CN1172856C - Method of producing rutile type nano titanium dioxide and obtained nano titanium dioxide using said method - Google Patents
Method of producing rutile type nano titanium dioxide and obtained nano titanium dioxide using said method Download PDFInfo
- Publication number
- CN1172856C CN1172856C CNB021043434A CN02104343A CN1172856C CN 1172856 C CN1172856 C CN 1172856C CN B021043434 A CNB021043434 A CN B021043434A CN 02104343 A CN02104343 A CN 02104343A CN 1172856 C CN1172856 C CN 1172856C
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- titanium tetrachloride
- rutile type
- nano titanium
- gel
- 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 117
- 238000000034 method Methods 0.000 title claims abstract description 28
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims description 37
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 2
- 229940099427 potassium bisulfite Drugs 0.000 claims description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019252 potassium sulphite Nutrition 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 13
- 238000005660 chlorination reaction Methods 0.000 abstract description 8
- 239000000843 powder Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 230000010802 Oxidation-Reduction Activity Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a method using a metastable chlorination method to produce rutile type nanometer titanium dioxide and the rutile type nanometer titanium dioxide obtained by the method. The rutile type nanometer titanium dioxide produced by the method of the present invention has total crystal form conversion, for example, the rutile type crystal forms are on the basis of at least 90% of the total weight of the entire titanium dioxide, and the particle diameters are effectively controlled within 100 nm. in addition, the method of the present invention has the advantages of strong operability, good repeatability and stable quality of obtained products.
Description
Technical Field
The invention relates to a method for producing nano titanium dioxide, in particular to a method for producing rutile type nano titanium dioxide by a metastable chlorination method. The invention also relates to rutile type nano titanium dioxide obtained by the method.
Prior Art
It is well known that titanium dioxide, especially nano-sized titanium dioxide, exhibits oxidation activity or reduction activity under light irradiation, i.e., photocatalytic activity. At present, people are gradually utilizing the ultraviolet shielding property, the visible light transmission property and the physical and chemical stability of the nano titanium dioxide, especially the photocatalytic activity of the nano titanium dioxide to carry out application development and functional material development.
Titanium dioxide can be classified into rutile type titanium dioxide, anatase type titanium dioxide and brookite type titanium dioxide according to the difference of lattice structures, and the crystal structures of the titanium dioxide are different, and the performances of the titanium dioxide are also different. Among them, the brookite-type titanium dioxide is very unstable and rarely produced and used due to lack of application properties. The anatase type nano titanium dioxide has better photocatalysis function and thus has wide application prospect. The rutile type nano titanium dioxide has excellent chemical stability, thermal stability, optical effect, photosensitive effect, photoelectric effect and other performances, and belongs to one of the most difficult and expensive functional materials.
In terms of the production of rutile type nano titanium dioxide, the sulfuric acid method is generally used in China, but the pollution is serious, and most products are low-grade anatase type nano titanium dioxide. However, if the chlorination process is adopted to produce rutile type nano titanium dioxide, the problem of high-temperature sintering in the field is always solved and not destroyed, so that the chlorination process in China is always not used. In addition, if organic titanium salts such as butyl titanate and the like are adopted to prepare rutile type nano titanium dioxide, the raw material cost is high, the crystal form conversion is incomplete, and the grain size is difficult to control within 100 nm. In order to obtain a nano particle size, the conversion rate of rutile type is often low, and is less than 90%.
DISCLOSURE OF THE INVENTION
In order to overcome the above problems in the prior art, the inventors of the present invention have conducted extensive and intensive studies in the field of nano-titanium dioxide production, and as a result, have found that rutile-type nano-titanium dioxide having stable chemical properties, excellent ultraviolet-shielding properties and good dispersibility can be synthesized from titanium tetrachloride by using a metastable chlorination process. The present invention has been completed based on this finding.
Therefore, an object of the present invention is to provide a method for producing rutile type nano titanium dioxide, which effectively prevents the problem of high-temperature sintering, controls the grain size of titanium dioxide within 100nm, and has a rutile type crystal form ratio of more than 90 wt% of thetotal titanium dioxide.
It is another object of the present invention to provide a rutile type nano titanium dioxide produced by the method of the present invention.
The invention provides a method for producing rutile type nano titanium dioxide, which comprises the following steps:
1) and (3) hydrolysis reaction: hydrolyzing a titanium tetrachloride raw material to obtain mixed liquid containing white precipitates;
2) sol-gel reaction: adding an acidic substance into the mixed liquid obtained in the step 1) to dissolve the white precipitate to form a uniform reaction solution, and then heating at the temperature of 50-150 ℃ to slowly evaporate the liquid to form sol-gel;
3) filtering and washing: filtering and repeatedly washing the product obtained in the step 2) with water until the pH value is 6-8;
4) and (3) drying: drying the product obtained in the step 3) at the temperature of-30 ℃ to 30 ℃ and under the vacuum degree of 5mmHg to 15mmHg to obtain a metastable titanium dioxide precursor of a self-forming particle system; and
5) high-temperature calcination: calcining the precursor obtained in the step 4) at the temperature of 200-1000 ℃ for 5 minutes to 6 hours.
In another aspect, the present invention provides a rutile type nano-titania having a particle diameter of 100nm or less and a rutile type crystal ratio of at least 90% by weight based on the weight of the entire nano-titania.
These and other objects, features and advantages of the present invention will become more apparent after a reading of the entire specification in conjunction with the accompanying drawings.
Brief Description of Drawings
FIG. 1 is an X-ray diffraction spectrum of rutile type nano-titanium dioxide obtained in example 3 of the present invention; and
FIG. 2 is a transmission electron micrograph of rutile type nano titanium dioxide obtained in example 3 of the present invention.
Detailed Description
In the rutile type nano titanium dioxide production process of the present invention, step 1) involves hydrolysis of titanium tetrachloride which is a raw material. The starting material used in this step may be technical grade titanium tetrachloride or reagent pure titanium tetrachloride. From a cost perspective, commercial grade titanium tetrachloride is preferred. The concentration of titanium tetrachloride is not particularly limited, but it is preferable to control the molar concentration thereof within the range of 0.01 to 30mol/l, preferably 0.05 to 10mol/l, more preferably 0.09 to 5 mol/l. The hydrolysis reaction of step 1) may be carried out at any pH, for example the pH may be from about 0 to 11, preferably from 0 to 8, more preferably from 0 to 5, most preferably from 1 to 3. It is preferred that a base is used in the hydrolysis step for some degree of neutralization, wherein bases that may be used include, for example, ammonium hydroxide (NH)4OH), sodium hydroxide (NaOH), potassium hydroxide (KOH), etc., preferably ammonium hydroxide. The amount of the base used is also not limited at all, and may be, for example, from 0.1 to 10 moles, preferably from 0.5 to 5 moles, more preferably from 1 to 3 moles, per mole of titanium tetrachloride. The temperature at which the hydrolysis reaction is carried out is not particularly limited, and may be carried out at room temperature (about 30 ℃) or at a low temperature, but is preferably carried out at room temperature. Sincethe hydrolysis reaction of titanium tetrachloride is strongly exothermic, cooling using a conventional cooling method such as liquid nitrogen cooling, freezing water bath, or the like is required. After the hydrolysis reaction is finished, obtainingTo a mixed liquid containing a white precipitate.
In the rutile type nano-titania production method of the present invention, step 2) involves the formation of sol-gel. Specifically, an acidic substance is added to the hydrolysate obtained in step 1), and the white precipitate is dissolved to form a uniform reaction solution, and then the reaction solution is heated at a temperature of 50 to 150 ℃, preferably 70 to 100 ℃ for 1 to 10 hours to slowly evaporate the liquid to form a sol-gel. The acidic substance used in this step may be hydrochloric acid, ammonium sulfide, sulfurous acid, stannous chloride, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, nitrous acidSodium or sodium dithionite, etc., preferably hydrochloric acid, ammonium sulfide, sulfurous acid, stannous chloride, sodium nitrite or sodium dithionite having reducing properties, more preferably hydrochloric acid or ammonium sulfide. The term "reducing property" as used herein means that a substance which can reduce other substances and is oxidized by itself, that is, a substance which loses electrons in a redox reaction is a reducing substance, that is, a reducing agent, which is a donor of electrons, and which is preferentially oxidized while causing reduction of titanium oxide to cause reduction of titanium oxide The reaction proceeds to the right, resulting in the formation of oxygen ion deficiencies, i.e., oxygen vacancies. The amount of the acidic substance used in this step is 0.01 to 5 moles, preferably 0.05 to 3 moles, more preferably 0.1 to 2 moles per mole of titanium tetrachloride.
In the rutile type nano titanium dioxide production method of the present invention, the step 3) involves filtration and water washing of the sol-gel obtained in the step 2). The purpose of the washing is to remove acid groups and other impurities. The washing should be repeated until the pH of the sol-gel is about 6 to 8, preferably 6.5 to 7.5.
In the rutile type nano titanium dioxide production method of the present invention, the step 4) involves drying of the washed sol-gel obtained in the step 3). This step is preferably carried out by: drying the washed sol-gel at-30 deg.C to 30 deg.C and 5-15mmHg for 3-6 hr to remove water and possible solvents, such as alcohol solvents, from the sol-gel to obtain metastable titanium dioxide precursor of the self-forming microparticle system.
In the rutile type nano titanium dioxide production method of the invention, the step 5) involves high-temperature calcination of the metastable titanium dioxide precursor obtained in the step 4). This step is preferably carried out at a temperature of 200-1000 deg.C, more preferably 500-980 deg.C in a calcination apparatus commonly used in the art. The atmosphere for the calcination is not limited at all, and the calcination may be carried out in an atmosphere of oxygen or air containing oxygen, or in the presence of an inert gas such as nitrogen, helium, argon, or the like. Although calcination under an oxygen atmosphere is most desirable, the calcination step is carried out using an air atmosphere in view of production safety, production cost and production satisfaction. The calcination time may be 5 minutes to 6 hours, preferably 0.5 to 3 hours.
The expression "metastable" as used herein in the terms "metastable chlorination process" and "metastable titanium dioxide precursor" means that during the sol-gel preparation process of the method of the present invention, the gel is formed from a heterogeneous, non-equilibrium, non-stable system,filtered, washed, and vacuum dried to form a thermodynamically unstable, metastable titanium dioxide precursor of the self-forming particulate system. The phase transition temperature of the precursor from anatase type to rutile type is less than 1000 ℃, and is obviously lower than that of the conventional stable titanium dioxide (the rutile type phase transition temperature range of the conventional stable titanium dioxide is about 1100-1400 ℃), which is a metastable physical property characteristic. In addition, the X-ray diffraction spectrum of the precursor shows a phenomenon of diffraction peak broadening, the proportion of surface atoms is large, surface unsaturated bonds are rich and the like, which all show that the nano titanium dioxide precursor belongs to a metastable substance. The term "metastable chlorination" is therefore used in this specification, in distinction from conventional chlorination.
Although not wishing to be bound by any theory, the inventor believes that in the method of the present invention, since the sol-gel reaction is used to firstly obtain uniform mixing between reactants at the molecular level in a short time, and then vacuum drying is adopted to obtain metastable titanium dioxide monomer or oligomer with uniformly distributed components and easy self-forming particle system, and the final product is obtained by high temperature calcination, the obtained nano titanium dioxide is not easy to bond with each other, hard agglomeration does not occur, sintering phenomenon does not occur, thus effectively controlling the growth of particle size, and titanium dioxide still with nano particle size is obtained while rutile type phase transformation is completed.
The rutile form of the nano-titanium dioxide produced by the process of the present invention has a relatively complete crystal form conversion, for example at least 90% by weight, preferably at least 95% by weight, of the rutile form based on the total weight of the nano-titanium dioxide obtained; the particle size distribution is uniform and the particle size is effectively controlled within 100 nm; in addition, the dispersibility is good. Finally, the method of the invention has strong operability and good reproducibility, and the obtained product has stable quality.
Examples
The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
Using a chilled water bath, 0.6mol of technical titanium tetrachloride (Tianjin chemical plant) was slowly added dropwise to 1000ml of 5% (w/v) NH4In the OH aqueous solution, white precipitate is generated uniformly under uniform stirring. Then, 0.12mol of ammonium sulfide (Beijing Chemicals Co.) was added under stirring to dissolve the white precipitate to obtain a transparent liquid. Heating the liquid at 95 deg.CIt was allowed to evaporate for 1.5 hours to remove excess water and obtain a sol-gel. The resulting sol-gel was filtered and washed 4 times with 500ml of water to give a pH of 7. And drying the washed sol-gel at 20 ℃ and 10mmHg for 3 hours to obtain white micro powder, namely a metastable titanium dioxide precursor. Calcining the white micro powder in a calcining furnace at 850 ℃ for 1 hour to obtain the rutile type nano titanium dioxide with the rutile type crystal form content of 93 percent.
Example 2
Using a chilled water bath, 0.6mol of technical titanium tetrachloride (Tianjin chemical plant) was slowly added dropwise to 1000ml of 5% (w/v) NH4In the OH aqueous solution, white precipitate is generated uniformly under uniform stirring. 0.12mol HCl (Beijing chemical plant) was then addedwith stirring to dissolve the white precipitate to give a clear liquid. At 95 DEG CThe liquid was then heated to evaporate for 1.5 hours to remove excess water and obtain a sol-gel. The resulting sol-gel was filtered and washed 4 times with 500ml of water to give a pH of 7. And drying the washed sol-gel at 20 ℃ and 10mmHg for 3 hours to obtain white micro powder, namely a metastable titanium dioxide precursor. Calcining the white micro powder in a calcining furnace at 900 ℃ for 0.5 hour to obtain rutile type nano titanium dioxide with the rutile type crystal form content of 96 percent.
Example 3
Using a chilled water bath, 0.6mol of technical titanium tetrachloride (Tianjin chemical plant) was slowly added dropwise to 1000ml of 5% (w/v) NH4In the OH aqueous solution, white precipitate is generated uniformly under uniform stirring. Then 0.15mol stannous chloride (Beijing chemical second factory) is added under stirring to dissolve the white precipitate to obtain a transparent liquid. The liquid was heated at 95 ℃ to evaporate for 2 hours, removing excess water to give a sol-gel. The resulting sol-gel was filtered and washed 4 times with 500ml of water to give a pH of 7. And drying the washed sol-gel at 20 ℃ and 10mmHg for 3 hours to obtain white micro powder, namely a metastable titanium dioxide precursor. Calcining the white micro powder in a calcining furnace at 880 ℃ for 1.5 hours to obtain the rutile type nano titanium dioxide with the rutile type crystal form content of 100%. The X-ray diffraction spectrogram and the transmission electron micrograph of the nano titanium dioxide are respectively shown in figure 1 and figure 2. The X-ray diffraction peaks are shown in table 1 below.
Table 1: x-ray diffraction peak results of rutile type nano-titania obtained in example 3
Peak number 2 theta intensity width d I/I0
1 14.040 360 1.020 6.30279 13
2 27.640 2791 0.840 3.22473 100
3 36.320 1586 0.840 2.47151 57
4 39.440 252 1.020 2.28289 9
5 41.400 919 0.840 2.17922 33
6 44.160 309 0.720 2.04921 11
7 54.560 1692 1.020 1.68063 61
8 56.720 565 1.440 1.62165 20
9 63.040 365 0.900 1.47342 13
10 64.160 324 0.600 1.45038 12
11 67.840 155 0.900 1.38038 6
12 69.240 617 0.960 1.35585 22
13 70.000 487 0.960 1.34298 17
14 70.800 144 0.540 1.32975 5
15 76.640 133 0.720 1.24231 5
16 82.440 195 0.960 1.16898 7
17 83.400 119 0.480 1.15794 4
18 84.040 128 0.600 1.15075 5
19 88.400 110 0.480 1.10490 4
20 89.760 262 1.020 1.09166 9
21 90.320 245 0.480 1.08634 9
22 90.840 178 0.600 1.08147 6
23 95.280 248 0.540 1.04246 9
24 96.560 220 0.480 1.03201 8
25 106.040 122 1.200 0.96427 4
Example 4
Using a chilled water bath, 0.6mol of technical titanium tetrachloride (Tianjin chemical plant) was slowly added dropwise to 1000ml of 5% (w/v) NH4In the OH aqueous solution, white precipitate is generated uniformly under uniform stirring. Then, 0.08mol of sodium nitrite (Beijing Chemicals Co.) was added under stirring to dissolve the white precipitate, thereby obtaining a transparent liquid. The liquid was heated at 95 ℃ to evaporate for 2 hours, removing excess water to give a sol-gel. The resulting sol-gel was filtered and washed 4 times with 500ml of water to give a pH of 7. And drying the washed sol-gel at 20 ℃ and 10mmHg for 3 hours to obtain white micro powder, namely a metastable titanium dioxide precursor. Calcining the white micro powder in a calcining furnace at 750 ℃ for 5 hours to obtain the golden redRutile type nano titanium dioxide with the content of the stone crystal form of 92 percent.
Example 5
Using a chilled water bath, 0.6mol of technical titanium tetrachloride (Tianjin chemical plant) was slowly added dropwise to 1000ml of 5% (w/v) NH4In the OH aqueous solution, white precipitate is generated uniformly under uniform stirring. Then, 0.18mol of sulfurous acid (Beijing Chemicals Co.) was added under stirring to dissolve the white precipitate to obtain a transparent liquid. The liquid was heated at 95 ℃ to evaporate for 2 hours, removing excess water to give a sol-gel. The resulting sol-gel was filtered and washed 4 times with 500ml of water to give a pH of 7. And drying the washed sol-gel at 20 ℃ and 10mmHg for 3 hours to obtain white micro powder, namely a metastable titanium dioxide precursor. Calcining the white micro powder in a calcining furnace for 3 hours at 810 ℃ to obtain rutile type nano titanium dioxide with the rutile type crystal form content of 95%.
Example 6
Adopting a freezing water bath to tetrachloroize 0.6mol of industrial gradeTitanium (Tianjin chemical plant) was slowly added dropwise to 1000ml 5% (w/v) NH4In the OH aqueous solution, white precipitate is generated uniformly under uniform stirring. Then, 0.25mol of sodium dithionite (Beijing Chemicals Co.) was added under stirring to dissolve the white precipitate and obtain a transparent liquid. The liquid was heated at 95 ℃ to evaporate for 3 hours, removing excess water to give a sol-gel. The resulting sol-gel was filtered and washed 4 times with 500ml of water to give a pH of 7. And drying the washed sol-gel at 20 ℃ and 10mmHg for 3 hours to obtain white micro powder, namely a metastable titanium dioxide precursor. Calcining the white micro powder in a calcining furnace at 820 ℃ for 4 hours to obtain rutile type nano titanium dioxide with 94 percent of rutile type crystal form content.
Claims (10)
1. A method for producing rutile type nano titanium dioxide, which comprises the following steps:
1) and (3) hydrolysis reaction: hydrolyzing a titanium tetrachloride raw material in the presence of an alkali selected from ammonium hydroxide, sodium hydroxide or potassium hydroxide to obtain a mixed liquid containing a white precipitate;
2) sol-gel reaction: adding an acidic substance into the mixed liquid obtained in the step 1) to dissolve the white precipitate to form a uniform reaction solution, and then heating the solution at the temperature of 50-150 ℃ to slowly evaporate the liquid to form sol-gel, wherein the acidic substance is selected from hydrochloric acid, ammonium sulfide, sulfurous acid, stannous chloride, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium nitrite or sodium dithionite;
3) filtering and washing: filtering and repeatedly washing the product obtained in the step 2) with water until the pH value is 6-8;
4) and (3) drying: drying the product obtained in the step 3) at the temperature of-30 ℃ to 30 ℃ and under the vacuum degree of 5mmHg to 15mmHg to obtain a metastable titanium dioxide precursor of a self-forming particle system; and
5) high-temperature calcination: calcining the precursor obtained in the step 4) at the temperature of 200-1000 ℃ for 5 minutes to 6 hours.
2. The process according to claim 1, wherein the titanium tetrachloride used in step 1) is technical grade titanium tetrachloride or reagent-pure titanium tetrachloride and has a concentration of from 0.01 to 30 mol/l.
3. The process according to claim 2, wherein the titanium tetrachloride used in step 1) has a concentration of 0.05 to 10 mol/l.
4. The method of claim 1, wherein step 1) is performed at a pH of 0-11.
5. The method of claim 4, wherein step 1) is performed at a pH of 0-8.
6. The process of claim 1, wherein the amount of base used is from 0.1 to 10 moles per mole of titanium tetrachloride.
7. A process according to claim 6, wherein the amount of base used is from 0.5 to 5 moles per mole of titanium tetrachloride.
8. The process as set forth in claim 1 wherein the acidic substance is used in an amount of 0.01 to 5 moles per mole of titanium tetrachloride.
9. The process according to claim 8, wherein the acidic substance is used in an amount of 0.05 to 3 moles per mole of titanium tetrachloride.
10. The method of claim 1, wherein the acidic material is hydrochloric acid or ammonium sulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021043434A CN1172856C (en) | 2002-03-01 | 2002-03-01 | Method of producing rutile type nano titanium dioxide and obtained nano titanium dioxide using said method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021043434A CN1172856C (en) | 2002-03-01 | 2002-03-01 | Method of producing rutile type nano titanium dioxide and obtained nano titanium dioxide using said method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1442367A CN1442367A (en) | 2003-09-17 |
| CN1172856C true CN1172856C (en) | 2004-10-27 |
Family
ID=27793088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021043434A Expired - Fee Related CN1172856C (en) | 2002-03-01 | 2002-03-01 | Method of producing rutile type nano titanium dioxide and obtained nano titanium dioxide using said method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1172856C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334261C (en) * | 2005-12-01 | 2007-08-29 | 华中师范大学 | Rutile type structure TiO2 single dispersed nano-monocrystal and its synthesis method |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315731C (en) * | 2002-03-01 | 2007-05-16 | 徐瑞芬 | Method of controlling nano titanium dioxide crystal form and obtained nano titanium dioxide using said method |
| CN101006015B (en) * | 2004-08-11 | 2012-04-25 | 昭和电工株式会社 | Fine particulate titanium dioxide, and production process and use thereof |
| CN100537434C (en) * | 2007-05-18 | 2009-09-09 | 广东省生态环境与土壤研究所 | Method for preparing Nano sol as ultraviolet protective agent |
| 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 |
| CN108502919A (en) * | 2017-02-27 | 2018-09-07 | 国药集团化学试剂有限公司 | A kind of preparation method of titanium dioxide fine particles |
-
2002
- 2002-03-01 CN CNB021043434A patent/CN1172856C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334261C (en) * | 2005-12-01 | 2007-08-29 | 华中师范大学 | Rutile type structure TiO2 single dispersed nano-monocrystal and its synthesis method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1442367A (en) | 2003-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1128106C (en) | Method for prodn. of mono-dispersed and crystalline TiO2 ultrafine powders from aqueous TiOCl2 solution using homogeneous precipitation | |
| CN111960464B (en) | Black titanium dioxide optical nano material rich in oxygen vacancy defects and preparation method and application thereof | |
| CN1348430A (en) | Method for manufacturing photocatalytic titanium dioxide powder | |
| CN1857769A (en) | Low temperature process of preparing carbon-doped mesoporous TiO2 visible light catalyst | |
| CN1814550A (en) | Method for preparing hano-level titanium dioxide by controlling crystal form | |
| CN102515270A (en) | Preparation method of mixed crystal-type nanoscale TiO2 having exposed (001) crystal faces | |
| CN114873637A (en) | Nano-octadecyl SrTiO 3 And preparation method and application thereof | |
| CN1613777A (en) | Preparation for nanometer anhydrous wolframic acid powder | |
| CN105439198B (en) | A kind of preparation method of high ethano/water dispersible nano-titanium dioxide powder | |
| CN1172856C (en) | Method of producing rutile type nano titanium dioxide and obtained nano titanium dioxide using said method | |
| CN1865153A (en) | Babrium titanate preparation method | |
| CN1765511A (en) | PH adjusting hydrothermal preparation method of active nano crystal mesoporous titanium dioxide photocatalytic material | |
| TWI272250B (en) | Visible light-activated photocatalyst and method for producing the same | |
| CN108529669B (en) | Preparation method of titanium dioxide aerogel and titanium dioxide aerogel | |
| CN1197780C (en) | Low temperature preparing process for anatase phase nano crystal titanium dioxide of light catalystic activity | |
| CN1248550A (en) | Process for preparing titanic schorl phase titanium dioxide nanometer crystal under room temp. | |
| CN105399138A (en) | Perovskite SrTiO3 tetragonal nanoparticle preparation method and product | |
| US7651675B2 (en) | Process for producing flaky titanium oxide capable of absorbing visible light | |
| CN100337740C (en) | Crystal titanium dioxide light catalyst and synthesis thereof | |
| CN1305560C (en) | Process for preparing highly efficient titania photocatalyst | |
| CN1530327A (en) | Preparing method for crystalline nanometer titania material with controllable size | |
| CN1363521A (en) | Process for preparing anatase crystal type nano TiO2 | |
| CN1843937A (en) | Method for preparing size-controllable electronic grade anatase titania nanopowder | |
| RU2709506C1 (en) | Method of producing a photocatalyst based on titanium dioxide doped with scandium | |
| CN1597534A (en) | Preparation method of nanometer rutile type titanium dioxide |
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 | ||
| ASS | Succession or assignment of patent right |
Owner name: BEIJING CHEMICAL ENGINEERING UNIV.; HUADA TIANRUI Free format text: FORMER OWNER: HUADA TIANRUI NANO-MATERIAL TECHNOLOGY CO., LTD., BEIJING Effective date: 20060120 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20060120 Address after: 100029, No. 15 East Third Ring Road, Chaoyang District, Beijing Co-patentee after: Huada Tianrui Nano-Material Technology Co., Ltd., Beijing Patentee after: Beijing University of Chemical Technology Address before: 100037 Beijing Institute of chemical management cadre, Haidian District, Beijing (North wa Road) Patentee before: Huada Tianrui Nano-Material Technology Co., Ltd., Beijing |
|
| ASS | Succession or assignment of patent right |
Free format text: FORMER OWNER: HUADA TIANRUI NANO-MATERIAL TECHNOLOGY CO., LTD., BEIJING |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20100512 Address after: 100029 Beijing, North Third Ring Road, No. 15 East Road, Chaoyang District Patentee after: Beijing University of Chemical Technology Address before: 100029 Beijing, North Third Ring Road, No. 15 East Road, Chaoyang District Co-patentee before: Huada Tianrui Nano-Material Technology Co., Ltd., Beijing Patentee before: Beijing University of Chemical Technology |
|
| ASS | Succession or assignment of patent right |
Owner name: JIANGSU KAOPULE NEW MATERIAL CO., LTD. Free format text: FORMER OWNER: BEIJING UNIVERSITY OF CHEMICAL TECHNOLOGY Effective date: 20100617 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 100029 NO.15, NORTH THIRD RING EAST ROAD, CHAOYANG DISTRICT, BEIJING TO: 213315 NO.36, WEISHANHU ROAD, XIXIASHU TOWN, XINBEI DISTRICT, CHANGZHOU CITY, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20100617 Address after: 213315 No. 36, Weishan Lake Road, Xixia villa town, Xinbei District, Jiangsu, Changzhou Patentee after: JIANGSU KAOPULE NEW MATERIAL CO., LTD. Address before: 100029 Beijing, North Third Ring Road, No. 15 East Road, Chaoyang District Patentee before: Beijing University of Chemical Technology |
|
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 213315 No. 36, Weishan Lake Road, Xixia villa town, Xinbei District, Jiangsu, Changzhou Patentee after: Jiangsu Kaopule New Materials Co., Ltd. Address before: 213315 No. 36, Weishan Lake Road, Xixia villa town, Xinbei District, Jiangsu, Changzhou Patentee before: JIANGSU KAOPULE NEW MATERIAL CO., LTD. |
|
| C56 | Change in the name or address of the patentee |
Owner name: JIANGSU KAOPULE NEW MATERIAL CO., LTD. Free format text: FORMER NAME: JIANGSU KAOPULE NEW MATERIAL INC. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 213315 No. 36, Weishan Lake Road, Xixia villa town, Xinbei District, Jiangsu, Changzhou Patentee after: JIANGSU KAOPULE NEW MATERIAL CO., LTD. Address before: 213315 No. 36, Weishan Lake Road, Xixia villa town, Xinbei District, Jiangsu, Changzhou Patentee before: Jiangsu Kaopule New Materials Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20041027 Termination date: 20170301 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |