CN1264754C - Preparation method of nanometer rutile type titanium dioxide - Google Patents
Preparation method of nanometer rutile type titanium dioxide Download PDFInfo
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- CN1264754C CN1264754C CN200410041414.5A CN200410041414A CN1264754C CN 1264754 C CN1264754 C CN 1264754C CN 200410041414 A CN200410041414 A CN 200410041414A CN 1264754 C CN1264754 C CN 1264754C
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- deionized water
- filtrate
- rutile
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000004408 titanium dioxide Substances 0.000 title abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000008367 deionised water Substances 0.000 claims abstract description 35
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 35
- 239000003513 alkali Substances 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000706 filtrate Substances 0.000 claims abstract description 22
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 229910003890 H2TiO3 Inorganic materials 0.000 claims abstract description 11
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 49
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 45
- 239000000126 substance Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 12
- 238000010009 beating Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 101710134784 Agnoprotein Proteins 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 12
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 235000012501 ammonium carbonate Nutrition 0.000 abstract 1
- 238000004537 pulping Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- -1 titanium alkoxide Chemical class 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- DQTJHJVUOOYAMD-UHFFFAOYSA-N oxotitanium(2+) dinitrate Chemical compound [O-][N+](=O)O[Ti](=O)O[N+]([O-])=O DQTJHJVUOOYAMD-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000003351 photoxidation Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a preparation method of nanometer rutile type titanium dioxide, which comprises the following steps: step 1: deionized water is added to wet H2TiO3, wherein the quality of the deionized water is 2 to 5 times of the H2TiO3, and the water content of the wet H2TiO3 is 58 to 70%; salvolatile is added to neutralize at room temperature after pulping, precipitation is separated after neutralization and filtration, and deionized water is added, dispersed, pulped and washed till the pH of the filtrate is 7 to 8; steps 2: NaOH is added to purified H2TiO3, stirred and dissolved by alkali at the temperature of 85 to 118 DEG C for 2.5 to 4.5 hours, an alkaline solution is separated, and the precipitation is washed by deionized water; step 3: HCl is added to H4TiO4 which is dissolved by alkali and washed by deionized water, dissolved by acid at the temperature of 85 to 115 DEG C for 60 to 170 minutes, filtrated and separated, and the precipitation is washed by deionized water till the pH of the filtrate is 7 to 8; and step 4: the precipitate which is dissolved with acid and washed with deionized water is dried at the temperature of 105 to 120 DEG C, ground, or slightly dispersed to obtain the nanometer rutile type TiO2 powder. The method is characterized in that a crystal form accelerating agent is not added, nanometer rutile type TiO2 is prepared at low temperature so that the cost is low, and the nanometer TiO2 prepared is almost 100% of a rutile type.
Description
One, technical field
The present invention relates to prepare the method for nm-class rutile-type TiO 2 with metatitanic acid.
Two, background technology
Titanium dioxide (TiO
2) be a kind of to the nontoxic multi-crystalline compounds of human body, three kinds of crystal habits are arranged: brookite type, Detitanium-ore-type and rutile-type.Brookite type TiO
2The crystal formation instability, the report of industrial application is not arranged at present as yet.Rutile TiO
2Than Detitanium-ore-type TiO
2The Stability Analysis of Structures densification, hardness, density, specific inductivity, specific refractory power, opacifying power, tinting strength and all higher to ultraviolet receptivity etc.Because Detitanium-ore-type TiO
2In the reflectivity of visible short part and photoxidation catalytic activity all than rutile TiO
2Height is so as tinting pigment the time, its weather resisteant energy and resistance to chalking can be all than rutile-type differences.Therefore, at senior paint, sun care preparations, Freshkeeping Packaging, fields such as fine ceramics and porcelain dielectric capacitor, rutile TiO
2Than Detitanium-ore-type TiO
2Have and use more widely and higher commercial value.
Nano rutile-type TiO
2Be the superfine microcrystallite of particle diameter in the 1-100nm scope, the functions such as surface effects, quantum size effect and macro quanta tunnel effect that have micron order crystal grain and bulky crystal not to have, thereby show fabulous resistance to chemical attack, photocatalytic activity and anti-uv-ray.So except the application that above-mentioned report is arranged, also be used as photosensor, photodissociation hydrophone spare, antifog glass, the organism Photodegradation catalyst, gas sensor, aspects such as temperature sensor and magnetic recording material are applied and good prospects for application.
Domestic and international synthesis of nano rutile TiO
2Method, mainly contain titanium alkoxide (Ti (OR)
4) liquid phase or gas phase hydrolysis method, titanium tetrachloride (TiCl
4) t method, gas phase oxyhydrogen flame hydrolysis method and liquid phase method and titanyl sulfate (TiOSO
4) the liquid phase peptisation etc.Used Ti (OR)
4, TiCl
4Price Deng raw material is all very expensive, and adopts TiCl
4Be raw material, equipment corrosion-resistant required high that investment cost is very big, also be difficult to avoid pollution simultaneously environment.Therefore, in this case, in order to prepare nano rutile-type TiO
2, more domestic patents have successively been announced employing titanium sulfate (Ti (SO
4)
2), TiOSO
4And H
2TiO
3Development results.As CN 104463C, adopt the H that is added with rutile crystal type promotor
2TiO
3, after the thermal treatment with polyoxyethylene glycol dispersion and emulsion and 700-800 ℃, 1.5-3hr, make rutile TiO
2, its specific surface area＞10m
2/ g, particle diameter～100nm.This is one piece of domestic employing sol-gel processing early, adds crystal type promoting reagent, changes the patent report of brilliant preparation through the electric furnace high-temperature roasting.Its weak point is: maturing temperature is difficult to change brilliant or only partly changes the brilliant rutile-type that is when low; Change brilliant good when maturing temperature is high, but grain growth exceeds the nano level scope, specific surface area data that it is listed and electromicroscopic photograph have also clearly demonstrated this situation, in addition, because the consumption of electric energy in the roasting makes production cost occupy high-leveled and difficult descend greatly.Patent: CN 1076319C; CN1078181C; CN 1343745A and CN 1308022A etc. have reported employing: precipitation from homogeneous solution agent (NH
2)
2CO; Or add and disperse transforming agent zinc sulfate; Or add the monoethanolamine dispersion agent and add crystal type promoting reagent chlorination oxygen titanium; Or add organic surface treatment agent Whitfield's ointment and add 60-90 number industrial organic oil extracting TiO
2, the high-temperature roasting of passing through temperature ranges different in the 560-1000 ℃ of scope subsequently more one by one prepares nano rutile-type TiO
2CN 1431154A is with Ti (SO
4)
2, TiOSO
4And H
2TiO
3For positive metatitanic acid (Ti (OH) is made in raw material and alkali effect
4), use organic complex (oxalic acid, EDTA or tartrate etc.) processing to make titanium organic complex solution and obtain the purpose product again: liquid nano titanium dioxide precursor.When this precursor is made nm-class rutile-type TiO 2 behind 700-800 ℃ of thermal treatment 1hr.CN 1124983C is adopting Ti (SO
4)
2, TiOSO
4And H
2TiO
3During for feedstock production, to H
2TiO
3Adopted and used H earlier
2SO
4TiOSO is made in processing
4, under alkali 0-80 ℃, act on, make Ti (OH) again
4, subsequently with HCl or HNO
3Make without high-temperature roasting for 30-100 ℃, specific surface area is 80-150m
2/ g, the nano rutile-type TiO of rutile content＞90-95%
2[J.Kor.Ceram.Soc., 38 (4), 331-336 (2001)] such as Seo Dong-Seok reported and used TiCl
4With NH
4The OH effect is made titanium hydroxide and is precipitated, and with NaOH 60-80 ℃ of effect down, acts on down with HCl 60-100 ℃ after washing more again, makes specific surface area up to 240-250m
2The nano rutile-type TiO of/g
2CN 1142100C TiOSO
4Be raw material,, after cleaning, use nitric acid treatment again, make titanyl nitrate through alkali precipitation, add crystal type promoting reagent (EDTA, Whitfield's ointment, citric acid .... etc.), 95-105 ℃, ordinary-pressure hydrolysis makes nano rutile-type TiO under the 0.5-4hr
2CN1324767A uses H
2TiO
3Be raw material, add alkali and make Ti (OH)
4, add H
2SO
4Dissolving generates Ti (SO
4)
2, add crystal type promoting reagent (0.2% zinc oxide, 0.1% magnesium oxide) 70-100 ℃ hydrolysis 3hr again, get nano-TiO
2Colloidal sol, after the alkali lye cohesion, flush away SO
4 2-And Na
+, add the HCl peptization again.Nano rutile-type TiO is made in a centrifugation 80-100 ℃ oven dry
2CN 1363520A Ti (SO
4)
2Be raw material, adopt the sour ammonium of four ammino zinc (II) to make hydrolysis crystal seed, get H through hydrolysis as neutralizing agent
2TiO
3, add alkali and make Ti (OH)
4. add acid again and make TiO 2 sol, add flocculation agent (polyoxyethylene glycol, trolamine ... etc.) make gel, 400-850 ℃ of 1-5hr roasting makes nano rutile-type TiO
2
Three, summary of the invention
The present invention is on the basis of patent announcement and relevant bibliographical information at home, obtains after a large amount of development work.The purpose of this invention is to provide a kind of: titanium material is cheap and easy to get; Technical process is simple and easy to control; The cost of product is low, purity is high, steady quality, is convenient to suitability for industrialized production nano rutile-type TiO
2Method.
Technical scheme of the present invention is as follows
A kind of method for making of nm-class rutile-type TiO 2, it may further comprise the steps:
Step 1: the wet H that produces in sulfuric acid method titanium pigment factory
2TiO
3In (water content is 58-70%), add the deionized water that 2-5 doubly measures quality, at room temperature, press mass ratio W after the making beating
(NH4) 2CO3: W
H2TiO=0.01-0.08 adds volatile salt [(NH
4)
2CO
3], violent stirring, neutralization, (NH
4)
2CO
3Neutralization is after filtering separation adds deionized water in the precipitation, and violent stirring is disperseed making beating, washing, wash to the pH of filtrate be 7-8, to remove H
2TiO
3In the SO of the metal ion, acid solution and the chemisorption that are mingled with
3, obtain through (NH after the filtration
4)
2CO
3Handle the H of purifying
2TiO
3
Step 2: with the H of step 1 purifying
2TiO
3, at TiO
2Under the content 200-350g/L, press the ratio of amount of substance, M
TiO2: M
NaOH=1.0: 2.8-4.2, add NaOH, after stirring the molten 2.5-4.5hr of alkali under 85-118 ℃, separate alkali lye, the pH=7-8 to filtrate is washed in the precipitate with deionized water washing, uses 0.5M BaCl
2Solution detects and does not contain SO
4 2-Ion.
Chemical equation in the molten and washing process of alkali is:
Step 3: with step 2 alkali molten and the washing after H
4TiO
4, at TiO
2Under the content 200-350g/L, press the ratio of amount of substance, M
TiO2: M
HCl=1.0: 1.2-2.2, add people HCl, at 85-115 ℃, after sour molten 60-170 minute, filtering separation is fallen acid solution, and precipitate with deionized water is washed the pH=7-8 to filtrate, uses 0.1NAgNO
3Solution detects and does not contain Cl
-Ion.
Chemical equation in the molten process of acid is:
This positive metatitanic acid dissolving after the acid and the Ti that has certain electric charge that generates of adding
4+And TiO
2+Adsorption zone electric process on the particle of titanium oxides such as positive metatitanic acid all makes the particle of titanium oxide disperse and is stabilized in the solution with the micelle form, and under the micelle condition, through heating, slaking and change brilliant back generation nano rutile-type TiO
2
Step 4: through the molten throw out that reaches after cleaning of step 3 acid,, grind or dispersion slightly, promptly obtain nano rutile-type TiO 105-120 ℃ of oven dry down
2Powder.
The method for making of nm-class rutile-type TiO 2 of the present invention is characterized in: do not add crystal type promoting reagent; Do not add emulsifying agent and complexing agent and dispersion agent; Do not adopt high-temperature roasting; Use H
2TiO
3Preparation nano rutile-type TiO under lower temperature of reaction
2, so cost is low, the nano rutile-type TiO that makes
2Almost 100% is rutile-type.
Four, description of drawings
Fig. 1 is the XRD spectra of the nm-class rutile-type TiO 2 of the inventive method preparation, wherein: 1 is the sample of embodiment 1 preparation, 2 is the sample of embodiment 2 preparations, 3 is the sample of embodiment 3 preparations, 4 is the sample of embodiment 4 preparations, 5 is the sample of embodiment 5 preparations, and 6 is the sample of embodiment 6 preparations.
Fig. 2 is the TEM photo of the nm-class rutile-type TiO 2 of the inventive method preparation, wherein: Fig. 2 .1 is the sample of embodiment 1 preparation, Fig. 2 .2 is the sample of embodiment 2 preparations, Fig. 2 .3 is the sample of embodiment 3 preparations, Fig. 2 .4 is the sample of embodiment 4 preparations, Fig. 2 .5 is the sample of embodiment 5 preparations, and Fig. 2 .6 is the sample of embodiment 6 preparations
Four, embodiment
Embodiment one
H will wet
2TiO
3(water content is 58-70%) adds the deionized water of 5 times of amounts, and mass ratio W is pressed in making beating under the room temperature
(NH4) 2CO3: W
H2TiO3=0.01 amount adds (NH
4)
2CO
3Neutralization is fully stirred, and filters, and separates (NH
4)
2CO
3Washings.Add deionized water and fully stir, repeatedly wash the pH=7-8 to filtrate, filtering separation obtains washing the H of purifying
2TiO
3, at TiO
2Under the content 200g/L, press the ratio M of amount of substance
TiO2: M
NaOHAdd NaOH at=1.0: 2.8, behind the 85 ℃ of molten stirring of following alkali 4.5hr, filters, and separates alkali lye.The precipitate with deionized water washing, filtrate is through BaCl
20.5M detecting, solution do not contain SO
4 2-Ion, and behind the pH=7-8, at TiO
2Under the content 200g/L, press the ratio M of amount of substance
TiO2: M
HClAdd people HCl at=1.0: 1.2, and 92 ℃ acid is after molten 150 minutes down, and filtration separates acid solution, and precipitate with deionized water is washed to filtrate pH=7-8, uses 0.1N AgNO
3Solution detects and does not contain Cl
-After gained is deposited in 105 ℃ of down oven dry, grinds or disperses slightly white powdery almost 100% is the nano rutile-type TiO of rutile-type
2XRD determining is a rutile TiO
2(JCPDS 21-1276); TEM photo (35153) particle diameter 30-60nm, fusiform; Specific surface area 135.9m
2/ g.
Embodiment two
H will wet
2TiO
3(water content is 58-70%) adds the deionized water of 2 times of amounts, and mass ratio W is pressed in making beating under the room temperature
(NH4) 2CO3: W
H2TiO3=0.02 amount adds (NH
4)
2CO
3Neutralization, the treating processes of purifying is identical with embodiment one.With the H behind the washing purifying
2TiO
3, at TiO
2Under the content 240g/L, press M
TiO2: M
NaOHAdd NaOH at=1.0: 3.2, behind 90 ℃ of molten 4.2.hr of alkali, separates alkali lye.The precipitate with deionized water washing, filtrate is through BaCl
20.5M detecting, solution do not contain SO
4 2-Ion, and behind the pH=7-8, at TiO
2Under the content 240g/L, press M
TiO2: M
HClAdd people HCl at=1.0: 1.5, and molten 100 minutes after-filtration of 98 ℃ of following acid separate acid solution.Precipitate with deionized water is washed to filtrate pH=7-8, uses 0.1N AgNO
3Solution detects and does not contain Cl
-Ion.After gained is deposited in 110 ℃ of down oven dry, grinds or disperses slightly white powdery almost 100% is the nano rutile-type TiO of rutile-type
2XRD determining is a rutile TiO
2(JCPDS 21-1276); TEM photo (35155) particle diameter 20-40nm, fusiform; Specific surface area 146.1m
2/ g.
Embodiment three
H will wet
2TiO
3(water content is 58-70%) adds the deionized water of 4 times of amounts, and mass ratio W is pressed in making beating under the room temperature
(NH4) 2CO3: W
H2TiO3=0.04 amount adds (NH
4)
2CO
3Neutralization, the treating processes of purifying is identical with embodiment one.With the H behind the washing purifying
2TiO
3, at TiO
2Under the content 270g/L, press the ratio M of amount of substance
TiO2: M
NaOHAdd NaOH at=1.0: 3.8, behind the 118 ℃ of molten stirring of alkali 4.0.hr, separates alkali lye.Precipitate with deionized water wash to filtrate through BaCl
20.5M detecting, solution do not contain SO
4 2-Ion, and behind the pH=7-8, at TiO
2Under the content 270g/L, press the ratio M of amount of substance
TiO2: M
HClAdd people HCl at=1.0: 2.0, and molten 120 minutes after-filtration of acid separate acid solution under 112 ℃.Precipitate with deionized water is washed to filtrate pH=7-8, uses 0.1N AgNO
3Solution detects and does not contain Cl
-Ion.After gained is deposited in 115 ℃ of down oven dry, grinds or disperses slightly white powdery almost 100% is the nano rutile-type TiO of rutile-type
2XRD determining is a rutile TiO
2(JCPDS 21-1276); TEM photo (42288) particle diameter 50-80nm, fusiform; Specific surface area 157.6m
2/ g.
Embodiment four
H will wet
2TiO
3(water content is 58-70%) adds the deionized water of 5 times of amounts, and mass ratio W is pressed in making beating under the room temperature
(NH4) 2CO3: W
H2TiO3=0.05 amount adds (NH
4)
2CO
3Neutralization, the treating processes of purifying is identical with embodiment one.With the H behind the washing purifying
2TiO
3, at TiO
2Under the content 300g/L, press the ratio M of amount of substance
TiO2: M
NaOHAdd NaOH at=1.0: 3.5, behind the 110 ℃ of molten stirring of alkali 3.2.hr, and filtering separation alkali lye.Precipitate with deionized water wash to filtrate through BaCl
20.5M detecting, solution do not contain SO
4 2-Ion, and behind the pH=7-8, at TiO
2Under the content 300g/L, press the ratio M of amount of substance
TiO2: M
HClAdd people HCl at=1.0: 1.7, and molten 60 minutes after-filtration of acid separate acid solution under 115 ℃.Precipitate with deionized water is washed to filtrate pH=7-8, uses 0.1N AgNO
3Solution detects and does not contain Cl
-Ion.After gained is deposited in 112 ℃ of down oven dry, grinds or disperses slightly white powdery almost 100% is the nano rutile-type TiO of rutile-type
2XRD determining is a rutile TiO
2(JCPDS 21-1276); TEM photo (42289) particle diameter 30-80nm, fusiform; Specific surface area 142.8m
2/ g.
Embodiment five
H will wet
2TiO
3(water content is 58-70%) adds the deionized water of 4 times of amounts, and mass ratio W is pressed in making beating under the room temperature
(NH4) 2CO3: W
H2TiO3=0.06 amount adds (NH
4)
2CO
3Neutralization, the treating processes of purifying is identical with embodiment one.With the H behind the washing purifying
2TiO
3, at TiO
2Under the content 3i20g/L, press the ratio M of amount of substance
TiO2: M
NaOH=1.0: 4.0, add NaOH, behind the 115 ℃ of molten stirring of alkali 2.5.hr, filtering separation alkali lye.Precipitate with deionized water wash to filtrate through BaCl
20.5M detecting, solution do not contain SO
4 2-Ion, and behind the pH=7-8, at TiO
2Under the content 320g/L, press the ratio M of amount of substance
TiO2: M
HClAdd people HCl at=1.0: 1.9, after under 108 ℃ sour molten 106 minutes, and the filtering separation acid solution.Precipitate with deionized water is washed to filtrate pH=7-8, uses 0.1NAgNO
3Solution detects and does not contain Cl
-Ion.After gained is deposited in 118 ℃ of down oven dry, grinds or disperses slightly white powdery almost 100% is the nano rutile-type TiO of rutile-type
2XRD determining is a rutile TiO
2(JCPDS 21-1276); TEM photo (35151), particle diameter 30-60nm, fusiform; Specific surface area 142.1m
2/ g.
Embodiment six
H will wet
2TiO
3(water content is 58-70%) adds the deionized water of 2 times of amounts, and mass ratio W is pressed in making beating under the room temperature
(NH4) 2CO3: W
H2TiO3=0.08 amount adds (NH
4)
2CO
3Neutralization, the treating processes of purifying is identical with embodiment one.With the H behind the washing purifying
2TiO
3, at TiO
2Under the content 350g/L, press the ratio M of amount of substance
TiO2: M
NaOHAdd NaOH at=1.0: 4.2,, behind the 104 ℃ of molten stirring of following alkali 3.8.hr, misgivings are separated alkali lye.Precipitate with deionized water wash to filtrate through BaCl
20.5M detecting, solution do not contain SO
4 2-Ion, and behind the pH=7-8, at TiO
2Under the content 350g/L, press the ratio M of amount of substance
TiO2: M
HClAdd people HCl at=1.0: 2.2, and molten 170 minutes after-filtration of acid separate acid solution under 85 ℃.Precipitate with deionized water is washed to filtrate pH=7-8, uses 0.1N AgNO
3Solution detects and does not contain Cl
-Ion.After gained is deposited in 120 ℃ of down oven dry, grinds or disperses slightly white powdery almost 100% is the nano rutile-type TiO of rutile-type
2XRD determining is a rutile TiO
2(JCPDS 21-1276); TEM photo (42252) particle diameter 30-70nm, fusiform; Specific surface area 153.2m
2/ g.
Claims (2)
1. the method for making of a nm-class rutile-type TiO 2 is characterized in that it may further comprise the steps:
Step 1: in water content is the wet H of 58-70%
2TiO
3In, add the deionized water that 2-5 doubly measures quality, at room temperature, press mass ratio W after the making beating
(NH4) 2CO3: W
H2TiO3=0.01-0.08 adds volatile salt, violent stirring, neutralization, (NH
4)
2CO
3Neutralization is after filtering separation adds deionized water in the precipitation, and violent stirring is disperseed making beating, washing, wash to the pH of filtrate be 7-8,
Step 2: with the H of step 1 purifying
2TiO
3, at TiO
2Under the content 200-350g/L, press the ratio of amount of substance, M
TiO2: M
NaOH=1.0: 2.8-4.2, add NaOH, after stirring the molten 2.5-4.5hr of alkali under 85-118 ℃, filtering separation is fallen alkali lye, and the pH=7-8 to filtrate is washed in the precipitate with deionized water washing,
Step 3: with step 2 alkali molten and the washing after H
4TiO
4, at TiO
2Under the content 200-350g/L, press the ratio of amount of substance, M
TiO2: M
HCl=1.0: 1.2-2.2, add HCl, at 85-115 ℃, after sour molten 60-170 minute, filtering separation is fallen acid solution, and precipitate with deionized water is washed the pH=7-8 to filtrate,
Step 4: through the molten throw out that reaches after cleaning of step 3 acid,, grind or dispersion slightly, promptly obtain nano rutile-type TiO 105-120 ℃ of oven dry down
2Powder.
2. method for making according to claim 1 is characterized in that: step 3 is precipitated to filtrate with deionized water wash and uses 0.1N AgNO
3Solution detects and does not contain Cl
-Ion.
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| CN104387807A (en) * | 2014-10-31 | 2015-03-04 | 天津市欣德泰铁粉有限公司 | Preparation method of composite titanium dioxide |
| CN106115775B (en) * | 2016-06-29 | 2017-10-31 | 攀枝花学院 | Adulterate the preparation method of positive metatitanic acid |
| CN109943103A (en) * | 2019-04-16 | 2019-06-28 | 正太新材料科技有限责任公司 | The preparation method and applications of rutile type titanium white |
| WO2022007764A1 (en) * | 2020-07-06 | 2022-01-13 | 宁波极微纳新材料科技有限公司 | Method for preparing titanium dioxide and method for improving titanium dioxide dispersibility |
| CN114105194B (en) * | 2021-12-24 | 2023-10-24 | 济南裕兴化工有限责任公司 | Method for promoting titanium white crystal form conversion |
| CN115716656B (en) * | 2022-11-25 | 2024-01-30 | 西南交通大学 | Crystal lattice twisted rutile phase titanium dioxide nano material and preparation method and application thereof |
| CN115806313B (en) * | 2022-12-26 | 2024-07-16 | 常州纳欧新材料科技有限公司 | Preparation method of micron-sized rutile titanium dioxide nanocrystalline aggregate |
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