CN112158882A - Preparation method of rutile type nano titanium dioxide - Google Patents
Preparation method of rutile type nano titanium dioxide Download PDFInfo
- Publication number
- CN112158882A CN112158882A CN202011048347.5A CN202011048347A CN112158882A CN 112158882 A CN112158882 A CN 112158882A CN 202011048347 A CN202011048347 A CN 202011048347A CN 112158882 A CN112158882 A CN 112158882A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- rutile type
- type nano
- nano titanium
- titanium tetrachloride
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of inorganic chemical industry, and particularly relates to a preparation method of rutile type nano titanium dioxide. The technical problem to be solved by the invention is to provide a method for preparing rutile type nano titanium dioxide, which can control the granularity and crystal form of the titanium dioxide without calcining. The method comprises the following steps: a. under the condition of ice-water bath, adding titanium tetrachloride into water to prepare a titanium tetrachloride solution; b. hydrolyzing titanium tetrachloride solution; c. after hydrolysis, solid-liquid separation is carried out to obtain a precipitate, and rutile type nano titanium dioxide is obtained after washing and drying. The method provided by the invention enables the particle size of the prepared titanium dioxide to be 50-100 nm, the crystal form of the prepared rutile type titanium dioxide to be more than 95%, and the prepared finished product is good in dispersity and stability.
Description
Technical Field
The invention belongs to the technical field of inorganic chemical industry, and particularly relates to a preparation method of rutile type nano titanium dioxide.
Background
Rutile titanium dioxide is widely used in high-grade pigments, cosmetics, and the like. The rutile-type nano titanium dioxide has small particles and large specific surface area, so that the rutile-type nano titanium dioxide has higher chemical activity. The addition of a certain proportion of nano rutile type titanium dioxide can obviously improve the ultraviolet absorptivity, light scattering property, dispersibility, rheological property and other properties of the system, and when the concentration is only 50ppm, the ultraviolet shielding rate of the system can reach more than 99 percent.
At present, the preparation method of the nano rutile titanium dioxide can be classified into two major types, namely a gas phase method and a liquid phase method. The nano rutile type titanium dioxide powder prepared by the vapor phase method has high purity and good dispersibility, but the required equipment is complex, the energy consumption is large, and the cost is high. In contrast, the liquid phase method has the advantages of less equipment investment, simple process, easy operation, low cost and the like, and is a method for preparing the nano rutile titanium dioxide which is widely adopted in laboratories and industries at present. The liquid phase method used at present comprises a sol-gel method and an alkoxide hydrolysis method, and expensive titanium alkoxide is used as a raw material, and the nano rutile titanium dioxide can be obtained only by high-temperature calcination at the temperature of more than 800 ℃. Therefore, the prior preparation method of the nano rutile titanium dioxide has high equipment investment and high operation cost, and the wide application of the product is hindered.
Patent document CN108033484A discloses a nano titanium dioxide with high uniformity and small size, a nano titanium dioxide dispersion liquid, and a preparation method and application thereof. The method comprises the following steps: s1: dissolving titanium tetrachloride in the ice water mixture, and stirring to obtain a clear light yellow clear liquid; s2: adding a surfactant into the clarified liquid obtained in the step S1, stirring and dissolving completely, then dropwise adding ammonia water at the speed of 40-80 mu L/S until the liquid is completely solidified, then adding water, stirring to form a white turbid liquid system, and then dropwise adding ammonia water until the pH value of the system is 6-8; s3: standing and layering the system obtained in the step S2 to obtain white precipitate, washing, centrifuging, drying and grinding to obtain white powder; s4: and calcining the white powder obtained in the step S3 at 350-800 ℃ to obtain the nano titanium dioxide. The white powder prepared by the method needs to be calcined at 350-800 ℃ to obtain the nano titanium dioxide, the energy consumption is large, and the grain size of the obtained nano titanium dioxide is relatively large by calcination.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing rutile type nano titanium dioxide, which can control the granularity and crystal form of the titanium dioxide without calcining.
The invention solves the technical problems by adopting the technical scheme that the invention provides a preparation method of rutile type nano titanium dioxide. The method comprises the following steps:
a. under the condition of ice-water bath, adding titanium tetrachloride into water to prepare a titanium tetrachloride solution;
b. hydrolyzing titanium tetrachloride solution;
c. after hydrolysis, solid-liquid separation is carried out to obtain a precipitate, and rutile type nano titanium dioxide is obtained after washing and drying.
In the preparation method of the rutile type nano titanium dioxide, in the step a, titanium tetrachloride is added into deionized water, and the volume ratio of the titanium tetrachloride to the deionized water is 1: 10.
Wherein, in the preparation method of the rutile type nano titanium dioxide, in the step b, the hydrolysis temperature is 70-75 ℃; the hydrolysis time was 3 h.
And further, in the step b, dropwise adding ammonia water in the hydrolysis process to control the end point pH value of the titanium tetrachloride solution to be 7.5-8.3 when the hydrolysis is carried out for 2 hours, then stopping adding the ammonia water, and continuing to react for 1 hour.
Further, in the step b, the speed of dropwise adding ammonia water is 6.0-9.0 mu L/s; the mass fraction of the ammonia water is 25-28%.
Wherein, in the preparation method of the rutile type nano titanium dioxide, in the step c, the drying temperature is 100-110 ℃; the drying time was 6 h.
The invention has the beneficial effects that:
the method controls the granularity and the crystal form of the titanium dioxide by controlling the dropping speed of the ammonia water and the terminal pH value of the titanium tetrachloride solution when the titanium dioxide is hydrolyzed for 2 hours, so that the granularity of the prepared titanium dioxide is 50-100 nm, the crystal form is more than 95 percent of rutile type titanium dioxide, and the prepared finished product has good dispersity and stability.
Detailed Description
Specifically, the invention provides a preparation method of rutile type nano titanium dioxide. The method comprises the following steps:
a. preparing titanium tetrachloride solution from titanium tetrachloride and deionized water according to the volume ratio of 1:10 under the condition of ice-water bath;
b. hydrolyzing the titanium tetrachloride solution at 70-75 ℃, dropwise adding ammonia water in the hydrolysis process at the speed of 6.0-9.0 mu L/s, controlling the end-point pH value of the titanium tetrachloride solution to be 7.5-8.3 when the titanium tetrachloride solution is hydrolyzed for 2 hours, stopping adding the ammonia water, and continuing to react for 1 hour;
c. after hydrolysis, standing to make the insoluble substance completely precipitate, solid-liquid separating to obtain precipitate, washing, drying at 100-110 deg.C for 6 hr to obtain rutile type nano titanium dioxide.
The invention prepares titanium tetrachloride aqueous solution under the condition of ice water bath (0 ℃), can effectively inhibit the hydrolysis of titanium tetrachloride in the preparation process, hydrolyzes at 70 ℃ -75 ℃, controls the hydrolysis rate and the crystal grain growth degree of titanium tetrachloride by controlling the dropping speed of ammonia water, and ensures that titanium dioxide with rutile type of more than 95% is obtained by controlling the end point pH value. In the present invention, no requirement is made on the pH value during the hydrolysis reaction.
In the step b, the terminal pH value of the solution is controlled to be 7.5-8.3 when the hydrolysis reaction is carried out for 2 hours, the formation of rutile titanium dioxide is facilitated in the pH value range, and the nano titanium dioxide with the rutile content of more than 95% can be obtained. The ammonia addition is stopped and the reaction is continued for 1h to ensure that the hydrolysis reaction can be fully carried out.
The present invention will be further illustrated by the following specific examples.
Example 1
200mL of deionized water is measured in a 500mL beaker by using a measuring cylinder, the beaker is placed in an ice water bath kettle and stirred by using an electric stirrer, the rotating speed is set to be 300 r/min, 20mL of titanium tetrachloride is transferred into the beaker by using a 5mL dropper for four times, and the stirring is carried out for 5 min. Taking out the beaker, placing the beaker in a water bath kettle at 70 ℃, stirring the beaker by using an electric stirrer at the rotating speed of 300 revolutions per minute, dropwise adding 25 to 28 mass percent of ammonia water into the beaker at a constant speed by using a 5mL dropper, wherein the dropwise adding speed of the ammonia water is 6.0 to 9.0 mu L/s, leading the pH value of the solution to be 7.5 when the hydrolysis is carried out for 2 hours, then stopping adding the ammonia water, and continuing to hydrolyze for 1 hour. The beaker was taken out and allowed to stand at room temperature for 15 minutes, the supernatant was decanted, and the precipitate was washed three times with deionized water, then dried at 100 ℃ for 6 hours in a forced air drying oven, and then ground with an agate mortar to obtain a white powder. The obtained rutile type nano titanium dioxide with the content of more than 95 percent has the grain size of 50-100 nm.
Example 2
200mL of deionized water is measured in a 500mL beaker by using a measuring cylinder, the beaker is placed in an ice water bath kettle and stirred by using an electric stirrer, the rotating speed is set to be 300 r/min, 20mL of titanium tetrachloride is transferred into the beaker by using a 5mL dropper for four times, and the stirring is carried out for 5 min. Taking out the beaker, placing the beaker in a water bath kettle at 70 ℃, stirring the beaker by using an electric stirrer at the rotating speed of 300 revolutions per minute, dropwise adding 25 to 28 mass percent of ammonia water into the beaker by using a 5mL dropper at a constant speed, wherein the dropwise adding speed of the ammonia water is 6.0 to 9.0 mu L/s, leading the pH value of the solution to be 8.0 when the hydrolysis is carried out for 2 hours, then stopping adding the ammonia water, and continuing to hydrolyze for 1 hour. The beaker was taken out and allowed to stand at room temperature for 15 minutes, the supernatant was decanted, and the precipitate was washed three times with deionized water, then dried at 100 ℃ for 6 hours in a forced air drying oven, and then ground with an agate mortar to obtain a white powder. The obtained rutile type nano titanium dioxide with the content of more than 95 percent has the grain size of 50-100 nm.
Example 3
200mL of deionized water is measured in a 500mL beaker by using a measuring cylinder, the beaker is placed in an ice water bath kettle and stirred by using an electric stirrer, the rotating speed is set to be 300 r/min, 20mL of titanium tetrachloride is transferred into the beaker by using a 5mL dropper for four times, and the stirring is carried out for 5 min. Taking out the beaker, placing the beaker in a water bath kettle at 75 ℃, stirring the beaker by using an electric stirrer at the rotating speed of 300 revolutions per minute, dropwise adding 25 to 28 mass percent of ammonia water into the beaker by using a 5mL dropper at a constant speed, wherein the dropwise adding speed of the ammonia water is 6.0 to 9.0 mu L/s, leading the pH value of the solution to be 8.0 when the hydrolysis is carried out for 2 hours, then stopping adding the ammonia water, and continuing to hydrolyze for 1 hour. The beaker was taken out and allowed to stand at room temperature for 15 minutes, the supernatant was decanted, and the precipitate was washed three times with deionized water, then dried at 110 ℃ for 6 hours in a forced air drying oven, and then ground with an agate mortar to obtain a white powder. The obtained rutile type nano titanium dioxide with the content of more than 95 percent has the grain size of 50-100 nm.
Claims (6)
1. The preparation method of the rutile type nano titanium dioxide is characterized by comprising the following steps: the method comprises the following steps:
a. under the condition of ice-water bath, adding titanium tetrachloride into water to prepare a titanium tetrachloride solution;
b. hydrolyzing titanium tetrachloride solution;
c. after hydrolysis, solid-liquid separation is carried out to obtain a precipitate, and rutile type nano titanium dioxide is obtained after washing and drying.
2. The method for preparing rutile type nano titanium dioxide as claimed in claim 1, wherein: in the step a, titanium tetrachloride is added into deionized water, and the volume ratio of the titanium tetrachloride to the deionized water is 1: 10.
3. The method for producing rutile-type nano titanium dioxide according to claim 1 or 2, characterized in that: in the step b, the hydrolysis temperature is 70-75 ℃; the hydrolysis time was 3 h.
4. The method for preparing rutile type nano titanium dioxide as claimed in claim 1, wherein: and in the step b, dropwise adding ammonia water in the hydrolysis process to control the end point pH value of the titanium tetrachloride solution to be 7.5-8.3 when the hydrolysis is carried out for 2 hours, then stopping adding the ammonia water, and continuing to react for 1 hour.
5. The method for preparing rutile type nano titanium dioxide as claimed in claim 4, wherein: in the step b, the speed of dropwise adding ammonia water is 6.0-9.0 mu L/s; the mass fraction of the ammonia water is 25-28%.
6. The method for preparing rutile type nano titanium dioxide as claimed in claim 1, wherein: in the step c, the drying temperature is 100-110 ℃; the drying time was 6 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011048347.5A CN112158882A (en) | 2020-09-29 | 2020-09-29 | Preparation method of rutile type nano titanium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011048347.5A CN112158882A (en) | 2020-09-29 | 2020-09-29 | Preparation method of rutile type nano titanium dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112158882A true CN112158882A (en) | 2021-01-01 |
Family
ID=73862060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011048347.5A Pending CN112158882A (en) | 2020-09-29 | 2020-09-29 | Preparation method of rutile type nano titanium dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112158882A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1440930A (en) * | 2002-02-26 | 2003-09-10 | 舟山明日纳米材料有限公司 | Prepn process of nano rutile-type titania |
| CN1490249A (en) * | 2002-10-15 | 2004-04-21 | 北京化工大学 | Preparing method for nano titanium dioxide |
| CN101007655A (en) * | 2007-01-22 | 2007-08-01 | 河北师范大学 | Process for preparing rutile phase spherical nano TiO2 |
| CN101698507A (en) * | 2009-11-23 | 2010-04-28 | 江苏河海纳米科技股份有限公司 | Method for quickly preparing rutile phase nano titanium dioxide |
| CN108033484A (en) * | 2017-11-01 | 2018-05-15 | 肇庆市华师大光电产业研究院 | A kind of high uniformity and small size nano-titanium dioxide, nano titanium oxide dispersion and its preparation method and application |
| CN108455665A (en) * | 2018-04-08 | 2018-08-28 | 攀钢集团攀枝花钢铁研究院有限公司 | The method that successive reaction prepares rutile type nano titanic oxide |
-
2020
- 2020-09-29 CN CN202011048347.5A patent/CN112158882A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1440930A (en) * | 2002-02-26 | 2003-09-10 | 舟山明日纳米材料有限公司 | Prepn process of nano rutile-type titania |
| CN1490249A (en) * | 2002-10-15 | 2004-04-21 | 北京化工大学 | Preparing method for nano titanium dioxide |
| CN101007655A (en) * | 2007-01-22 | 2007-08-01 | 河北师范大学 | Process for preparing rutile phase spherical nano TiO2 |
| CN101698507A (en) * | 2009-11-23 | 2010-04-28 | 江苏河海纳米科技股份有限公司 | Method for quickly preparing rutile phase nano titanium dioxide |
| CN108033484A (en) * | 2017-11-01 | 2018-05-15 | 肇庆市华师大光电产业研究院 | A kind of high uniformity and small size nano-titanium dioxide, nano titanium oxide dispersion and its preparation method and application |
| CN108455665A (en) * | 2018-04-08 | 2018-08-28 | 攀钢集团攀枝花钢铁研究院有限公司 | The method that successive reaction prepares rutile type nano titanic oxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103435096B (en) | Method for preparing size controllable nano stannic oxide | |
| CN1281507C (en) | Method for repairing nano stick of zinc oxide in even diameter | |
| CN102730754A (en) | Preparation method of aqueous nano-TiO2 colloid | |
| CN112209440A (en) | Process for preparing M-phase vanadium dioxide nano powder | |
| CN112266244A (en) | Preparation method of high-sintering-activity zirconium oxide powder | |
| CN103435097B (en) | Preparation method and application of nano zirconia | |
| CN108516578A (en) | A kind of sub-micron indium oxide raw powder's production technology | |
| CN113044879B (en) | Method for improving quality of titanium dioxide by sulfuric acid method | |
| CN108083334A (en) | A kind of preparation method of monodisperse spherical nano zirconium dioxide powder body material | |
| CN103708548A (en) | Method for synthetizing monoclinic crystal zirconium dioxide nanoparticles between oil water interfaces by using seed crystal method | |
| CN112209438A (en) | Method for preparing nano vanadium dioxide from ethylene glycol vanadyl | |
| CN112158882A (en) | Preparation method of rutile type nano titanium dioxide | |
| CN112158883A (en) | Process for preparing vanadium dioxide nano powder | |
| CN114671460B (en) | Method for removing impurities from industrial meta-titanic acid in sulfuric acid method titanium dioxide short-process technology | |
| CN110482584B (en) | Method for preparing spherical calcium carbonate by using egg shells | |
| CN108455665A (en) | The method that successive reaction prepares rutile type nano titanic oxide | |
| CN1206021C (en) | Collosol gel production method of nano NiO material | |
| CN101759228B (en) | Preparation method for microemulsion solvent thermosynthesis of monodisperse titanium dioxide nanocrystalline | |
| CN100392023C (en) | Nanometer rutile titania sedimentation for preparing mica titanium nanometer composite material | |
| CN1257841C (en) | Prepn process of nano rutile-type titania | |
| CN102211776A (en) | Preparation method of spherical pyrophyllite micro powder | |
| CN112209389A (en) | Preparation method of superfine nano silicon dioxide spheres | |
| CN112266019A (en) | Method for preparing M-phase vanadium dioxide by single ultrasonic atomization homogeneous precipitation method | |
| CN104211112B (en) | Epigranular micro/nano TiO2 spherical particle, and preparation method and application thereof | |
| CN112174205A (en) | Vanadyl hydroxide stabilized ethanol solution dispersion system and preparation of M-phase VO by using same2Method for preparing nano powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210101 |
|
| RJ01 | Rejection of invention patent application after publication |