CN109850939B - Preparation method of disordered mesoporous nano titanium dioxide - Google Patents
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Abstract
The invention relates to a preparation method of disordered mesoporous nano titanium dioxide, which comprises the following steps: a, taking titanium acidolysis solution in the production of titanium dioxide by a sulfuric acid method, adding part of the titanium acidolysis solution into sodium hydroxide solution, and stirring to obtain primary mixed solution; b, adding the residual titanium acidolysis solution into the mixed solution, and stirring to obtain a secondary mixed solution; heating the white suspension to boiling, filtering and washing after heat preservation to obtain a filter cake, and pulping the filter cake to obtain slurry; e, heating the slurry, adding ammonia water, adjusting the pH value to 5.0-8.0, dehydrating the sol, and then putting the sol into a muffle furnace for calcining to obtain granular titanium dioxide; and f, crushing the granular titanium dioxide to obtain the disordered mesoporous nano titanium dioxide with the annular structure. The method has the advantages of simple operation, low cost, no pollution and easy realization of industrialization.
Description
Technical Field
The invention particularly relates to a preparation method of disordered mesoporous nano titanium dioxide, and belongs to the technical field of preparation of denitration honeycomb catalyst carriers.
Background
TiO2Has high chemical stability, corrosion resistance and toxicity resistance, and shows great potential and long life as a catalyst carrier material. From the current research reports, the research on the preparation of mesoporous titanium dioxide has been conducted through the preparation of amorphous mesoporous titanium dioxide and the preparation of semi-crystalline mesoporous titanium dioxide, and the current research focuses on the research of ordered mesoporous titanium dioxide with a highly crystalline framework structure. However, in some catalytic reactions, the ordered pore channels of the catalyst are not favorable for the diffusion of reactants, so that the catalytic activity of the catalyst is low. No matter in the preparation or catalytic application of the mesoporous catalyst, how to solve the problem of diffusion of substances in mesoporous channels is the key of the development of the mesoporous catalyst. This requires TiO as a catalyst support2Having a disordered mesoporous structure, i.e. poresThe channel is formed by stacking particles, the pore size distribution is wide, the pore channel shape is complex and irregular, and the pore channel is not communicated with each other.
The titanium dioxide with the disordered mesoporous structure has high specific surface area and proper pore size, can provide more adsorption sites in SCR catalysis, enables reactants to be gathered on the surface of the catalyst, and improves the contact probability of the reactants and an active center. Meanwhile, compared with a catalyst carrier with an ordered mesoporous structure, the problem of diffusion of reactants in mesoporous channels is solved, and the catalytic efficiency is obviously improved. In addition, the titanium dioxide with the disordered mesoporous structure has high mechanical strength and high thermal stability, can be loaded on metal plates, ceramics and glass fiber base materials to be made into a plate shape, a honeycomb shape or a corrugated plate shape, and is finally integrated in a steel shell to form the whole SCR reactor.
Chinese patent 201711450236.5 discloses a highly effective mesoporous nano TiO2The mesoporous nano TiO with ordered mesoporous channels is prepared by taking a butyl titanate TBOT solution, polyethylene glycol 400 and cetyl trimethyl ammonium bromide CTAB as raw materials2The mesoporous nano TiO2The latex paint has strong reinforcement and high catalytic activity, enhances the stability of a latex paint film, has a strong effect of killing bacteria in indoor air, endows the latex paint with long-acting antibacterial and bactericidal effects, and effectively improves the indoor sanitary condition. But the mesoporous nano TiO2The raw material requirement is high in the preparation process, and the prepared mesoporous micro-ordered pore channel is not beneficial to rapid diffusion of reactants in the denitration catalyst under a high-temperature condition and is not suitable for a carrier of the denitration catalyst.
Chinese patent 201610077118.3 discloses a preparation method of a two-dimensional layered titanium dioxide nano photocatalytic material, which prepares a layered titanium dioxide photocatalyst in a polytetrafluoroethylene high-pressure reaction kettle by a coprecipitation method and a hydrothermal method. In the process of preparing the nano titanium dioxide, NaOH is used as a raw material, Na ions are introduced, the method is unfavorable for denitration catalysts, the prepared titanium dioxide is of a layered structure, the diffusion of reactants in the denitration catalytic reaction process is not facilitated, the requirement on equipment is high, the consumed time is long, and the industrialization is not easy to realize. The nano titanium dioxide prepared by the method is used for photocatalysis and is not suitable for denitration catalysts.
Chinese patent 201510378201.X discloses TiO2The preparation method of the hollow all-mesoporous nanofiber comprises the step of preparing the hollow all-mesoporous nanofiber, wherein the nanofiber has a porous structure comprising mesopores and has both a hollow structure and an all-mesoporous structure. According to the invention, a proper amount of paraffin oil is added, and through electrostatic spinning, the precursor is coated inside by a continuous phase under the action of electrostatic force, so that TiO which has both hollow and full mesopores is effectively synthesized2Nano fiber, full mesoporous nano fiber TiO synthesized by the method2Although the photocatalyst is applied to hydrogen production by photolysis of water and has excellent high efficiency and stability, the photocatalyst is not suitable for a denitration catalyst, the synthesis process is complex, the requirement on equipment precision is high, and industrialization is not easy to realize.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of disordered mesoporous nano titanium dioxide, which comprises the following steps:
a, heating acidolysis titanium liquid in the production of titanium dioxide by a sulfuric acid method to 70-90 ℃, adding part of the acidolysis titanium liquid into sodium hydroxide solution at 70-90 ℃, stirring, heating to 90-120 ℃, and keeping the temperature for 0-30min to obtain primary mixed liquid;
b, adding the residual titanium acidolysis solution obtained in the step a into the mixed solution obtained in the step a, and stirring to obtain a secondary mixed solution;
c, heating the secondary mixed solution obtained in the step b to boiling, keeping the temperature until the solution turns grey, and standing for 10-60 min to obtain a white suspension;
d, stirring the white suspension obtained in the step c, heating to boil, preserving heat for 2-4 h, filtering and washing to obtain a filter cake, and pulping the filter cake to obtain slurry;
e, heating the slurry obtained in the step d to 60-120 ℃, adding ammonia water, adjusting the pH value to 5.0-8.0, observing the slurry to form a sol state, preserving the temperature for 2-6h, dehydrating the sol, and calcining the sol in a muffle furnace at 400-600 ℃ to obtain granular titanium dioxide;
f, crushing the granular titanium dioxide obtained in the step e to obtain the disordered mesoporous nano titanium dioxide with the annular structure.
Further, the titanium solution acidolyzed in the step a is prepared, wherein TiO is2The concentration of (A) is 180g/L-210 g/L; ti3+The concentration of (A) is 0.7-2.7 g/L; fe2+With TiO2The mass ratio of (A) to (B) is 0.25-0.35; f value is 1.55-2.00; the specific gravity is 1.521-1.552g/cm3。
Further, the mass concentration of the sodium hydroxide in the step a is 8-16%.
Further, the total volume ratio of the sodium hydroxide solution to the titanium acidolysis solution in the step a is 100: 300-200: 300.
The invention has the following advantages: 1. the method takes black titanium liquid produced by titanium white by a sulfuric acid method as a raw material, the raw material is cheap and easy to obtain, the concentration of sodium hydroxide and titanyl sulfate is required, ammonia water is added in the process of preparing the denitration titanium dioxide to form sol by adjusting the volume ratio of the sodium hydroxide to the titanyl sulfate, and the amorphous mesoporous nano titanium dioxide with the annular structure for the denitration catalyst is prepared by dehydration and calcination.
2. The diameter of the disordered mesoporous nano titanium dioxide prepared by the method can be controlled to be about 20nm, the pore diameter distribution is narrow, and the powder morphology is a uniformly dispersed annular structure. The disordered mesoporous titanium dioxide has high specific surface area and proper pore size, can provide more adsorption sites in SCR catalysis, enables reactants to be gathered on the surface of the catalyst, and improves the contact probability of the reactants and active centers.
3. The method has low requirement on equipment, the prepared disordered mesoporous nano titanium dioxide has uniform particle size distribution and uniformly dispersed annular structure, and is beneficial to the diffusion of reactants in mesoporous channels, the catalytic activity of the catalyst is improved, the shrinkage rate of the denitration catalyst is reduced, the yield of the catalyst is improved, the method is suitable for the extrusion and molding processes of the denitration catalyst, and the mechanical strength and the thermal stability of the catalyst are improved.
4. The method is based on industrial raw materials, is simple to operate, has short process flow, causes little pollution to the environment and is easy to realize industrial production.
Drawings
FIG. 1 is a scanning electron microscope image of disordered mesoporous nano titanium dioxide prepared in example 1;
FIG. 2 is a scanning electron microscope image of the disordered mesoporous nano titanium dioxide prepared in example 2;
FIG. 3 is a scanning electron microscope image of the disordered mesoporous nano-titania prepared in example 3.
Detailed Description
Example 1
a, taking TiO meeting the titanium liquid index2:180g/L；Ti3+:0.7g/L；Fe2+0.25 parts of/TiO 2; f value: 1.55; specific gravity: 1.521g/cm3Heating the industrial-grade titanium liquid to 70 ℃;
b, preparing 8% sodium hydroxide, and heating to 70 ℃;
c, adding the 1/10 titanium solution in the step a into a sodium hydroxide solution, stirring uniformly, raising the temperature to 90 ℃, preserving heat for 15min, and curing;
d in this example as NaOH: TiO22Mixing industrial-grade titanium solution and sodium hydroxide solution in a ratio of 100:300 (volume ratio);
e, adding the residual titanium liquid obtained in the step a into the mixed liquid obtained in the step c, and uniformly mixing;
f, heating the mixed solution obtained in the step e to boiling, keeping the temperature until the solution turns to be ash, and stopping stirring for 10 min;
g, starting stirring the white suspension liquid obtained in the step f, heating to boil, and keeping the temperature for 2 hours;
h, washing the materials reacted in the step g with water, preparing slurry from a filter cake, heating to 80 ℃, adding ammonia water, adjusting the pH to 5.0, observing the slurry to form a sol state, preserving the temperature for 2h, dehydrating the solution, and then putting the solution into a muffle furnace to calcine for 2h at 400 ℃;
and i, crushing the granular titanium dioxide obtained in the step h to obtain the disordered mesoporous nano titanium dioxide with the annular structure.
And j, detecting the morphology of the powder by using a scanning electron microscope for the disordered mesoporous nano titanium dioxide prepared in the step i.
Example 2
a, taking TiO meeting the titanium liquid index2:190g/L；Ti3+:0.9g/L；Fe2+/TiO20.31; f value: 1.80; specific gravity: 1.525, heating to 85 ℃;
b, preparing 16% sodium hydroxide, and heating to 80 ℃;
c, adding the 1/10 titanium solution in the step a into a sodium hydroxide solution, stirring uniformly, raising the temperature to 100 ℃, preserving heat for 15min, and curing;
d in this example as NaOH: TiO22Mixing the industrial-grade titanium solution and the sodium hydroxide solution in a ratio of 140: 300 (volume ratio);
e, adding the residual titanium liquid in the step a into the mixed liquid in the step c, stirring for 15min, and uniformly mixing;
f, heating the mixed solution obtained in the step e to boiling, keeping the temperature until the solution turns grey, and stopping stirring for 30 min;
g, starting stirring the white suspension liquid obtained in the step f, heating to boil, and preserving heat for 3 hours;
h, washing the materials reacted in the step g with water, preparing slurry from a filter cake, heating to 60 ℃, adding ammonia water, adjusting the pH to 7.2, observing the slurry to form a sol state, preserving the temperature for 3h, dehydrating the solution, and then putting the solution into a muffle furnace to calcine for 2h at 480 ℃;
and i, crushing the granular titanium dioxide obtained in the step h to obtain the disordered mesoporous nano titanium dioxide with the annular structure.
And (e) detecting the morphology of the powder by using a scanning electron microscope for the disordered mesoporous nano titanium dioxide prepared in the step (i).
Example 3
a, taking TiO meeting the titanium liquid index2:210g/L；Ti3+:2.7g/L；Fe2+/TiO20.35; f value: 2.00; specific gravity: 1.552 of industrial-grade titanium liquid, and heating to 90 ℃;
b, preparing 16% sodium hydroxide, and heating to 90 ℃;
c, adding the 1/10 titanium solution in the step a into a sodium hydroxide solution, uniformly stirring, raising the temperature to 120 ℃, and preserving heat for 30min for curing;
d in this example as NaOH: TiO22Mixing industrial-grade titanium solution and sodium hydroxide solution in a ratio of 200:300 (volume ratio);
e, adding the residual titanium liquid in the step a into the mixed liquid in the step c, stirring for 15min, and uniformly mixing;
f, heating the mixed solution obtained in the step e to boiling, keeping the temperature until the solution turns grey, and stopping stirring for 60 min;
g, starting stirring the white suspension liquid obtained in the step f, heating to boil, and keeping the temperature for 4 hours;
h, washing the materials reacted in the step g with water, preparing slurry from a filter cake, heating to 120 ℃, adding ammonia water, adjusting the pH to 8.0, observing the slurry to form a sol state, preserving the temperature for 6h, dehydrating the solution, and then putting the solution into a muffle furnace to calcine for 2h at 600 ℃;
and i, crushing the granular titanium dioxide obtained in the step h to obtain the disordered mesoporous nano titanium dioxide with the annular structure.
And j, detecting the morphology of the powder by using a scanning electron microscope for the disordered mesoporous nano titanium dioxide prepared in the step i.
As can be seen from fig. 1 to 3, the disordered mesoporous nano titania prepared in examples 1 to 3 has an obvious ring structure, a pore diameter of 15 to 35nm, narrow pore size distribution, a uniformly dispersed ring structure in powder morphology, and a disordered mesoporous channel, which is beneficial to the diffusion of reactants in the mesoporous channel, improves the catalytic activity of the catalyst, and reduces the shrinkage rate of the denitration catalyst.
Claims (1)
1. The preparation method of the disordered mesoporous nano titanium dioxide is characterized by comprising the following steps:
a, heating acidolysis titanium liquid in the production of titanium dioxide by a sulfuric acid method to 70-90 ℃, adding part of the acidolysis titanium liquid into sodium hydroxide solution at 70-90 ℃, stirring, heating to 90-120 ℃, and keeping the temperature for 0-30min to obtain primary mixed liquid;
b, adding the residual titanium acidolysis solution obtained in the step a into the mixed solution obtained in the step a, and stirring to obtain a secondary mixed solution;
c, heating the secondary mixed solution obtained in the step b to boiling, keeping the temperature until the solution turns grey, and standing for 10-60 min to obtain a white suspension;
d, stirring the white suspension obtained in the step c, heating to boil, preserving heat for 2-4 h, filtering and washing to obtain a filter cake, and pulping the filter cake to obtain slurry;
e, heating the slurry obtained in the step d to 60-120 ℃, adding ammonia water, adjusting the pH value to 5.0-8.0, observing the slurry to form a sol state, preserving the temperature for 2-6h, dehydrating the sol, and calcining the sol in a muffle furnace at 400-600 ℃ to obtain granular titanium dioxide;
f, crushing the granular titanium dioxide obtained in the step e to obtain disordered mesoporous nano titanium dioxide with a ring-shaped structure;
the titanium solution acidolyzed in the step a is prepared, wherein TiO2The concentration of (A) is 180g/L-210 g/L; ti3+The concentration of (A) is 0.7-2.7 g/L; fe2+With TiO2The mass ratio of (A) to (B) is 0.25-0.35; f value is 1.55-2.00; the specific gravity is 1.521-1.552g/cm3；
In the step a, the mass concentration of the sodium hydroxide is 8-16%;
the total volume ratio of the sodium hydroxide solution to the titanium acidolysis solution in the step a is 100: 300-200: 300.
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| CN1348430A (en) * | 1999-04-23 | 2002-05-08 | 内诺株式会社 | Method for manufacturing photocatalytic titanium dioxide powder |
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| CN106654246A (en) * | 2017-01-22 | 2017-05-10 | 福建师范大学 | Preparation method of circular porous TiO2 nanosheet and application thereof |
| CN106830069A (en) * | 2017-02-15 | 2017-06-13 | 齐鲁工业大学 | A kind of flower-shaped mesoporous TiO 2 hierarchy and preparation method thereof |
| CN106938856A (en) * | 2016-01-05 | 2017-07-11 | 首都师范大学 | A kind of ring-type TiO2(B) and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20060110317A1 (en) * | 2004-11-23 | 2006-05-25 | Carmine Torardi | Mesoporous amorphous oxide of titanium |
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1348430A (en) * | 1999-04-23 | 2002-05-08 | 内诺株式会社 | Method for manufacturing photocatalytic titanium dioxide powder |
| CN1490249A (en) * | 2002-10-15 | 2004-04-21 | 北京化工大学 | Preparing method for nano titanium dioxide |
| CN1636879A (en) * | 2004-12-02 | 2005-07-13 | 攀钢集团攀枝花钢铁研究院 | Preparation method of nano mesoporous titanium dioxide powder |
| WO2012066547A1 (en) * | 2010-11-21 | 2012-05-24 | Joma International As | Method for producing small size titanium oxide particles |
| CN104667901A (en) * | 2013-11-29 | 2015-06-03 | 中国科学院兰州化学物理研究所 | Preparation method for denitration catalyst carrier nano titanium dioxide |
| CN106938856A (en) * | 2016-01-05 | 2017-07-11 | 首都师范大学 | A kind of ring-type TiO2(B) and preparation method thereof |
| CN106654246A (en) * | 2017-01-22 | 2017-05-10 | 福建师范大学 | Preparation method of circular porous TiO2 nanosheet and application thereof |
| CN106830069A (en) * | 2017-02-15 | 2017-06-13 | 齐鲁工业大学 | A kind of flower-shaped mesoporous TiO 2 hierarchy and preparation method thereof |
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