CN1283555C - Method for preparing rutile nano titanium dioxide - Google Patents
Method for preparing rutile nano titanium dioxide Download PDFInfo
- Publication number
- CN1283555C CN1283555C CN 200310106562 CN200310106562A CN1283555C CN 1283555 C CN1283555 C CN 1283555C CN 200310106562 CN200310106562 CN 200310106562 CN 200310106562 A CN200310106562 A CN 200310106562A CN 1283555 C CN1283555 C CN 1283555C
- Authority
- CN
- China
- Prior art keywords
- rutile
- titanium dioxide
- carrier
- preparation
- nano
- 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.)
- Expired - Fee Related
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000012065 filter cake Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 230000000694 effects Effects 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- -1 titanic acid ester Chemical class 0.000 claims description 4
- 229920000858 Cyclodextrin Polymers 0.000 claims description 3
- 241000158728 Meliaceae Species 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 241000195493 Cryptophyta Species 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 15
- 239000002245 particle Substances 0.000 abstract description 10
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 3
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 150000003609 titanium compounds Chemical class 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 24
- 239000013078 crystal Substances 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- IDIJOAIHTRIPRC-UHFFFAOYSA-J hexaaluminum;sodium;2,2,4,4,6,6,8,8,10,10,12,12-dodecaoxido-1,3,5,7,9,11-hexaoxa-2,4,6,8,10,12-hexasilacyclododecane;iron(2+);triborate;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Fe+2].[Fe+2].[Fe+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-][Si]1([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O1 IDIJOAIHTRIPRC-UHFFFAOYSA-J 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229910000246 schorl Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003115 biocidal effect 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
- 230000007812 deficiency Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明涉及一种金红石相纳米二氧化钛粉体的制备方法，采用的技术方案是：将载体加到含分散剂的溶剂体系中，在超声波作用下使载体充分分散；调节分散液的pH值为1.0～2.0；将溶液浓度为0.5～2.0mol/L的含钛化合物水溶液缓慢加入到上述分散液中，在超声波作用下，缓慢加入碱液，反应1～3小时；静置2～3小时后进行过滤、洗涤处理，将得到滤饼直接在500～900℃的温度下煅烧至载体除尽，制得松散状金红石型纳米二氧化钛粉体。由于反应在常温常压下进行，所得产品不需碾磨即为粉体，因此，具有粒径可控，分布窄，纯度高，不团聚，且工艺简单、流程短、成本低、易大规模生产的特点。The invention relates to a preparation method of rutile phase nano-titanium dioxide powder. The technical scheme adopted is: adding a carrier to a solvent system containing a dispersant, fully dispersing the carrier under the action of ultrasonic waves; adjusting the pH value of the dispersion to 1.0 ～2.0; Slowly add the titanium compound aqueous solution with a solution concentration of 0.5～2.0mol/L to the above dispersion liquid, slowly add lye under the action of ultrasonic waves, and react for 1～3 hours; after standing for 2～3 hours, carry out Filtration and washing treatment, the obtained filter cake is directly calcined at a temperature of 500-900° C. until the carrier is completely removed, and a loose rutile nano-titanium dioxide powder is obtained. Since the reaction is carried out at normal temperature and pressure, the obtained product is powder without grinding, so it has controllable particle size, narrow distribution, high purity, no agglomeration, simple process, short process, low cost, and easy large-scale characteristics of production.
Description
Technical field
The present invention relates to a kind of preparation method of rutile-phase nano-titanium dioxide powder, belong to field of inorganic material preparing technology.
Background technology
Nano titanium oxide is the extremely wide nano material of a kind of application, and it has nanoparticle (1～100nm) distinctive small-size effect, quantum size effect, surface effects and macro quanta tunnel effect.Its extremely strong ultraviolet screener ability can make it make ultraviolet screening agent at makeup, field of textiles; Its high light oxidation capacity and chemical stability, nontoxicity make it be expected to become a kind of good photocatalyst material, are used to purify air, deodorizing, antifouling, antibiotic; Its good optical character can make coating and paint produce the effect of effect, improves coating and paint quality greatly; Can be used in addition in the emulsion paint, improve colour vividness, resistance to deterioration and the weathering resistance etc. of filming.
The above-mentioned performance of nano titanium oxide can be not fully exerted depend on size of particles, form, structure and use in agglomeration.Say that from crystal formation nano titanium oxide mainly contains anatase, rutile, plate attitude ore deposit.Because rutile has the impayable excellent properties of many other crystal formations (as good opacifying property, chemical stability, ultraviolet screener effect), application prospect is the most wide, is widely used in fields such as senior pigment, makeup, non-linear photon material.
The method that is used to prepare nano titanium oxide at present is a lot, but be used to produce amorphous or sharp attitude type mostly, produce the also few of high pure gold redrock phase nano-titanium dioxide, generally be rutile and sharp attitude and deposit, and, therefore be not easy to make the red schorl phase titanium dioxide of small particle size because sharp attitude type needs high temperature to the rutile-type transformation.Nanometer rutile phase titanic oxide preparation method generally is divided into vapor phase process and liquid phase method, relatively is typically the chloride oxidation method in the vapor phase process, powder purity height, and granularity is little, but technical equipment is had relatively high expectations, and energy consumption is big, the cost height.Liquid phase method relatively is typically sol-gel method, this method general using titanium alcohol ester is a raw material, cost is higher, and technical process is longer, easily produce hard aggregation in the powder last handling process, be not easy to obtain the rutile-phase nano-titanium dioxide of small particle size, and in the sol-gel building-up process, the factor that causes titanium dioxide crystal form to change is a lot, the nano titanium oxide that often obtains multiple crystal formation and deposit.Inorganic titanium salt hydrolysis direct precipitation method be the easiest also be most economical method, but because in the hydrolytic process, the subtle change of external conditions (as concentration, temperature, pH value etc.) all can produce very big influence to the result, and phase inversion at high temperature carries out, and therefore generally can only obtain micron order rutile-phase nano-titanium dioxide powder.Though hydrothermal method can directly generate gold redrock nano-titanium dioxide, its equipment requirements height, complicated operation, cost is higher.Publication number is in the Chinese patent " method of preparing titanic schorl phase titanium dioxide nanometer crystal under room temp " of CN1248550A, disclosing a kind of is main raw material with the titanium tetrachloride, adopt the method for prepared titanic schorl phase titanium dioxide nanometer crystals such as mineral acid hydrolysis, vacuum-drying, because it is relatively stricter that this method requires control of process condition, especially the concentration of titanium tetrachloride is bigger to the hydrolysis rate influence, and the required heavyization time is longer, therefore, productive rate is lower, is unfavorable for suitability for industrialized production.
Therefore explore that performance is good, cost is low, flow process is short and be convenient to the nanometer rutile phase titanic oxide powder preparing novel process of scale operation significant to the excellent properties of giving full play to nano titanium oxide.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of titanium dioxide rutile phase content height, controlled, the narrowly distributing of particle diameter, and technology is simple, flow process short, the method for preparing the rutile-phase nano-titanium dioxide material of easy scale operation.
Its concrete technical process is as follows:
1. carrier is added in the solvent system that contains dispersion agent, the carrier consumption is 10～50g/L, under the ultrasonic wave effect carrier is fully disperseed;
2. the pH value with concentrated hydrochloric acid or concentrated nitric acid adjusting dispersion liquid is 1.0～2.0;
3. the titanium-containing compound aqueous solution that with strength of solution is 0.5～2.0mol/L slowly joins in the above-mentioned dispersion liquid, under the ultrasonic wave effect, slowly adds alkali lye, reacts 1～3 hour, and the mol ratio of alkali lye add-on and titanium-containing compound is 3～6: 1;
4. leave standstill after 2～3 hours filter, carrying out washing treatment, directly eliminate obtaining filter cake at 500～900 ℃ temperature lower calcination to carrier, make loose shape rutile-type nano titania powder.
In the preparation method of above-mentioned rutile-phase nano-titanium dioxide, described carrier is modified lignin mahogany sulfonate, cyclodextrin, powdered carbon, starch, algae, macromolecule network polymkeric substance or its mixture; Described titanium-containing compound is TiCl
4, Ti (SO
4)
2, titanic acid ester or its mixture; Described dispersion agent is ethylenediamine tetraacetic acid (EDTA), citric acid, T-80 or Yelkin TTS class, and the concentration of dispersion agent is 0.5～2.0g/L; Described solvent is ethanol, butanols, hexanaphthene, Virahol, water or its mixed solvent; Described alkali lye is urea, ammoniacal liquor, sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus or its mixture; Described ultrasonic frequency is 20～50KHz, and power is 100～500W.
Outstanding advantage of the present invention is:
1. selected carrier has absorption and iris action, has avoided the reunion and the bonding of product, prevented growing up of crystal grain in the postorder phase inversion process, so the gained diameter of particle is little, and it is very narrow to distribute, in ± 1nm.
2. be reflected under the ultrasonic wave effect and carry out, the crystalline phase transformation ratio is more abundant, and therefore, the nano-powder rutile phase content of preparation is up to 99%.
3. products obtained therefrom need not milled and is nano-powder, and narrow diameter distribution, and therefore, powder has fabulous dispersiveness in the aqueous solution, places the long period and does not have obvious agglomeration.
4. reaction is carried out at normal temperatures and pressures, and technical process is short, easily suitability for industrialized production.
Description of drawings
Fig. 1 is the laser particle size analysis figure of the prepared rutile-phase nano-titanium dioxide powder of one embodiment of the invention;
Fig. 2 is the X diffraction analysis figure as a result of the prepared rutile-phase nano-titanium dioxide powder of one embodiment of the invention;
Fig. 3 is the transmission electron microscope picture of the prepared rutile-phase nano-titanium dioxide powder of one embodiment of the invention.
Embodiment
Below by embodiment also in conjunction with the accompanying drawings, technical scheme of the present invention is further elaborated.
Embodiment 1:
The 2g cyclodextrin is added to 100ml contains in the ethanol/water mixed solvent of Yelkin TTS 0.8g/L, under the ultrasonic wave effect, it is fully disperseed; PH value with concentrated hydrochloric acid adjusting dispersion liquid is 1.1 then; With concentration is that the titanium tetrachloride aqueous solution of 0.5mol/L slowly joins in the above-mentioned dispersion liquid, is 30KHz in frequency, and power is under the ultrasonic wave effect of 250W, drips concentration and be 30% ammoniacal liquor, and reaction is 1.5 hours under the room temperature; Leave standstill after 2 hours and filter, wash, 700 ℃ of temperature lower calcinations 1 hour, promptly getting particle diameter was the off-white powder shape rutile type nano titanic oxide of 9.5nm with the filter cake that obtains.
Referring to accompanying drawing 1, by the laser particle size analyzer analytical results as can be known, by the rutile-phase nano-titanium dioxide powder that embodiment 1 described preparation method makes, median size is 9.5nm, size distribution ± 0.1nm.
Referring to accompanying drawing 2, the rutile-phase nano-titanium dioxide powder that makes by embodiment 1 described preparation method, X diffraction analysis result shows: 2 corresponding respectively θ of main peaks are 27.39,36.03,41.19,54.28, and are in full accord with rutile material phase analysis normal data (JCPDF).
Referring to accompanying drawing 3, by the rutile-phase nano-titanium dioxide powder that embodiment 1 described preparation method makes, shown in the transmission electron microscope image, dispersion of particles and homogeneity are very good.
Embodiment 2:
The 2g modified lignin mahogany sulfonate is added to 150ml to be contained in ethanol/cyclohexane/water mixed solvent of ethylenediamine tetraacetic acid (EDTA) 2.0g/L, under the ultrasonic wave effect, carrier is fully disperseed, pH value with concentrated hydrochloric acid adjusting dispersion liquid is 1.5 then, with concentration is that the butyl (tetra) titanate aqueous solution of 1.5mol/L slowly joins in the above-mentioned dispersion liquid, in frequency is 30KHz, power is under the ultrasonic wave effect of 300W, dropping concentration is 30% ammoniacal liquor, other step gets 19.5nm off-white powder shape rutile type nano titanic oxide with embodiment 1.
1g powdered carbon and 1g starch are added to 150ml to be contained in ethanol/cyclohexane/water mixed solvent of citric acid 2.0g/L, under the ultrasonic wave effect, it is fully disperseed, pH value with concentrated nitric acid adjusting dispersion liquid is 1.0 then, with concentration is that the titanium tetrachloride aqueous solution of 0.5mol/L slowly joins in the above-mentioned dispersion liquid, in frequency is 30KHz, power is under the ultrasonic wave effect of 250W, dropping concentration is 30% ammoniacal liquor, reaction is after 1.5 hours under the room temperature, left standstill 2 hours, filter then, washing 700 ℃ of temperature lower calcinations 1 hour, promptly gets 24.5nm off-white powder shape rutile type nano titanic oxide with filter cake.
The 2g powdered carbon is added to 100ml contains in the ethanol/water mixed solvent of Yelkin TTS 0.8g/L, other step is with embodiment 1, and the gained diameter of particle is 25.2nm, the off-white powder shape.
The foregoing description shows, by changing kind of carrier and processing condition, can obtain the powder of different-grain diameter.
Claims (7)
1. the preparation method of a rutile-phase nano-titanium dioxide is characterized in that:
(1) carrier is added in the solvent system that contains dispersion agent, the carrier consumption is 10～50g/L, under the ultrasonic wave effect carrier is fully disperseed;
(2) the pH value with concentrated hydrochloric acid or concentrated nitric acid adjusting dispersion liquid is 1.0～2.0;
(3) be that the titanium-containing compound aqueous solution of 0.5～2.0mol/L slowly joins in the above-mentioned dispersion liquid with strength of solution, under the ultrasonic wave effect, slowly add alkali lye, reacted 1～3 hour, the mol ratio of alkali lye add-on and titanium-containing compound is 3～6: 1;
(4) leave standstill after 2～3 hours filter, carrying out washing treatment, directly eliminate obtaining filter cake at 500～900 ℃ temperature lower calcination to carrier, make loose shape rutile-type nano titania powder.
2. the preparation method of rutile-phase nano-titanium dioxide according to claim 1, it is characterized in that: described carrier is modified lignin mahogany sulfonate, cyclodextrin, powdered carbon, starch, algae, macromolecule network polymkeric substance or its mixture.
3. the preparation method of rutile-phase nano-titanium dioxide according to claim 1, it is characterized in that: described titanium-containing compound is TiCl
4, Ti (SO
4)
2, titanic acid ester or its mixture.
4. the preparation method of rutile-phase nano-titanium dioxide according to claim 1, it is characterized in that: described dispersion agent is ethylenediamine tetraacetic acid (EDTA), citric acid, T-80 or Yelkin TTS class, and the concentration of dispersion agent is 0.5～2.0g/L.
5. the preparation method of rutile-phase nano-titanium dioxide according to claim 1, it is characterized in that: described solvent is ethanol, butanols, hexanaphthene, Virahol, water or its mixed solvent.
6. the preparation method of rutile-phase nano-titanium dioxide according to claim 1, it is characterized in that: described alkali lye is urea, ammoniacal liquor, sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus or its mixture.
7. the preparation method of rutile-phase nano-titanium dioxide according to claim 1, it is characterized in that: described ultrasonic frequency is 20～50KHz, power is 100～500W.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310106562 CN1283555C (en) | 2003-12-03 | 2003-12-03 | Method for preparing rutile nano titanium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310106562 CN1283555C (en) | 2003-12-03 | 2003-12-03 | Method for preparing rutile nano titanium dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1546384A CN1546384A (en) | 2004-11-17 |
| CN1283555C true CN1283555C (en) | 2006-11-08 |
Family
ID=34334241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310106562 Expired - Fee Related CN1283555C (en) | 2003-12-03 | 2003-12-03 | Method for preparing rutile nano titanium dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1283555C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318307C (en) * | 2005-03-07 | 2007-05-30 | 李端 | Process for preparing titanic schorl titanium dioxide by adding powder reducing agent mode |
| CN101319405B (en) * | 2007-06-08 | 2011-05-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for manufacturing TiO2 nanotubes and/or TiO2 nanowhiskers |
| TWI487668B (en) * | 2009-02-19 | 2015-06-11 | Sakai Chemical Industry Co | Dispersion of rutile-type titanium oxide particles, method for producing the same, and use thereof |
| CN102145918A (en) * | 2011-04-18 | 2011-08-10 | 东华大学 | Method for preparing rutile titanium dioxide nanoparticles by using highly strong acid |
| CN103833377A (en) * | 2014-03-21 | 2014-06-04 | 景德镇陶瓷学院 | Particle size control method of ceramic powder prepared by wet chemical method |
| CN107324381A (en) * | 2017-07-14 | 2017-11-07 | 昆明理工大学 | A kind of preparation method of nano-titanium dioxide powder |
| CN107935035B (en) * | 2017-11-24 | 2019-08-02 | 河南科斗新材料研究院有限公司 | A kind of preparation method and applications of oil soluble nano titania particle |
| CN110787650A (en) * | 2019-11-22 | 2020-02-14 | 深圳市君脉膜科技有限公司 | Preparation method of porous nano antibacterial particles and composite hollow membrane |
| CN110813102A (en) * | 2019-11-22 | 2020-02-21 | 深圳市君脉膜科技有限公司 | Preparation method of porous nano antibacterial particles and composite tubular membrane |
-
2003
- 2003-12-03 CN CN 200310106562 patent/CN1283555C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1546384A (en) | 2004-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Synthesis of TiO2 nanotubes coupled with CdS nanoparticles and production of hydrogen by photocatalytic water decomposition | |
| Cassaignon et al. | From TiCl3 to TiO2 nanoparticles (anatase, brookite and rutile): Thermohydrolysis and oxidation in aqueous medium | |
| Yin et al. | Low temperature synthesis of nanosize rutile titania crystal in liquid media | |
| Lee et al. | Effect of HCl concentration and reaction time on the change in the crystalline state of TiO2 prepared from aqueous TiCl4 solution by precipitation | |
| CN101456583B (en) | Synthetic method for preparing rutile type nano titanium dioxide sol or powder at low temperature | |
| CN100391852C (en) | A method of controlling crystal form to prepare nanoscale titanium dioxide | |
| CN101333002B (en) | Titanium dioxide nanopowder with special morphology and preparation method thereof | |
| CN101306838A (en) | Method for preparing high- stable neutral mixed crystal nanometer TiO2 hydrosol | |
| CN1283555C (en) | Method for preparing rutile nano titanium dioxide | |
| CN105016382B (en) | Method for preparing pure gold redstone type titanium dioxide nanorod | |
| CN102219255B (en) | Preparation method for mixed crystal form nanometer titanium dioxide turbid liquor with high stability | |
| CN1865155A (en) | Method for synthesizing soluble titanium dioxide nano crystal in low temperature | |
| CN1086364C (en) | Process for preparing titanic schorl phase titanium dioxide nanometer crystal under room temp. | |
| CN1147431C (en) | A kind of preparation method of anatase phase nano TiO2 | |
| CN100500281C (en) | Preparation method of soluble titanium dioxide nanocrystals | |
| CN105727922B (en) | A kind of Li adulterates SrTiO3The preparation method and product of ten octahedron nanometer particles | |
| CN104909405B (en) | Spindle nano titanium oxide based on cellulose base template and preparation method thereof | |
| CN100445209C (en) | A kind of preparation method of nano titanium dioxide powder | |
| CN1277749C (en) | Process for preparing rutile phase titanium dioxide nano-powder | |
| KR101764016B1 (en) | Method for preparation of pure anatase type TiO2 powders | |
| CN101805017B (en) | Preparation method of rutile type titanium dioxide nano particle | |
| CN102198393B (en) | Method for preparing mixed crystal nanometer titanium dioxide suspension from double precursors | |
| CN1239398C (en) | Method for preparing nano-sized titanium dioxide by solid phase reaction | |
| Chen et al. | Synthesis of nanocrystalline TiO2 particles by hydrolysis of titanyl organic compounds at low temperature | |
| CN1142100C (en) | Process for preparing nm-class rutile-type TiO2 |
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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |