstract description 58
- 238000003916 acid precipitation Methods 0.000 claims abstract description 44
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000007062 hydrolysis Effects 0.000 claims abstract description 20
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 6
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 4
- XVBXJBGOQQLLAO-UHFFFAOYSA-J [Ti+4].C=C.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O Chemical compound [Ti+4].C=C.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O XVBXJBGOQQLLAO-UHFFFAOYSA-J 0.000 claims abstract description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims abstract description 3
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims abstract description 3
- FXWGWZQOSOJYOC-UHFFFAOYSA-N propane-1,2,3-triol;titanium Chemical compound [Ti].OCC(O)CO FXWGWZQOSOJYOC-UHFFFAOYSA-N 0.000 claims abstract description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 238000005119 centrifugation Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical group [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
- 239000002070 nanowire Substances 0.000 abstract description 10
- 239000002071 nanotube Substances 0.000 abstract description 4
- 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 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 18
- 229910001416 lithium ion Inorganic materials 0.000 description 18
- 230000001699 photocatalysis Effects 0.000 description 16
- 238000007146 photocatalysis Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000007599 discharging Methods 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000006250 one-dimensional material Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- 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
-
- B01J35/39—
-
- B01J35/50—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The preparation method of a kind of titanate of disclosure, metatitanic acid and titanium dioxide, wherein, the preparation method of titanate includes: by hydrolysis, titanium source is obtained hydrated titanium Acid precipitation, one or several the combination in titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium tetrafluoride, titanium ethanolate, titanium propanolate, butyl titanate, titanium ethylene glycolate, glycerol titanium, ammonium titanium fluoride of the described titanium source；It is dispersed in the aqueous hydrogen peroxide solution containing highly basic by described hydrated titanium Acid precipitation to carry out hydro-thermal reaction to obtain to have and receive the Hemicentrotus seu Strongylocentrotus shape titanate of differentiating stage structure.Some shortcomings that a kind of titanate provided herein, metatitanic acid have when can make up with the preparation method of titanium dioxide titanate, metatitanic acid and titanic oxide material are prepared into nano wire or nano tube structure.
Description
Technical field
The application relates to the preparation of environmental protection, energy field material, the preparation method particularly relating to a kind of titanate, metatitanic acid and titanium dioxide.
Background technology
Titanate, metatitanic acid and titanium dioxide have broad application prospects in fields such as lithium ion battery, photocatalysis, DSSC, photocatalytic water and sensors due to them, it has also become the focus of Material Field research.The properties of above-mentioned titanate, metatitanic acid and titanic oxide material is closely related with their pattern.
Compared to nanometer monocrystalline granule, one-dimensional material (such as nanotube, nano wire) can reduce intergranular crystal boundary, be conducive to carrier transporting on long axis direction, it is the desirable construction unit of assemble nanometer functional device, optoelectronic device structure, is expected to become nano-device functionalization and integrated critical material.Monodimension nanometer material has following Some features: (1), in photocatalysis field, is conducive to photo-generate electron-hole to free migration on long axis direction, reduces the recombination probability of electron hole, improve photocatalysis efficiency；(2), in field of lithium ion battery, major axis is conducive to the effective mobility of electronics, short axle to be conducive to quickly the embedding of lithium ion/embedding to go out process, and compared to nano-particle, one-dimentional structure has good charge-discharge performance；(3), in field of dye-sensitized solar cells, one-dimensional nano structure expection can greatly reduce intergranular crystal boundary, is conducive to electronics transmission on light anode, can be greatly improved the efficiency of battery.
But, after titanate, metatitanic acid and titanic oxide material are prepared into the one-dimensional nano structure such as nano wire or nanotube, suffer drawbacks that: as in photocatalysis field, after photocatalysis terminates, nano-photocatalyst is not easily recycled；In field of lithium ion battery, nano material often has relatively low tap density, contacts the shortcomings such as bad between granule with granule so that nano material electrode does not generally possess higher volume and capacity ratio and good fast charging and discharging performance.
Summary of the invention
Inventor finds through great many of experiments, titanate, metatitanic acid and titanic oxide material is made and receives differentiating stage structure, it is possible to while making full use of the nanostructured characteristic of material, is effectively maintained the micrometer structure function of material.Receiving in differentiating stage structural material, the hierarchy microsphere being made up of 1-dimention nano pipe, nano wire is by being a kind of ideal differentiating stage structure of receiving, such as Hemicentrotus seu Strongylocentrotus shape hierarchy microsphere.1-dimention nano pipe in photocatalysis field, this hierarchy, nano wire can promote its photocatalysis efficiency, and micron order ball can accelerate its sedimentation or membrane separating effect.In field of lithium ion battery, the composition 1-dimention nano pipe of hierarchy, nanometer wire nanostructured be conducive to electronics transmit on long axis direction, short axle be then conducive to lithium ion quickly embed and embedding go out；Meanwhile, this hierarchy generally micron order ball, spherical structure has good bulk density in traditional electrode preparation, and ball is more tight with contacting of variole intergranular, can improve the fast charging and discharging performance of battery to a great extent.
Therefore, the preparation method that the application provides a kind of titanate, metatitanic acid and titanium dioxide, some shortcomings having during to make up and titanate, metatitanic acid and titanic oxide material are prepared into nano wire or nano tube structure.
The preparation method that the application provides a kind of titanate, including:
Titanium source is obtained hydrated titanium Acid precipitation by hydrolysis, one or several the combination in titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium tetrafluoride, titanium ethanolate, titanium propanolate, butyl titanate, titanium ethylene glycolate, glycerol titanium, ammonium titanium fluoride of the described titanium source；
It is dispersed in the aqueous hydrogen peroxide solution containing highly basic by described hydrated titanium Acid precipitation to carry out hydro-thermal reaction to obtain to have and receive the Hemicentrotus seu Strongylocentrotus shape titanate of differentiating stage structure.
Preferably, in the described aqueous hydrogen peroxide solution containing highly basic, paper mill wastewater is 0.01 mole and often rises to 5 moles every liter, and in the described aqueous hydrogen peroxide solution containing highly basic, the volume fraction of hydrogen peroxide is 0.1% to 8%.
Preferably, the described aqueous hydrogen peroxide solution containing highly basic is add highly basic in aqueous hydrogen peroxide solution or add hydrogen peroxide acquisition in strong base solution；A kind of in sodium hydroxide and potassium hydroxide of described highly basic or their combination.
Preferably, described titanium source carries out purifying the described hydrated titanium Acid precipitation of acquisition after hydrolysis；Described purification is for removing the foreign ion in hydrated titanium Acid precipitation, and described purification mode adopts the combination of one or several modes in washing-centrifugation, washing-membrance separation, washing-filtration and dialysis.
Preferably, described hydrolysis is that described titanium source disperses direct hydrolysis in deionized water generate hydrated titanium Acid precipitation, or, described hydrolysis is the aqueous solution by adding alkaline matter to described titanium source, makes the hydrolysis of titanium source generate hydrated titanium Acid precipitation.
Preferably, the mass fraction that described hydrated titanium Acid precipitation is dispersed in the described aqueous hydrogen peroxide solution containing highly basic is 0.001% to 5%.
Preferably, the temperature of described hydro-thermal reaction is 60 degrees Celsius to 200 degrees Celsius, and the time of hydro-thermal reaction is 2 to 48 hours.
The preparation method that the application also provides for the metatitanic acid of a kind of preparation method based on the above titanate, the preparation method of this metatitanic acid also includes:
Obtain to have through acid exchange by the described Hemicentrotus seu Strongylocentrotus shape titanate receiving differentiating stage structure and receive the Hemicentrotus seu Strongylocentrotus shape metatitanic acid of differentiating stage structure.
Preferably, described acid exchange includes:
The described Hemicentrotus seu Strongylocentrotus shape titanate washing receiving differentiating stage structure is separated；
The Hemicentrotus seu Strongylocentrotus shape titanate of differentiating stage structure received after described washing being separated is put into and is carried out hydrion exchange in acid solution and obtain to have and receive the Hemicentrotus seu Strongylocentrotus shape metatitanic acid of differentiating stage structure, described acid solution is selected from one or several in nitric acid, hydrochloric acid, sulphuric acid, acetic acid, and the concentration of acid solution is 0.0001 mole and often rises to 0.1 mole every liter；
Having of described acquisition is received the Hemicentrotus seu Strongylocentrotus shape metatitanic acid of differentiating stage structure carries out washing and separate.
The preparation method that the application also provides for the titanium dioxide of a kind of preparation method based on metatitanic acid as above, the preparation method of this titanium dioxide also includes:
By annealed for the described Hemicentrotus seu Strongylocentrotus shape metatitanic acid receiving differentiating stage structure process to obtain to have receive the Hemicentrotus seu Strongylocentrotus shape titanium dioxide of differentiating stage structure, described annealing temperature is 300 degrees Celsius to 800 degrees Celsius, and annealing time is 1 hour to 5 hours.
What the present invention prepared have receives the Hemicentrotus seu Strongylocentrotus shape titanate of differentiating stage structure, metatitanic acid and titanium dioxide and is made up of 1-dimention nano pipe, nano wire, generally micron level spherical, illustrate good cycle performance of lithium ion battery, especially under fast charging and discharging speed, remain to keep higher capacity, be a desirable ion cathode material lithium structure.What the present invention prepared have receives the Hemicentrotus seu Strongylocentrotus shape titanium dioxide of differentiating stage structure and has higher battery capacity equally, and charging/discharging voltage comparatively smoothly, advantageous as lithium ion battery negative material.Additionally, having of preparing of the application is received the Hemicentrotus seu Strongylocentrotus shape titanium dioxide of differentiating stage structure and had good photocatalysis performance, due to its generally micron particles, photocatalysis can sharp separation recycling after terminating.
In sum, it is an advantage of the current invention that:
1, preparation method provided herein can be prepared respectively to have and receive the Hemicentrotus seu Strongylocentrotus shape titanate of differentiating stage structure, Hemicentrotus seu Strongylocentrotus shape metatitanic acid and Hemicentrotus seu Strongylocentrotus shape titanium dioxide；
2, the Hemicentrotus seu Strongylocentrotus shape structure that preparation method provided herein obtains is made up of 1-dimention nano pipe or nano wire, while can making full use of one-dimensional nano structure characteristic, is effectively maintained the micrometer structure function of material, is that other method cannot realize；
3, preparation method provided herein low in raw material price, be easy to get, production cost is relatively low；In building-up process additive-free, safety and environmental protection is pollution-free；
4, preparation method preparation technology provided herein is simple, and technological parameter is easy to control, it is easy to large-scale industrial production.
Prepared by the present invention have receives the Hemicentrotus seu Strongylocentrotus shape metatitanic acid of differentiating stage structure and is in that for the advantage of lithium ion battery negative material:
1, capacity height and cycle efficieny are good, and repeatedly charge/discharge capacity declines hardly；
2, big capacity is still kept under fast charging and discharging speed.
Prepared by the present invention have receives the Hemicentrotus seu Strongylocentrotus shape titanium dioxide of differentiating stage structure and is in that for the advantage of lithium ion battery negative material:
1, comparatively steady and relatively low charging/discharging voltage, charge and discharge platform respectively 1.86 volts and 1.78 volts, high-voltage lithium ion batteries is prepared advantageous as negative material；
2, capacity height and cycle efficieny are good, and repeatedly charge/discharge capacity declines hardly.
Prepared by the present invention have receives the Hemicentrotus seu Strongylocentrotus shape titanium dioxide of differentiating stage structure and is in that for light-catalysed advantage:
1, photocatalysis efficiency is high；
2, easily separated recovery, can settle after photocatalysis voluntarily.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, the accompanying drawing used required in embodiment or description of the prior art will be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those skilled in the art, under the premise not paying creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the preparation method flow chart of a kind of titanate of the present invention, metatitanic acid and titanium dioxide；
Fig. 2 is the X-ray diffractogram of the Hemicentrotus seu Strongylocentrotus shape sodium titanate (figure a) for preparing of embodiment 1 and Hemicentrotus seu Strongylocentrotus shape metatitanic acid (scheming b)；
Fig. 3 is the scanning electron microscope (SEM) photograph of Hemicentrotus seu Strongylocentrotus shape sodium titanate (figure a), Hemicentrotus seu Strongylocentrotus shape metatitanic acid (figure b) and Hemicentrotus seu Strongylocentrotus shape titanium dioxide (figure c) that embodiment 1 prepares；They are all made up of 1-dimention nano pipe or nano wire, generally micron level spherical；
Fig. 4 be the Hemicentrotus seu Strongylocentrotus shape metatitanic acid for preparing of embodiment 1 for lithium ion battery: figure a is 50mAg-1Time capacity circulating figure, figure b be the capacity circulating figure under different charge-discharge velocity；
Fig. 5 be the Hemicentrotus seu Strongylocentrotus shape titanium dioxide for preparing of embodiment 1 for lithium ion battery: figure a is 50mAg-1Time first charge-discharge Capacity Plan, figure b be 50mAg-1Time capacity circulating figure；
Fig. 6 is the Hemicentrotus seu Strongylocentrotus shape metatitanic acid X-ray diffractogram of the Hemicentrotus seu Strongylocentrotus shape titanium dioxide that annealing obtained after 2 hours under 400 degrees Celsius (figure a) and 600 degrees Celsius (figure b) respectively that embodiment 1 prepares, wherein 400 degrees Celsius process afterproduct is Anatase, and 600 degrees Celsius process the compound phase that afterproduct is Anatase and Rutile Type；
Fig. 7 is that the Hemicentrotus seu Strongylocentrotus shape titanium dioxide for preparing of embodiment 1 is for the auto-deposition performance schematic diagram in photocatalysis half an hour after；
The scanning electron microscope (SEM) photograph of the Hemicentrotus seu Strongylocentrotus shape sodium titanate that Fig. 8 prepares when being and naoh concentration is changed in embodiment 12 moles every liter (figure a) and 4 moles every liter (figure b) respectively；Hemicentrotus seu Strongylocentrotus shape sodium titanate can obtain, after acid exchanges, the Hemicentrotus seu Strongylocentrotus shape metatitanic acid that pattern remains unchanged, and can obtain the Hemicentrotus seu Strongylocentrotus shape titanium dioxide that pattern remains unchanged after the annealed process of Hemicentrotus seu Strongylocentrotus shape metatitanic acid.
Detailed description of the invention
In order to make those skilled in the art be more fully understood that the technical scheme in the application, below in conjunction with the accompanying drawing in the embodiment of the present application, technical scheme in the embodiment of the present application is clearly and completely described, obviously, described embodiment is only some embodiments of the present application, rather than whole embodiments.Based on the embodiment in the application, the every other embodiment that those of ordinary skill in the art obtain under the premise not making creative work, all should belong to the scope of protection of the invention.
Embodiment 1
Refer to Fig. 1, under stirring condition, 0.5 gram of titanium sulfate is scattered in 50 ml deionized water, ordinary-temp hydrolysis generates hydrated titanium Acid precipitation, by above-mentioned hydrated titanium Acid precipitation centrifugation, after respectively with 50 ml deionized water wash 3 times, be centrifugally separating to obtain the hydrated titanium Acid precipitation after washing.Hydrated titanium Acid precipitation after above-mentioned washing is dispersed in the aqueous solution that 40 milliliters of naoh concentrations are 1 mole every liter and hydrogen peroxide concentration is 2%.After stirring 1 hour, mixed liquor is transferred in water heating kettle, heating to 150 degrees Celsius, constant temperature 12 hours, prepare to have and receive the Hemicentrotus seu Strongylocentrotus shape sodium titanate of differentiating stage structure.Transferring in beaker by described Hemicentrotus seu Strongylocentrotus shape sodium titanate solid, ultrasonic disperse, with deionized water wash 5 times, centrifugation.It is subsequently added the salpeter solution of 0.01 mole every liter to solution souring, ultrasonic and stand 6 hours so that H+Ion is completely by Na+Ion exchanges, and with deionized water wash, centrifugation, 60 degrees Celsius of lower vacuum dryings, obtains having and receives the Hemicentrotus seu Strongylocentrotus shape metatitanic acid of differentiating stage structure.Take and receive the Hemicentrotus seu Strongylocentrotus shape metatitanic acid of differentiating stage structure described in part and put in Noah's ark, make annealing treatment 2 hours under 400 degrees Celsius, obtain having and receive the Hemicentrotus seu Strongylocentrotus shape anatase phase titanium dioxide of differentiating stage structure.
Hemicentrotus seu Strongylocentrotus shape sodium titanate that the present embodiment prepares and the X-ray diffractogram of Hemicentrotus seu Strongylocentrotus shape metatitanic acid are as shown in Figure 2.In Fig. 2, figure a is the X-ray diffractogram of the Hemicentrotus seu Strongylocentrotus shape sodium titanate that the present embodiment prepares, and figure b is the X-ray diffractogram of the Hemicentrotus seu Strongylocentrotus shape metatitanic acid that the present embodiment prepares.
The scanning electron microscope (SEM) photograph of Hemicentrotus seu Strongylocentrotus shape sodium titanate, Hemicentrotus seu Strongylocentrotus shape metatitanic acid and Hemicentrotus seu Strongylocentrotus shape titanium dioxide that the present embodiment prepares is as shown in Figure 3.In Fig. 3, figure a is the scanning electron microscope (SEM) photograph of the Hemicentrotus seu Strongylocentrotus shape sodium titanate that the present embodiment prepares, and figure b is the scanning electron microscope (SEM) photograph of the Hemicentrotus seu Strongylocentrotus shape metatitanic acid that the present embodiment prepares, and figure c is the scanning electron microscope (SEM) photograph of the Hemicentrotus seu Strongylocentrotus shape titanium dioxide that the present embodiment prepares.From figure 3, it can be seen that they are all made up of 1-dimention nano pipe or nano wire, generally micron level spherical, i.e. Hemicentrotus seu Strongylocentrotus shape.
The Hemicentrotus seu Strongylocentrotus shape metatitanic acid that the present embodiment prepares for lithium ion battery capacity circulating figure as shown in Figure 4.In Fig. 4, figure a is 50mAg-1Time capacity circulating figure, figure b be the capacity circulating figure under different charge-discharge velocity.As seen from Figure 4, the Hemicentrotus seu Strongylocentrotus shape metatitanic acid prepared by the present embodiment is in that for the advantage of lithium ion battery negative material: 1, capacity height and cycle efficieny are good, and repeatedly charge/discharge capacity declines hardly；2, big capacity is still kept under fast charging and discharging speed.
The Hemicentrotus seu Strongylocentrotus shape titanium dioxide that the present embodiment prepares for lithium ion battery capacity circulating figure as shown in Figure 5.In Fig. 5, figure a is 50mAg-1Time first charge-discharge Capacity Plan, figure b be 50mAg-1Time capacity circulating figure.As seen from Figure 5, Hemicentrotus seu Strongylocentrotus shape titanium dioxide prepared by the present embodiment is in that for the advantage of lithium ion battery negative material: 1, comparatively steady and relatively low charging/discharging voltage, charge and discharge platform respectively 1.86 volts and 1.78 volts, prepares high-voltage lithium ion batteries advantageous as negative material；2, capacity height and cycle efficieny are good, and repeatedly charge/discharge capacity declines hardly；3, big capacity is still kept under fast charging and discharging speed.
The X-ray diffractogram of the Hemicentrotus seu Strongylocentrotus shape titanium dioxide that the Hemicentrotus seu Strongylocentrotus shape metatitanic acid that the present embodiment prepares obtains after making annealing treatment 2 hours under 400 degrees Celsius and 600 degrees Celsius respectively is as shown in Figure 6.In Fig. 6, figure a is the X-ray diffractogram of the Hemicentrotus seu Strongylocentrotus shape titanium dioxide obtained after Hemicentrotus seu Strongylocentrotus shape metatitanic acid makes annealing treatment 2 hours under 400 degrees Celsius, and processing afterproduct at this temperature is Anatase；Figure b is the X-ray diffractogram of the Hemicentrotus seu Strongylocentrotus shape titanium dioxide obtained after Hemicentrotus seu Strongylocentrotus shape metatitanic acid makes annealing treatment 2 hours under 600 degrees Celsius, processes the compound phase that afterproduct is Anatase and Rutile Type at this temperature.
The Hemicentrotus seu Strongylocentrotus shape titanium dioxide that the present embodiment prepares is for the auto-deposition performance in photocatalysis half an hour after as shown in Figure 7.When the Hemicentrotus seu Strongylocentrotus shape titanium dioxide that the present embodiment prepares as seen from Figure 7 is for photocatalysis, there is easily separated recovery, the advantage that can settle voluntarily after photocatalysis.
The scanning electron microscope (SEM) photograph of the Hemicentrotus seu Strongylocentrotus shape sodium titanate prepared when naoh concentration is changed in the present embodiment 2 moles every liter and 4 moles every liter respectively is as shown in Figure 8.In Fig. 8, the scanning electron microscope (SEM) photograph of the Hemicentrotus seu Strongylocentrotus shape sodium titanate that figure a prepares when being and naoh concentration is changed into 2 moles every liter respectively；The scanning electron microscope (SEM) photograph of the Hemicentrotus seu Strongylocentrotus shape sodium titanate that figure b prepares when being and naoh concentration is changed into 4 moles every liter respectively.In the present embodiment, Hemicentrotus seu Strongylocentrotus shape sodium titanate can obtain, after acid exchanges, the Hemicentrotus seu Strongylocentrotus shape metatitanic acid that pattern remains unchanged, and can obtain the Hemicentrotus seu Strongylocentrotus shape titanium dioxide that pattern remains unchanged after the annealed process of Hemicentrotus seu Strongylocentrotus shape metatitanic acid.
Embodiment 2
Refer to Fig. 1, under stirring condition, 0.5 gram of titanium sulfate is scattered in 50 ml deionized water, ordinary-temp hydrolysis generates hydrated titanium Acid precipitation, by above-mentioned hydrated titanium Acid precipitation centrifugation, after respectively with 50 ml deionized water wash 3 times, be centrifugally separating to obtain the hydrated titanium Acid precipitation after washing.Hydrated titanium Acid precipitation after above-mentioned washing is dispersed in the aqueous solution that 40 milliliters of naoh concentrations are 1 mole every liter and hydrogen peroxide concentration is 2%.After stirring 1 hour, mixed liquor is transferred in water heating kettle, heating to 150 degrees Celsius, constant temperature 12 hours, prepare to have and receive the Hemicentrotus seu Strongylocentrotus shape sodium titanate of differentiating stage structure.Transferring in beaker by Hemicentrotus seu Strongylocentrotus shape sodium titanate solid, ultrasonic disperse, with deionized water wash 3 times, centrifugation.It is subsequently added the salpeter solution of 0.01 mole every liter to solution souring, ultrasonic and stand 6 hours so that H+Ion is completely by Na+Ion exchanges, and with deionized water wash, centrifugation, 60 degrees Celsius of vacuum dryings, obtains having and receives the Hemicentrotus seu Strongylocentrotus shape metatitanic acid of differentiating stage structure.Take the described Hemicentrotus seu Strongylocentrotus shape metatitanic acid of part and put in Noah's ark, make annealing treatment 2 hours under 600 degrees Celsius, obtain having and receive the titanium dioxide of the Hemicentrotus seu Strongylocentrotus shape Anatase of differentiating stage structure and Rutile Type compound crystalline phase.
Embodiment 3
Refer to Fig. 1, under stirring condition, 1 gram of titanium sulfate is scattered in 50 ml deionized water, ordinary-temp hydrolysis generates hydrated titanium Acid precipitation, by above-mentioned hydrated titanium Acid precipitation centrifugation, after respectively with 50 ml deionized water wash 5 times, be centrifugally separating to obtain the hydrated titanium Acid precipitation after washing.Hydrated titanium Acid precipitation after above-mentioned washing is dispersed in the aqueous solution that 40 milliliters of concentration of potassium hydroxide are 2 moles every liter and hydrogen peroxide concentration is 6%.After stirring 1 hour, mixed liquor is transferred in water heating kettle, heating to 150 degrees Celsius, constant temperature 12 hours, prepare to have and receive the Hemicentrotus seu Strongylocentrotus shape potassium titanate of differentiating stage structure.Transferring in beaker by described Hemicentrotus seu Strongylocentrotus shape potassium titanate solid, ultrasonic disperse, with deionized water wash 5 times, centrifugation.It is subsequently added 0.1 mole of every liter of salpeter solution to solution souring, ultrasonic and stand 6 hours so that H+Ion is completely by K+Ion exchanges, and with deionized water wash, centrifugation, 60 degrees Celsius of vacuum dryings, obtains having and receives the Hemicentrotus seu Strongylocentrotus shape metatitanic acid of differentiating stage structure.Take the described Hemicentrotus seu Strongylocentrotus shape metatitanic acid of part and put in Noah's ark, make annealing treatment 3 hours under 400 degrees Celsius, obtain Hemicentrotus seu Strongylocentrotus shape anatase phase titanium dioxide.
Embodiment 4
Refer to Fig. 1, under stirring condition, 1 gram of titanyl sulfate is scattered in 30 ml deionized water, ordinary-temp hydrolysis generates hydrated titanium Acid precipitation, by above-mentioned hydrated titanium Acid precipitation centrifugation, after respectively with 30 ml deionized water wash 5 times, be centrifugally separating to obtain the hydrated titanium Acid precipitation after washing.Hydrated titanium Acid precipitation after above-mentioned washing is dispersed in the aqueous solution that 40 milliliters of naoh concentrations are 2 moles every liter and hydrogen peroxide concentration is 2%.After stirring 1 hour, mixed liquor is transferred in water heating kettle, heating to 120 degrees Celsius, constant temperature 24 hours, prepare to have and receive the Hemicentrotus seu Strongylocentrotus shape sodium titanate of differentiating stage structure.Transferring in beaker by described Hemicentrotus seu Strongylocentrotus shape sodium titanate solid, ultrasonic disperse, with deionized water wash 4 times, centrifugation.It is subsequently added 0.01 mole of every liter of salpeter solution to solution souring, ultrasonic and stand 6 hours so that H+Ion is completely by Na+Ion exchanges, and with deionized water wash, centrifugation, 60 degrees Celsius of vacuum dryings, obtains having and receives the Hemicentrotus seu Strongylocentrotus shape metatitanic acid of differentiating stage structure.Take the described Hemicentrotus seu Strongylocentrotus shape metatitanic acid of part and put in Noah's ark, make annealing treatment 2 hours under 500 degrees Celsius, obtain having and receive the Hemicentrotus seu Strongylocentrotus shape anatase phase titanium dioxide of differentiating stage structure.
Embodiment 5
Refer to Fig. 1, under stirring condition, 1 milliliter of isopropyl titanate is scattered in 50 ml deionized water, ordinary-temp hydrolysis generates hydrated titanium Acid precipitation, by above-mentioned hydrated titanium Acid precipitation centrifugation, after respectively with 50 ml deionized water wash 3 times, be centrifugally separating to obtain the hydrated titanium Acid precipitation after washing.Hydrated titanium Acid precipitation after above-mentioned washing is dispersed in the aqueous solution that 40 milliliters of naoh concentrations are 0.5 mole every liter and hydrogen peroxide concentration is 5%.After stirring 1 hour, mixed liquor is transferred in water heating kettle, heating to 160 degrees Celsius, constant temperature 12 hours, prepare to have and receive the Hemicentrotus seu Strongylocentrotus shape sodium titanate of differentiating stage structure.Transferring in beaker by described Hemicentrotus seu Strongylocentrotus shape sodium titanate solid, ultrasonic disperse, with deionized water wash 5 times, centrifugation.It is subsequently added 0.01 mole of every liter of salpeter solution to solution souring, ultrasonic and stand 6 hours so that H+Ion is completely by Na+Ion exchanges, and with deionized water wash, centrifugation, 60 degrees Celsius of vacuum dryings, obtains having and receives the Hemicentrotus seu Strongylocentrotus shape metatitanic acid of differentiating stage structure.Take part Hemicentrotus seu Strongylocentrotus shape metatitanic acid and put in Noah's ark, make annealing treatment 2 hours under 400 degrees Celsius, obtain having and receive the Hemicentrotus seu Strongylocentrotus shape anatase phase titanium dioxide of differentiating stage structure.
Embodiment 6
Refer to Fig. 1, under stirring condition, 2 milliliters of titanium tetrachlorides are scattered in 50 ml deionized water, ordinary-temp hydrolysis generates hydrated titanium Acid precipitation, by above-mentioned hydrated titanium Acid precipitation centrifugation, after respectively with 50 ml deionized water wash 5 times, be centrifugally separating to obtain the hydrated titanium Acid precipitation after washing.Hydrated titanium Acid precipitation after above-mentioned washing is dispersed in the aqueous solution that 40 milliliters of naoh concentrations are 2 moles every liter and hydrogen peroxide concentration is 5%.After stirring 1 hour, mixed liquor is transferred in water heating kettle, heating to 120 degrees Celsius, constant temperature 24 hours, prepare to have and receive the Hemicentrotus seu Strongylocentrotus shape sodium titanate of differentiating stage structure.Transferring in beaker by described Hemicentrotus seu Strongylocentrotus shape sodium titanate solid, ultrasonic disperse, with deionized water wash 3 times, centrifugation.It is subsequently added the salpeter solution of 0.1 mole every liter to solution souring, ultrasonic and stand 6 hours so that H+Ion is completely by Na+Ion exchanges, and with deionized water wash, centrifugation, 60 degrees Celsius of vacuum dryings, obtains having and receives the Hemicentrotus seu Strongylocentrotus shape metatitanic acid of differentiating stage structure.Take the described Hemicentrotus seu Strongylocentrotus shape metatitanic acid of part and put in Noah's ark, make annealing treatment 2 hours under 400 degrees Celsius, obtain having and receive the Hemicentrotus seu Strongylocentrotus shape anatase phase titanium dioxide of differentiating stage structure.
Embodiment 7
Refer to Fig. 1, under stirring condition, 2 milliliters of butyl titanates are scattered in 50 ml deionized water, ordinary-temp hydrolysis generates hydrated titanium Acid precipitation, by above-mentioned hydrated titanium Acid precipitation centrifugation, after respectively with 50 ml deionized water wash 5 times, be centrifugally separating to obtain the hydrated titanium Acid precipitation after washing.Hydrated titanium Acid precipitation after above-mentioned washing is dispersed in the aqueous solution that 40 milliliters of naoh concentrations are 1 mole every liter and hydrogen peroxide concentration is 2%.After stirring 1 hour, mixed liquor is transferred in water heating kettle, heating to 180 degrees Celsius, constant temperature 12 hours, prepare to have and receive the Hemicentrotus seu Strongylocentrotus shape sodium titanate of differentiating stage structure.Transferring in beaker by described Hemicentrotus seu Strongylocentrotus shape sodium titanate solid, ultrasonic disperse, with deionized water wash 3 times, centrifugation.It is subsequently added 0.01 mole of every liter of salpeter solution to solution souring, ultrasonic and stand 6 hours so that H+Ion is completely by Na+Ion exchanges, and with deionized water wash, centrifugation, 60 degrees Celsius of vacuum dryings, obtains having and receives the Hemicentrotus seu Strongylocentrotus shape metatitanic acid of differentiating stage structure.Take the described Hemicentrotus seu Strongylocentrotus shape metatitanic acid of part and put in Noah's ark, make annealing treatment 2 hours under 400 degrees Celsius, obtain having and receive the Hemicentrotus seu Strongylocentrotus shape anatase phase titanium dioxide of differentiating stage structure.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.Skilled person will appreciate that of the industry; the present invention is not restricted to the described embodiments; described in above-described embodiment and description is that principles of the invention is described; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements both fall within the scope of protection of present invention.Claimed scope is defined by appending claims and equivalent thereof.
Claims (8)
1. the preparation method of a metatitanic acid, it is characterised in that including:
Titanium source is obtained hydrated titanium Acid precipitation by hydrolysis, one or several the combination in titanium ethanolate, titanium propanolate, butyl titanate, titanium ethylene glycolate, glycerol titanium, titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium tetrafluoride, ammonium titanium fluoride of the described titanium source；
It is dispersed in the aqueous hydrogen peroxide solution containing highly basic by described hydrated titanium Acid precipitation to carry out hydro-thermal reaction to obtain to have and receive the Hemicentrotus seu Strongylocentrotus shape titanate of differentiating stage structure；In the described aqueous hydrogen peroxide solution containing highly basic, paper mill wastewater is 0.01 mole and often rises to 5 moles every liter, and in the described aqueous hydrogen peroxide solution containing highly basic, the volume fraction of hydrogen peroxide is 0.1% to 8%；
Obtain to have through acid exchange by described Hemicentrotus seu Strongylocentrotus shape titanate and receive the Hemicentrotus seu Strongylocentrotus shape metatitanic acid of differentiating stage structure.
2. the preparation method of metatitanic acid as claimed in claim 1, it is characterised in that: the described aqueous hydrogen peroxide solution containing highly basic is add highly basic in aqueous hydrogen peroxide solution or add hydrogen peroxide acquisition in strong base solution；A kind of in sodium hydroxide and potassium hydroxide of described highly basic or their combination.
3. the preparation method of metatitanic acid as claimed in claim 1, it is characterised in that: described titanium source carries out purifying the described hydrated titanium Acid precipitation of acquisition after hydrolysis；Described purification is for removing the foreign ion in hydrated titanium Acid precipitation, and described purification mode adopts the combination of one or several modes in washing-centrifugation, washing-membrance separation, washing-filtration and dialysis.
4. the preparation method of metatitanic acid as claimed in claim 1, it is characterized in that: described hydrolysis generates hydrated titanium Acid precipitation for described titanium source disperses direct hydrolysis in deionized water, or, described hydrolysis is the aqueous solution by adding alkaline matter to described titanium source, makes the hydrolysis of titanium source generate hydrated titanium Acid precipitation.
5. the preparation method of metatitanic acid as claimed in claim 1, it is characterised in that: the mass fraction that described hydrated titanium Acid precipitation is dispersed in the described aqueous hydrogen peroxide solution containing highly basic is 0.001% to 5%.
6. the preparation method of metatitanic acid as claimed in claim 1, it is characterised in that: the temperature of described hydro-thermal reaction is 60 degrees Celsius to 200 degrees Celsius, and the time is 2 hours to 48 hours.
7. the preparation method of metatitanic acid as claimed in claim 1, it is characterised in that described acid exchange includes:
The washing of described Hemicentrotus seu Strongylocentrotus shape titanate is separated；
Hemicentrotus seu Strongylocentrotus shape titanate after described washing being separated is put into and is carried out hydrion exchange in acid solution and obtain to have and receive the Hemicentrotus seu Strongylocentrotus shape metatitanic acid of differentiating stage structure, described acid solution is selected from one or several in nitric acid, hydrochloric acid, sulphuric acid, acetic acid, and the concentration of acid solution is 0.0001 mole and often rises to 0.1 mole every liter；
Having of described acquisition is received the Hemicentrotus seu Strongylocentrotus shape metatitanic acid of differentiating stage structure carries out washing and separate.
8. the preparation method based on the titanium dioxide of the preparation method of the metatitanic acid as described in claim 1 to 7 any one, it is characterised in that also include:
By annealed for described Hemicentrotus seu Strongylocentrotus shape metatitanic acid process to obtain to have receive the Hemicentrotus seu Strongylocentrotus shape titanium dioxide of differentiating stage structure, described annealing temperature is 300 degrees Celsius to 800 degrees Celsius, and the time is 1 hour to 5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410581104.6A CN104261465B (en) | 2014-10-27 | 2014-10-27 | A kind of preparation method of titanate, metatitanic acid and titanium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410581104.6A CN104261465B (en) | 2014-10-27 | 2014-10-27 | A kind of preparation method of titanate, metatitanic acid and titanium dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104261465A CN104261465A (en) | 2015-01-07 |
| CN104261465B true CN104261465B (en) | 2016-07-06 |
Family
ID=52153093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410581104.6A Active CN104261465B (en) | 2014-10-27 | 2014-10-27 | A kind of preparation method of titanate, metatitanic acid and titanium dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104261465B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3617147A1 (en) * | 2018-08-30 | 2020-03-04 | Petrochina Company Limited | Process for preparing titanic acid salt, titanic acid, and titanium oxide having controllable particle size and hierarchical structure |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107661754B (en) * | 2016-07-27 | 2020-09-18 | 中国科学院理化技术研究所 | Preparation method of silicon dioxide/titanic acid nano-chain compound and composite film |
| CN108097246A (en) * | 2017-12-15 | 2018-06-01 | 长沙理工大学 | A kind of three-dimensional sea urchin type Ag/RGO/TiO2Composite material and its preparation method and application |
| CN110015686A (en) * | 2018-01-08 | 2019-07-16 | 神华集团有限责任公司 | Titanium slag recycles the method for titanium dioxide and the method from denitrating catalyst recycling tungsten, titanium and vanadium |
| CN109279649B (en) | 2018-08-30 | 2021-01-29 | 中国石油天然气股份有限公司 | Preparation method of lithium titanate with nanotube hierarchical structure, application of lithium titanate and product |
| CN109326791B (en) * | 2018-09-03 | 2021-08-03 | 中国石油天然气股份有限公司 | Linear porous lithium titanate material and preparation and product thereof |
| CN108975390B (en) * | 2018-09-06 | 2021-01-29 | 中国石油天然气股份有限公司 | Linear hierarchical structure lithium titanate and preparation method and application thereof |
| CN109364949A (en) * | 2018-09-25 | 2019-02-22 | 武汉大学苏州研究院 | Ultraviolet-visible-near infrared light response PbS/TiO2Nanotube reunion microballoon hetero-junctions, preparation method and use |
| CN109926016A (en) * | 2019-04-04 | 2019-06-25 | 广州大学 | A kind of adsorbent material, preparation method and its application |
| CN114291843B (en) * | 2022-01-07 | 2023-09-29 | 中国科学院东北地理与农业生态研究所 | Multistage sodium titanate microtube and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327949A (en) * | 2008-05-26 | 2008-12-24 | 武汉理工大学 | Preparation of one-dimensional titanate radical nanopipe material and use thereof |
| CN101643240A (en) * | 2008-11-25 | 2010-02-10 | 中国科学院合肥物质科学研究院 | Method for preparing nanometer titanate with controllable appearances by utilizing industrial raw materials |
| CN104056611A (en) * | 2014-07-16 | 2014-09-24 | 李建明 | Method for preparing nano TiO2 |
| CN104098132A (en) * | 2014-07-30 | 2014-10-15 | 李建明 | Preparation method for {100} crystal plane anatase TiO2 nano-particles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8440162B1 (en) * | 2006-12-18 | 2013-05-14 | The Research Foundation Of State University Of New York | Titanate and titania nanostructures and nanostructure assemblies, and methods of making same |
-
2014
- 2014-10-27 CN CN201410581104.6A patent/CN104261465B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327949A (en) * | 2008-05-26 | 2008-12-24 | 武汉理工大学 | Preparation of one-dimensional titanate radical nanopipe material and use thereof |
| CN101643240A (en) * | 2008-11-25 | 2010-02-10 | 中国科学院合肥物质科学研究院 | Method for preparing nanometer titanate with controllable appearances by utilizing industrial raw materials |
| CN104056611A (en) * | 2014-07-16 | 2014-09-24 | 李建明 | Method for preparing nano TiO2 |
| CN104098132A (en) * | 2014-07-30 | 2014-10-15 | 李建明 | Preparation method for {100} crystal plane anatase TiO2 nano-particles |
Non-Patent Citations (4)
| Title |
|---|
| "A Facile Method for Synthesizing TiO2 Sea-Urchin-Like Structures and Their Applications in Solar Energy Harvesting";WANG Wen-Hui et al.;《CHIN. PHYS. LETT.》;20111231;第28卷(第7期);第078103-1到078103-4页 * |
| "Alkaline hydrothermal synthesis of homogeneous titania microspheres with urchin-like nanoarchitectures for dye effluent treatments";Jin-Ming Wu et al;《Journal of Hazardous Materials》;20110810;第194卷;第338-344页 * |
| "Synthesis and Growth Mechanism of Titanate and Titania One-Dimensional Nanostructures Self-Assembled into Hollow Micrometer-Scale Spherical Aggregates";Yuanbing Mao et al.;《J. Phys. Chem. B》;20051218;第10卷(第2期);第703页第4段实验部分、706页第4段TEM/HRTEM观测以及图1、图5和图6 * |
| "Three-dimensional sea-urchin-like hierarchical TiO2 microspheres synthesized by a one-pot hydrothermal method and their enhanced photocatalytic activity";Yi Zhou et al.;《Materials Research Bulletin》;20130305;第48卷;第2420-2425页 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3617147A1 (en) * | 2018-08-30 | 2020-03-04 | Petrochina Company Limited | Process for preparing titanic acid salt, titanic acid, and titanium oxide having controllable particle size and hierarchical structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104261465A (en) | 2015-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104261465B (en) | A kind of preparation method of titanate, metatitanic acid and titanium dioxide | |
| EP3617147B1 (en) | Process for preparing titanic acid salt, titanic acid, and titanium oxide having controllable particle size and hierarchical structure | |
| CN104201364A (en) | Method for preparing spinel lithium titanate | |
| CN109319832A (en) | A kind of threadiness poriferous titanium dioxide material and the preparation method and application thereof | |
| CN1725530A (en) | Preparation method of spinel lithium titanate nano tube/wire for lithium battery and capacitor | |
| CN102531050B (en) | Method for preparing TiO2 (B) nano wires and application of prepared TiO2 (B) nano wires | |
| CN106219510A (en) | The method that a kind of highly basic activation pomelo peel prepares three-dimensional carbon nano material | |
| CN109019675A (en) | A kind of nanostructure titanate and its preparation method and application | |
| Liu et al. | Dye-sensitized solar cells based on surficial TiO2 modification | |
| CN110723737A (en) | Wool ball type Ti3C2Preparation method and application of (MXene) nano material | |
| CN108946805A (en) | A kind of preparation method of poriferous titanium dioxide nano wire | |
| CN104198560B (en) | A kind of preparation method of the porous silica titanium compound film of graphene modified | |
| CN103318956A (en) | Titanium dioxide nanowire preparation method | |
| CN109279649B (en) | Preparation method of lithium titanate with nanotube hierarchical structure, application of lithium titanate and product | |
| CN104900861A (en) | Hydrogen lithium titanate Li-H-Ti-O material and preparation method thereof | |
| CN105944738A (en) | Preparation method of TiO2/MoS2 composite material based on surface modification | |
| CN105514436A (en) | Preparation method for graphene-coated titanium dioxide nanotube | |
| CN104667903A (en) | Catalyst for catalytic degradation of pollutants by ultraviolet light and preparation method of catalyst | |
| CN107890861A (en) | One kind has the preparation method of the titanium dioxide lamella/graphene composite film of { 001 } crystal face | |
| CN109326790A (en) | A kind of 1-dimention nano threadiness sodium titanate and its preparation method and application | |
| CN109326791A (en) | A kind of porous lithium titanate material of threadiness and its preparation and product | |
| CN109179492B (en) | Lithium titanate nano-particles and preparation method and application thereof | |
| CN104386743B (en) | A kind of Detitanium-ore-type TiO 2the solvothermal preparation method of nanotube | |
| CN103240068A (en) | Preparation method of self-doped titanium dioxide nanorod | |
| CN102231304B (en) | Method for preparing nano TiO2 (titanium dioxide) pastes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200304 Address after: No. 999, Haifeng North Road, Cixi Binhai Economic Development Zone, Ningbo City, Zhejiang Province Patentee after: Ningbo micro nano New Material Technology Co., Ltd Address before: 100083 Beijing city Haidian District No. 6 Xueyuan Road Furun 1 building A block 1706 Patentee before: Li Jianming |
|
| TR01 | Transfer of patent right |