CN109179495B - Preparation method of high-dispersion nano titanium dioxide - Google Patents
Preparation method of high-dispersion nano titanium dioxide Download PDFInfo
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- CN109179495B CN109179495B CN201810984392.8A CN201810984392A CN109179495B CN 109179495 B CN109179495 B CN 109179495B CN 201810984392 A CN201810984392 A CN 201810984392A CN 109179495 B CN109179495 B CN 109179495B
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000006185 dispersion Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000243 solution Substances 0.000 claims abstract description 38
- 238000004821 distillation Methods 0.000 claims abstract description 29
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 26
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 26
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 24
- 238000005273 aeration Methods 0.000 claims abstract description 22
- 239000011812 mixed powder Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 13
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 235000019441 ethanol Nutrition 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 31
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 19
- 230000035484 reaction time Effects 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 30
- 239000004408 titanium dioxide Substances 0.000 abstract description 15
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 abstract description 11
- 239000002245 particle Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000004887 air purification Methods 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of high-dispersion nano titanium dioxide, which comprises the following steps: step 1, adding tetrabutyl titanate into absolute ethyl alcohol, then adding ethyl cellulose, and carrying out ultrasonic reaction for 30-60min to obtain a titanium alcohol solution; step 2, adding aluminum chloride into the titanic acid solution, stirring at constant temperature until the aluminum chloride is completely dissolved, and then putting the mixture into a distillation reaction kettle for carrying out reduced pressure distillation reaction for 10-30min to obtain a concentrated solution; step 3, heating and distilling the concentrated ammonia water to form ammonia water steam, then introducing the ammonia water steam into the concentrated solution for aeration reaction for 10-20min until no precipitate is generated, and obtaining mixed suspension; step 4, carrying out gradient distillation reaction on the mixed suspension for 4-7h to obtain mixed powder; and 5, dissolving hydrogen chloride in absolute ethyl alcohol to obtain a mixed solution, adding the mixed powder into the mixed solution, performing ultrasonic reaction for 20-30min, filtering, and drying to obtain the nano titanium dioxide powder. The invention solves the problems of uneven granularity and poor photocatalytic activity of titanium dioxide prepared by the prior art.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a preparation method of high-dispersion nano titanium dioxide.
Background
The titanium dioxide photocatalytic material as one of semiconductor photocatalysts is a novel environment-friendly material which is researched most at present, and the property of the photocatalyst is a key factor in the photocatalytic oxidation process. The photocatalytic performance of the titanium dioxide is greatly influenced by factors such as crystal form, grain size, grain diameter, surface state and the like. The nano-particle with large surface area has good catalytic activity and selectivity due to the surface effect and the volume effect. The conduction band energy level and the valence band energy level of the nano titanium dioxide are changed into discrete energy levels due to the quantum size effect, the energy gap is widened, the conduction band potential becomes more negative, and the valence band potential becomes more positive, which means that the nano titanium dioxide has stronger oxidation and reduction capabilities; and because the particle size of the nano particles is small, a photon-generated carrier is easier to migrate to the surface from the inside of the particles than coarse particles, the recombination probability of electrons and holes is obviously reduced, and the photocatalysis performance is also improved. Therefore, the preparation of titanium dioxide having a large specific surface area and a small particle size has been the focus of research in the field of photocatalysis.
With the improvement of living standard of people, environmental materials are paid more attention to by people, and the titanium dioxide photocatalyst has excellent performances of high oxidation activity, strong catalytic performance, stable activity, good moisture resistance, strong sterilization capability and the like, and is widely applied to the aspects of wastewater degradation, harmful gas elimination, sterilization, air purification and the like. However, the existing methods for preparing titanium dioxide powder, such as the traditional solid phase reaction and sintering method, the modern chemical vapor deposition method, the physical vapor deposition method, the chemical vapor infiltration method, the sol-gel method and the like, have the defects of complex process and high cost, and the obtained titanium dioxide powder is often in a mixed crystal form, has uneven granularity and poor photocatalytic degradation activity.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of high-dispersion nano titanium dioxide, which solves the problems of uneven granularity and poor photocatalytic activity of the titanium dioxide prepared by the prior art, and prepares high-dispersion nano titanium dioxide particles by using ethyl cellulose as a dispersing agent and a binder and using aluminum chloride as a settling agent and an agglomeration blocking agent.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of high-dispersion nano titanium dioxide comprises the following steps:
step 1, adding tetrabutyl titanate into absolute ethyl alcohol, then adding ethyl cellulose, and carrying out ultrasonic reaction for 30-60min to obtain a titanium alcohol solution;
step 2, adding aluminum chloride into the titanic acid solution, stirring at constant temperature until the aluminum chloride is completely dissolved, and then putting the mixture into a distillation reaction kettle for carrying out reduced pressure distillation reaction for 10-30min to obtain a concentrated solution;
step 3, heating and distilling the concentrated ammonia water to form ammonia water steam, then introducing the ammonia water steam into the concentrated solution for aeration reaction for 10-20min until no precipitate is generated, and obtaining mixed suspension;
step 4, carrying out gradient distillation reaction on the mixed suspension for 4-7h to obtain mixed powder;
and 5, dissolving hydrogen chloride in absolute ethyl alcohol to obtain a mixed solution, adding the mixed powder into the mixed solution, performing ultrasonic reaction for 20-30min, filtering, and drying to obtain the nano titanium dioxide powder.
The concentration of the n-butyl titanate in the step 1 in the absolute ethyl alcohol is 30-50g/L, and the addition amount of the ethyl cellulose is 80-90% of the mass of the n-butyl titanate.
The temperature of the ultrasonic reaction in the step 1 is 60-70 ℃, and the ultrasonic frequency is 20-40 kHz.
The adding amount of the aluminum chloride in the step 2 is 2-4 times of the mass of the n-butyl titanate.
The pressure of the reduced pressure distillation reaction in the step 2 is 60-80% of the atmospheric pressure, the temperature is 70-90 ℃, and the volume of the concentrated solution is 10-15% of the titanic acid solution.
The heating temperature of the strong ammonia water in the step 3 is 90-95 ℃.
The aeration rate of the aeration reaction in the step 3 is 10-20mL/min, and the aeration temperature is 30-40 ℃.
The procedure of the gradient distillation reaction in step 4 is as follows:
| temperature of | Time |
| 70-80℃ | 0.5-1.0h |
| 100-105℃ | 1-2h |
| 120-130℃ | Time remaining |
The concentration of the hydrogen chloride in the step 5 in the absolute ethyl alcohol is 20-25 g/L.
The concentration of the mixed powder in the mixed solution in the step 5 is 30-40g/L, the temperature of the ultrasonic reaction is 60-70 ℃, the ultrasonic frequency is 50-70kHz, and the drying temperature is 70-90 ℃.
Step 1, dissolving n-butyl titanate in absolute ethyl alcohol to form an alcohol solution; the ethyl cellulose is added into the alcohol solution, can be dissolved in absolute ethyl alcohol, and has good dispersion effect on the n-butyl titanate; the ultrasonic reaction can separate butyl ester groups in the n-butyl titanate, and the ethyl cellulose can form a semi-wrapping characteristic to obtain the titanic acid solution.
And 2, adding aluminum chloride into the titanium alcohol solution, forming a good dissolving system by utilizing the solubility of the aluminum chloride in absolute ethyl alcohol, removing the absolute ethyl alcohol by means of reduced pressure distillation, and compressing the titanic acid solution to form a concentrated solution.
Step 3, heating and distilling the concentrated ammonia water to form mixed gas of ammonia gas and water vapor taking the ammonia gas as a main body, introducing the mixed gas into absolute ethyl alcohol in an aeration mode, wherein the ammonia gas and the water vapor form an ammonia water structure and react with aluminum chloride to obtain ammonium chloride and aluminum hydroxide precipitate, and simultaneously, the water vapor and n-butyl titanate can perform hydrolysis reaction to form butyl ester and titanium dioxide; because the ethyl cellulose can be used as a dispersing agent to disperse titanium dioxide particles and aluminum hydroxide particles, and the ethyl cellulose has certain semi-wrapping property on the titanium dioxide, the problem of agglomeration among the nano titanium dioxide particles is solved.
And 4, adopting a gradient distillation mode to sequentially discharge the absolute ethyl alcohol, the butyl ester, the ammonium chloride and the water vapor, wherein the absolute ethyl alcohol and the butyl ester are preferentially discharged due to different boiling point temperatures, at the moment, the ethyl cellulose is used as a dispersing agent and also used as an adhesive to connect the titanium dioxide and the aluminum hydroxide, and mixed powder with well dispersed titanium dioxide is formed along with the discharge of the water vapor.
And 5, dissolving hydrogen chloride in absolute ethyl alcohol to form a mixed solution, adding the mixed powder into the mixed solution, converting aluminum hydroxide into aluminum chloride by using the hydrogen chloride, dissolving the aluminum chloride in the absolute ethyl alcohol, well dissolving ethyl cellulose in the absolute ethyl alcohol, and obtaining nano titanium dioxide powder by filtering and drying, wherein the nano titanium dioxide is not dissolved in the absolute ethyl alcohol to form a precipitate. The dissolution of the ethyl cellulose in the absolute ethyl alcohol and the dissolution of the aluminum chloride in the absolute ethyl alcohol in the step do not contain other impurities, and the ethyl cellulose and the aluminum chloride can be recycled in the step 1 and the step 2, so that the cost is reduced.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the problems of uneven granularity and poor photocatalytic activity of titanium dioxide prepared by the prior art, and prepares high-dispersity nano titanium dioxide particles by using ethyl cellulose as a dispersing agent and a binder and using aluminum chloride as a settling agent and an agglomeration blocking agent.
2. The invention makes full use of the solubility difference of ethyl cellulose in water and absolute ethyl alcohol, can effectively control the particle size of the nano titanium dioxide and achieve the effect of controllable particle size.
3. The aluminum chloride and the ethyl cellulose in the invention are used as main auxiliary agents and can be recycled, thereby not only ensuring the continuity of industrial continuous production, but also reducing the cost of raw materials and greatly reducing the environmental protection pressure.
Detailed Description
The present invention is described in detail with reference to examples, but the present invention is not limited to the claims.
Example 1
A preparation method of high-dispersion nano titanium dioxide comprises the following steps:
step 1, adding tetrabutyl titanate into absolute ethyl alcohol, then adding ethyl cellulose, and carrying out ultrasonic reaction for 30min to obtain titanium alcohol solution;
step 2, adding aluminum chloride into the titanic acid solution, stirring at constant temperature until the aluminum chloride is completely dissolved, and then putting the mixture into a distillation reaction kettle for carrying out reduced pressure distillation reaction for 10min to obtain a concentrated solution;
step 3, heating and distilling the concentrated ammonia water to form ammonia water steam, then introducing the ammonia water steam into the concentrated solution for aeration reaction for 10min until no precipitate is generated, and obtaining mixed suspension;
step 4, carrying out gradient distillation reaction on the mixed suspension for 4 hours to obtain mixed powder;
and 5, dissolving hydrogen chloride in absolute ethyl alcohol to obtain a mixed solution, adding the mixed powder into the mixed solution, performing ultrasonic reaction for 20min, filtering, and drying to obtain the nano titanium dioxide powder.
The concentration of the n-butyl titanate in the step 1 in the absolute ethyl alcohol is 30g/L, and the adding amount of the ethyl cellulose is 80% of the mass of the n-butyl titanate.
The temperature of the ultrasonic reaction in the step 1 is 60 ℃, and the ultrasonic frequency is 20 kHz.
The adding amount of the aluminum chloride in the step 2 is 2 times of the mass of the n-butyl titanate.
The pressure of the reduced pressure distillation reaction in the step 2 is 60% of the atmospheric pressure, the temperature is 70 ℃, and the volume of the concentrated solution is 10% of the volume of the titanic acid solution.
The heating temperature of the concentrated ammonia water in the step 3 is 90 ℃.
The aeration rate of the aeration reaction in the step 3 is 10mL/min, and the aeration temperature is 30 ℃.
The procedure of the gradient distillation reaction in step 4 is as follows:
| temperature of | Time |
| 70℃ | 0.5h |
| 100℃ | 1h |
| 120℃ | Time remaining |
The concentration of the hydrogen chloride in the absolute ethyl alcohol in the step 5 is 20 g/L.
The concentration of the mixed powder in the mixed solution in the step 5 is 30g/L, the temperature of the ultrasonic reaction is 60 ℃, the ultrasonic frequency is 50kHz, and the drying temperature is 70 ℃.
Example 2
A preparation method of high-dispersion nano titanium dioxide comprises the following steps:
step 1, adding tetrabutyl titanate into absolute ethyl alcohol, then adding ethyl cellulose, and carrying out ultrasonic reaction for 60min to obtain titanium alcohol solution;
step 2, adding aluminum chloride into the titanic acid solution, stirring at constant temperature until the aluminum chloride is completely dissolved, and then putting the mixture into a distillation reaction kettle for carrying out reduced pressure distillation reaction for 30min to obtain a concentrated solution;
step 3, heating and distilling the concentrated ammonia water to form ammonia water steam, then introducing the ammonia water steam into the concentrated solution for aeration reaction for 20min until no precipitate is generated, and obtaining mixed suspension;
step 4, carrying out gradient distillation reaction on the mixed suspension for 7 hours to obtain mixed powder;
and 5, dissolving hydrogen chloride in absolute ethyl alcohol to obtain a mixed solution, adding the mixed powder into the mixed solution, performing ultrasonic reaction for 30min, filtering, and drying to obtain the nano titanium dioxide powder.
The concentration of the n-butyl titanate in the step 1 in the absolute ethyl alcohol is 50g/L, and the adding amount of the ethyl cellulose is 90% of the mass of the n-butyl titanate.
The temperature of the ultrasonic reaction in the step 1 is 70 ℃, and the ultrasonic frequency is 40 kHz.
The adding amount of the aluminum chloride in the step 2 is 4 times of the mass of the n-butyl titanate.
The pressure of the reduced pressure distillation reaction in the step 2 is 80% of the atmospheric pressure, the temperature is 90 ℃, and the volume of the concentrated solution is 15% of the volume of the titanic acid solution.
The heating temperature of the strong ammonia water in the step 3 is 5 ℃.
The aeration rate of the aeration reaction in the step 3 is 20mL/min, and the aeration temperature is 40 ℃.
The procedure of the gradient distillation reaction in step 4 is as follows:
| temperature of | Time |
| 80℃ | 1.0h |
| 105℃ | 2h |
| 130℃ | Time remaining |
The concentration of the hydrogen chloride in the step 5 in the absolute ethyl alcohol is 25 g/L.
The concentration of the mixed powder in the mixed solution in the step 5 is 40g/L, the temperature of the ultrasonic reaction is 70 ℃, the ultrasonic frequency is 70kHz, and the drying temperature is 90 ℃.
Example 3
A preparation method of high-dispersion nano titanium dioxide comprises the following steps:
step 1, adding tetrabutyl titanate into absolute ethyl alcohol, then adding ethyl cellulose, and carrying out ultrasonic reaction for 50min to obtain titanium alcohol solution;
step 2, adding aluminum chloride into the titanic acid solution, stirring at constant temperature until the aluminum chloride is completely dissolved, and then putting the mixture into a distillation reaction kettle for carrying out reduced pressure distillation reaction for 20min to obtain a concentrated solution;
step 3, heating and distilling the concentrated ammonia water to form ammonia water steam, then introducing the ammonia water steam into the concentrated solution for aeration reaction for 15min until no precipitate is generated, and obtaining mixed suspension;
step 4, carrying out gradient distillation reaction on the mixed suspension for 6 hours to obtain mixed powder;
and 5, dissolving hydrogen chloride in absolute ethyl alcohol to obtain a mixed solution, adding the mixed powder into the mixed solution, performing ultrasonic reaction for 25min, filtering, and drying to obtain the nano titanium dioxide powder.
The concentration of the n-butyl titanate in the step 1 in the absolute ethyl alcohol is 40g/L, and the adding amount of the ethyl cellulose is 85% of the mass of the n-butyl titanate.
The temperature of the ultrasonic reaction in the step 1 is 65 ℃, and the ultrasonic frequency is 30 kHz.
The adding amount of the aluminum chloride in the step 2 is 3 times of the mass of the n-butyl titanate.
The pressure of the reduced pressure distillation reaction in the step 2 is 70% of the atmospheric pressure, the temperature is 80 ℃, and the volume of the concentrated solution is 13% of the volume of the titanic acid solution.
The heating temperature of the concentrated ammonia water in the step 3 is 93 ℃.
The aeration rate of the aeration reaction in the step 3 is 15mL/min, and the aeration temperature is 35 ℃.
The procedure of the gradient distillation reaction in step 4 is as follows:
| temperature of | Time |
| 75℃ | 0.8h |
| 103℃ | 2h |
| 125℃ | Time remaining |
The concentration of the hydrogen chloride in the step 5 in the absolute ethyl alcohol is 23 g/L.
The concentration of the mixed powder in the mixed solution in the step 5 is 35g/L, the temperature of the ultrasonic reaction is 65 ℃, the ultrasonic frequency is 60kHz, and the drying temperature is 80 ℃.
Performance testing
The comparative example employed a commercial P25 photocatalyst.
Test method 1 according to the national standard "method for detecting the performance of photocatalytic air purification material
Test method 2 purification test method of photocatalytic material aqueous solution system according to national standard
Test method 3 evaluation of photocatalytic antibacterial material and product antibacterial property according to the national standard
Particle size distribution test
| Particle size | Ratio of | |
| Example 1 | 10-15nm | 97％ |
| Example 2 | 20-30nm | 98％ |
| Example 3 | 5-10nm | 99％ |
| Comparative example | 40-60nm | 87％ |
In summary, the invention has the following advantages:
1. the invention solves the problems of uneven granularity and poor photocatalytic activity of titanium dioxide prepared by the prior art, and prepares high-dispersity nano titanium dioxide particles by using ethyl cellulose as a dispersing agent and a binder and using aluminum chloride as a settling agent and an agglomeration blocking agent.
2. The invention makes full use of the solubility difference of ethyl cellulose in water and absolute ethyl alcohol, can effectively control the particle size of the nano titanium dioxide and achieve the effect of controllable particle size.
3. The aluminum chloride and the ethyl cellulose in the invention are used as main auxiliary agents and can be recycled, thereby not only ensuring the continuity of industrial continuous production, but also reducing the cost of raw materials and greatly reducing the environmental protection pressure.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (9)
1. A preparation method of high-dispersion nano titanium dioxide is characterized by comprising the following steps: the method comprises the following steps:
step 1, adding tetrabutyl titanate into absolute ethyl alcohol, then adding ethyl cellulose, and carrying out ultrasonic reaction for 30-60min to obtain a titanium alcohol solution; the adding amount of the ethyl cellulose is 80-90% of the mass of the n-butyl titanate;
step 2, adding aluminum chloride into the titanium alcohol solution, stirring at constant temperature until the aluminum chloride is completely dissolved, and then putting the mixture into a distillation reaction kettle for carrying out reduced pressure distillation reaction for 10-30min to obtain a concentrated solution; the adding amount of the aluminum chloride is 2-4 times of the mass of the n-butyl titanate;
step 3, heating and distilling the concentrated ammonia water to form ammonia water steam, then introducing the ammonia water steam into the concentrated solution for aeration reaction for 10-20min until no precipitate is generated, and obtaining mixed suspension;
step 4, carrying out gradient distillation reaction on the mixed suspension for 4-7h to obtain mixed powder;
and 5, dissolving hydrogen chloride in absolute ethyl alcohol to obtain a mixed solution, adding the mixed powder into the mixed solution, performing ultrasonic reaction for 20-30min, filtering, and drying to obtain the nano titanium dioxide powder.
2. The method for preparing high-dispersion nano titanium dioxide according to claim 1, wherein the method comprises the following steps: the concentration of the n-butyl titanate in the step 1 in the absolute ethyl alcohol is 30-50 g/L.
3. The method for preparing high-dispersion nano titanium dioxide according to claim 1, wherein the method comprises the following steps: the temperature of the ultrasonic reaction in the step 1 is 60-70 ℃, and the ultrasonic frequency is 20-40 kHz.
4. The method for preparing high-dispersion nano titanium dioxide according to claim 1, wherein the method comprises the following steps: the temperature of the ultrasonic reaction in the step 1 is 60-70 ℃, and the ultrasonic frequency is 20-40 kHz.
5. The method for preparing high-dispersion nano titanium dioxide according to claim 1, wherein the method comprises the following steps: the heating temperature of the strong ammonia water in the step 3 is 90-95 ℃.
6. The method for preparing high-dispersion nano titanium dioxide according to claim 1, wherein the method comprises the following steps: the aeration rate of the aeration reaction in the step 3 is 10-20mL/min, and the aeration temperature is 30-40 ℃.
7. The method for preparing high-dispersion nano titanium dioxide according to claim 1, wherein the method comprises the following steps: the procedure of the gradient distillation reaction in step 4 is as follows: reacting for 0.5-1.0 h at 70-80 ℃; reacting for 1-2 h at the temperature of 100 ℃ and 105 ℃; 120 ℃ and 130 ℃, and the remaining reaction time.
8. The method for preparing high-dispersion nano titanium dioxide according to claim 1, wherein the method comprises the following steps: the concentration of the hydrogen chloride in the step 5 in the absolute ethyl alcohol is 20-25 g/L.
9. The method for preparing high-dispersion nano titanium dioxide according to claim 1, wherein the method comprises the following steps: the concentration of the mixed powder in the mixed solution in the step 5 is 30-40g/L, the temperature of the ultrasonic reaction is 60-70 ℃, the ultrasonic frequency is 50-70kHz, and the drying temperature is 70-90 ℃.
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