CN111533166A - Method for preparing organic silicon modified rutile type titanium dioxide by titanium tetrachloride coprecipitation method - Google Patents
Method for preparing organic silicon modified rutile type titanium dioxide by titanium tetrachloride coprecipitation method Download PDFInfo
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- CN111533166A CN111533166A CN202010278225.9A CN202010278225A CN111533166A CN 111533166 A CN111533166 A CN 111533166A CN 202010278225 A CN202010278225 A CN 202010278225A CN 111533166 A CN111533166 A CN 111533166A
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- titanium dioxide
- titanium tetrachloride
- coprecipitation
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- organic silicon
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 34
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 title claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 23
- 239000010703 silicon Substances 0.000 title claims abstract description 23
- 238000000975 co-precipitation Methods 0.000 title claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 16
- 239000004408 titanium dioxide Substances 0.000 title claims description 9
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 6
- 229910003074 TiCl4 Inorganic materials 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 22
- -1 silicon modified rutile titanium dioxide Chemical class 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract description 2
- 230000023556 desulfurization Effects 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for preparing organic silicon modified rutile titanium dioxide by a titanium tetrachloride coprecipitation method, which comprises the following steps: (1) preparation of titanium tetrachloride aqueous solution: preparing analytically pure TiCl4 into an aqueous solution with the concentration of 180-220g/l calculated by TiO2, (2) coprecipitation: adding 5 percent tetraethoxysilane into the prepared titanium tetrachloride water solution, adding ammonia water as a precipitator, and slowly stirring for 1h, (3) filtering and washing: filtering and washing the precipitate prepared in the step (2) to be clean; (4) and (3) calcining: the washed product is calcined for 2 hours at 400 ℃, 600 ℃ and 800 ℃. The invention has the advantages that the prepared catalyst has strong activity, large specific surface area, good thermal stability and high conversion rate of the rutile titanium dioxide at low temperature, thereby having good desulfurization and denitrification effects, and simultaneously being simpler than the preparation method for preparing the rutile titanium dioxide by a sulfuric acid method.
Description
Technical Field
The invention relates to the field of rutile titanium dioxide production, in particular to a method for preparing organic silicon modified rutile titanium dioxide by a titanium tetrachloride coprecipitation method.
Background
The ilmenite resources in China are extremely rich, the process used for producing the titanium dioxide basically adopts a sulfuric acid method, and most manufacturers can only produce acute products which have low added value and are in a nearly saturated state in the market. The refractive index of rutile titanium dioxide is 2.73, the rutile titanium dioxide is the highest in white dyes, the rutile titanium dioxide has high covering rate, good tinting strength and stable photochemical performance, is the white pigment which is most widely applied, is used in the fields of coatings, plastics, papermaking, chemical fibers, printing ink and enamel, has large market demand, basically depends on purchasing products in the United states and Japan to meet the needs of domestic markets, and needs to spend a large amount of foreign exchange every year.
Although individual manufacturers in China can also produce rutile type titanium dioxide, the specific surface area is small, and the low conversion rate below 600 ℃ becomes one of the bottlenecks restricting the production of the product.
Disclosure of Invention
The invention aims to solve the technical problems that the specific surface area of rutile titanium dioxide is small, and the conversion rate of the rutile titanium dioxide at low temperature is low, and provides a method for preparing organic silicon modified rutile titanium dioxide by a titanium tetrachloride coprecipitation method.
The technical scheme of the invention is as follows: a method for preparing organic silicon modified rutile titanium dioxide by a titanium tetrachloride coprecipitation method comprises the following steps:
(1) preparation of titanium tetrachloride aqueous solution: analytically pure TiCl4Preparing into aqueous solution with TiO concentration2180-220g/l;
(2) coprecipitation: adding 5% of organic silicon into the prepared titanium tetrachloride water solution, adding ammonia water as a precipitator, and slowly stirring for 1h;
(3) filtering and washing: filtering and washing the precipitate prepared in the step (2) to be clean;
(4) and (3) calcining: the washed product is calcined for 2 hours at 400 ℃, 600 ℃ and 800 ℃.
The organosilicon in the scheme is tetraethoxysilane.
The invention has the advantages that the prepared catalyst has strong activity, large specific surface area, good thermal stability and high conversion rate of the rutile titanium dioxide at low temperature, thereby having good desulfurization and denitrification effects, and simultaneously being simpler than the preparation method for preparing the rutile titanium dioxide by a sulfuric acid method.
Detailed Description
The technical solution of the present invention is clearly and completely described below with reference to the following embodiments. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments based on the embodiments in the present invention, without any inventive work, will be apparent to those skilled in the art from the following description.
Example 1: a method for preparing organic silicon modified rutile titanium dioxide by a titanium tetrachloride coprecipitation method comprises the following steps:
(1) preparation of titanium tetrachloride aqueous solution: analytically pure TiCl4Preparing into aqueous solution with TiO concentration2The reaction in the step is violent, a large amount of HCl gas is generated and must be carried out in a ventilation kitchen, and the adding speed of distilled water must be slow;
(2) coprecipitation: adding 5% tetraethoxysilane into the prepared titanium tetrachloride water solution, adding ammonia water as a precipitator, and slowly stirring for 1h;
(3) filtering and washing: filtering and washing the precipitate prepared in the step (2) to be clean;
(4) and (3) calcining: the washed product is calcined for 2 hours at 400 ℃, 600 ℃ and 800 ℃.
Comparative example 2
The method for preparing the inorganic silicon modified rutile titanium dioxide by the titanium tetrachloride coprecipitation method comprises the following steps:
(1) preparation of titanium tetrachloride aqueous solution: analytically pure TiCl4 was prepared as an aqueous solution with a concentration of around 200g/l (calculated as TiO 2). The reaction of the step is violent, a large amount of HCl gas is generated and must be carried out in a ventilation kitchen, and the adding speed of distilled water must be slow;
(2) coprecipitation: adding 5% inorganic silicon into the prepared titanium tetrachloride water solution, adding ammonia water as a precipitator, and slowly stirring for 1h;
(3) filtering and washing: filtering and washing the precipitate prepared in the step (2) to be clean;
(4) and (3) calcining: the washed product is calcined for 2 hours at 400 ℃, 600 ℃ and 800 ℃.
Comparative example 3
The method for preparing the organic silicon modified rutile type titanium dioxide by the sulfuric acid method comprises the following steps:
(1) preparing rutile type titanium dioxide by a sulfuric acid method: adding 5% of calcined seed crystal into 500mL of metatitanic acid dihydrate, and stirring for 2h;
(2) adding 5% tetraethoxysilane into metatitanic acid in the step, continuously stirring for 2 hours, and adjusting the pH value to 8.5 by using ammonia water;
(3) and (3) filtering: filtering the metatitanic acid prepared in the step (2);
(4) and (3) calcining: calcining the filtered product at 400 ℃, 600 ℃ and 800 ℃ for 2h respectively.
Comparative example 4
The method for preparing the inorganic silicon modified rutile titanium dioxide by the sulfuric acid method comprises the following steps:
(1) preparing rutile type titanium dioxide by a sulfuric acid method: adding 5% of calcined seed crystal into 500mL of metatitanic acid dihydrate, and stirring for 2h;
(2) adding 5% of inorganic silicon into metatitanic acid in the step, continuously stirring for 2 hours, and adjusting the pH value to 7 by using ammonia water;
(3) and (3) filtering: filtering the metatitanic acid prepared in the step (2);
(4) and (3) calcining: calcining the filtered product at 400 ℃, 600 ℃ and 800 ℃ for 2h respectively.
The specific properties of the catalysts prepared in example 1 and comparative examples 2 to 4 were measured as follows:
| different silicon sources | Specific surface area at 400 DEG C | Specific surface area of 600 DEG C | Specific surface area of 800 DEG C |
| Titanium tetrachloride coprecipitation (organosilicon) | 83.49 | 72.37 | 68.56 |
| Titanium tetrachloride coprecipitation (inorganic silicon) | 81.34 | 50.65 | 34.24 |
| Sulfuric acid process (organosilicon) | 80.16 | 65.15 | 55.74 |
| Sulfuric acid process (inorganic silicon) | 137.9 | 86.28 | 11.01 |
TABLE 1
As can be seen from Table 1, the loading mechanism of the invention is that tetraethoxysilane is hydrolyzed and coprecipitated by ammonia water to form silica gel which is attached to titanium dioxide, and the finished product obtained by loading organic silicon by a titanium tetrachloride coprecipitation method has larger specific surface area than inorganic silicon and finished products obtained by a sulfuric acid method, because the organic silicon has larger bond energy, high thermal stability and is not easy to decompose, the trend of the change of the specific surface area is slower when the temperature is increased from 400 ℃ to 800 ℃, and the inorganic silicon mainly has weaker bonding force between si-o bonds and has lower thermal stability.
The rutile titanium dioxide has stable structure, silicon has catalytic property, and the specific surface is stable under high-temperature calcination, which shows that the thermal stability and the catalytic activity are good.
TABLE 2
As can be seen from Table 2, the rutile conversion ratio of example 1 of the present invention is slightly higher than that of comparative example 2, and is much higher than that of comparative examples 3-4. The sulfuric acid method preparation needs to control the seed crystal addition amount and the acid-soluble alkali-soluble temperature, and metatitanic acid is converted into orthotitanic acid, so that the variables are too large and are not easy to control.
Claims (2)
1. The method for preparing the organic silicon modified rutile type titanium dioxide by the titanium tetrachloride coprecipitation method is characterized by comprising the following steps: it comprises the following steps:
(1) preparation of titanium tetrachloride aqueous solution: analytically pure TiCl4Preparing into aqueous solution with TiO concentration2180-220g/l;
(2) coprecipitation: adding 5% of organic silicon into the prepared titanium tetrachloride water solution, adding ammonia water as a precipitator, and slowly stirring for 1h;
(3) filtering and washing: filtering and washing the precipitate prepared in the step (2) to be clean;
(4) and (3) calcining: the washed product is calcined for 2 hours at 400 ℃, 600 ℃ and 800 ℃.
2. The process for producing an organosilicon-modified rutile titanium dioxide by coprecipitation of titanium tetrachloride according to claim 1, wherein: the silicone is tetraethoxysilane.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010278225.9A CN111533166A (en) | 2020-04-10 | 2020-04-10 | Method for preparing organic silicon modified rutile type titanium dioxide by titanium tetrachloride coprecipitation method |
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| CN202010278225.9A CN111533166A (en) | 2020-04-10 | 2020-04-10 | Method for preparing organic silicon modified rutile type titanium dioxide by titanium tetrachloride coprecipitation method |
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Citations (9)
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|---|---|---|---|---|
| CN1381531A (en) * | 2002-04-19 | 2002-11-27 | 中山大学 | Controllable bionic process for preparing spherical rutile-type nano TiO2 |
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| CN1706749A (en) * | 2004-06-11 | 2005-12-14 | 刘文泉 | Synthesis process of high-adsorption nanometer TiO2 powder in solution |
| CN102218305A (en) * | 2011-04-21 | 2011-10-19 | 江苏大学 | Method for preparing rutile-type porous TiO2 nanometer photocatalyst at room temperature |
| CN102849794A (en) * | 2012-08-30 | 2013-01-02 | 北京工业大学 | Preparation method for Ti-O Magneli phase compound with high specific surface area |
| US20130143729A1 (en) * | 2010-08-17 | 2013-06-06 | Takanori MORITA | Process for producing dispersion of particles of rutile titanium oxide |
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-
2020
- 2020-04-10 CN CN202010278225.9A patent/CN111533166A/en active Pending
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