CN114042449B - Sulfur dioxide poisoning resistant catalyst for treating nitrogen oxide-containing waste gas, waste gas treating agent and application thereof - Google Patents

Sulfur dioxide poisoning resistant catalyst for treating nitrogen oxide-containing waste gas, waste gas treating agent and application thereof Download PDF

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CN114042449B
CN114042449B CN202111428987.3A CN202111428987A CN114042449B CN 114042449 B CN114042449 B CN 114042449B CN 202111428987 A CN202111428987 A CN 202111428987A CN 114042449 B CN114042449 B CN 114042449B
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CN114042449A (en
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胡晨鸣
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Shanxi Shuangling Chemical Joint Stock Co ltd
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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Abstract

The invention relates to the technical field of waste gas treatment, and discloses a sulfur dioxide poisoning resistant catalyst for treating waste gas containing nitrogen oxides, a waste gas treating agent and application thereof. The sulfur dioxide poisoning resistant catalyst sequentially comprises a denitration active inner core, a hollow layer and a titanium dioxide shell from inside to outside; the titanium dioxide shell has a porous structure. The catalyst of the invention has better SO resistance 2 Poisoning ability, and simultaneously, the hollow layer between the denitration active inner core and the titanium dioxide shell and the porous structure of the titanium dioxide shell are utilized to facilitate NH 3 And NO x And living thingsThe contact of sexual centers can better improve the denitration activity of the catalyst.

Description

Sulfur dioxide poisoning resistant catalyst for treating nitrogen oxide-containing waste gas, waste gas treating agent and application thereof
Technical Field
The invention relates to the technical field of waste gas treatment, in particular to a sulfur dioxide poisoning resistant catalyst for treating nitrogen oxide-containing waste gas, a waste gas treating agent and application thereof.
Background
Nitrogen Oxides (NO) x ) Mainly comprises Nitric Oxide (NO), nitrogen dioxide (NO 2 ) Dinitrogen monoxide (N) 2 O) and dinitrogen pentoxide (N) 2 O 5 ) And the like, is one of main atmospheric pollutants, can cause acid rain, ozone holes, photochemical smog and the like, and seriously endanger the ecological environment and the human health. Currently, ammonia selective catalytic reduction of NO x Technique (NH) 3 SCR) is considered one of the most effective means of denitration, in which the denitration catalyst plays an important role, and is also the NH at present 3 Hot spots and difficulties of SCR process research. NH can be added according to the temperature of the catalyst 3 SCR separation into high temperature NH 3 SCR and low temperature NH 3 -SCR。
Low temperature NH 3 Catalysts commonly used in SCR processes include MnO x 、Fe 2 O 3 、CeO 2 、CuO、CrO x Etc. the active temperature is below 300 ℃ compared with high-temperature NH 3 The SCR catalyst has wider application prospect, but at the same time, the NH at low temperature 3 SCR catalysts are resistant to SO 2 Poor poisoning ability, and limits its industrial large-scale application. Low temperature NH 3 SO of SCR catalyst 2 The poisoning mechanism mainly includes three aspects: (1) SO (SO) 2 With NH 3 And NO x Competing adsorption on the catalyst, hampering the progress of the reaction; (2) SO (SO) 2 Is easily oxidized into SO 3 Then with NH 3 The reaction generates ammonium sulfate and ammonium bisulfate which cover the catalytic active sites, so that the catalyst is deactivated; (3) SO (SO) 2 Or SO 3 Directly contact-reacts with active metal on the surface of the catalyst to cause sulfation of the active metal sites, which hinders the redox cycle process of the active components of the catalyst.
Disclosure of Invention
In order to solve the technical problems, the invention provides a sulfur dioxide poisoning resistant catalyst for treating nitrogen oxide-containing waste gas, a waste gas treating agent and application thereof. According to the invention, the hollow layer and the titanium dioxide shell with the porous structure are sequentially coated outside the denitration active inner core, SO that the SO resistance of the catalyst can be effectively improved 2 Poisoning ability and denitration activity.
The specific technical scheme of the invention is as follows:
the sulfur dioxide poisoning resistant catalyst for treating the nitrogen oxide-containing waste gas comprises a denitration active inner core, a hollow layer and a titanium dioxide shell from inside to outside in sequence; the titanium dioxide shell has a porous structure.
By coating the titanium dioxide shell outside the denitration active inner core, SO can be blocked 2 Contact with denitration active core to reduce SO 2 With NH 3 And NO x Competitive adsorption on the catalyst, inhibiting the formation of ammonium sulfate and ammonium bisulfate and sulfation of active centers on the core, thereby improving SO resistance of the catalyst 2 The poisoning capacity, and the titanium dioxide shell can also increase the acid sites on the surface of the catalyst, so that the denitration activity of the catalyst is improved.
However, if the titanium dioxide is directly coated on the denitration active core, the active center of the denitration active core is covered, and the effect of the titanium dioxide coating on the denitration activity of the catalyst is limited. Therefore, the invention arranges a hollow layer between the denitration active core and the titanium dioxide shell, and adopts the titanium dioxide shell with a porous structure, which can prevent titanium dioxide from covering the active center of the denitration active core and is beneficial to NH 3 And NO x Contact with the active center can thus better enhance the denitration activity of the catalyst.
Preferably, the denitration active core comprises MnO x 、CeO 2 And Fe (Fe) 2 O 3 At least one of them.
Preferably, the diameter of the denitration active core is 100-200 nm, the thickness of the hollow layer is 40-60 nm, and the thickness of the titanium dioxide shell is 60-100 nm.
The preparation method of the sulfur dioxide poisoning resistant catalyst comprises the following steps:
(1) Coating SiO 2 : adding the denitration active kernel and the dispersing agent into ethanol water solution, fully dispersing, regulating the pH to 8-9 by ammonia water, dropwise adding tetraethoxysilane/ethanol solution under stirring, continuously stirring for 6-7 h after the dropwise adding is finished, and obtaining a product A after suction filtration, drying, calcination, crushing and sieving;
(2) Coating TiO 2 /SiO 2 : mixing tetrabutyl titanate, diethanolamine and ethanol, dripping ethanol water solution, mixing uniformly, and preparing TiO 2 Sol; mixing tetraethoxysilane with ethanol water solution to obtain SiO 2 Sol; tiO is mixed with 2 Sol and SiO 2 Mixing the sol uniformly, adding the product A into the mixture, fully dispersing the mixture, standing the mixture for 12 to 14 hours, and carrying out suction filtration, drying, calcination, crushing and sieving to obtain the product B;
(3) SiO removal 2 : dispersing the product B into a sodium hydroxide solution with the weight percent of 4-6%, stirring and reacting for 1.5-2.0 h, and obtaining the sulfur dioxide poisoning resistant catalyst after suction filtration, washing and drying.
The invention sequentially coats SiO outside the denitration active core by a sol-gel method 2 Intermediate layer and porous TiO 2 /SiO 2 The shell is compounded, and then the sodium hydroxide solution is utilized to partially remove TiO 2 /SiO 2 Silica and SiO in composite shells 2 An intermediate layer to form a hollow layer (still having a suitable amount of SiO remaining) between the outer shell and the denitration active core 2 Supporting) and increasing the porosity in the outer layer, favoring NH 3 And NO x Contacts with active center on the inner core to improve denitration activity of the catalyst.
In the step (3), the finally obtained catalyst has higher denitration activity and structural strength by controlling the treatment time of the sodium hydroxide solution. When the sodium hydroxide solution is treated for too long, the silica in the shell and the middle layer is removed too much, SO that the shell of the catalyst is easy to collapse during the use process to influence SO resistance 2 Poisoning ability; when the treatment time of the sodium hydroxide solution is too short, excessive silica residues in the shell and the middle layer can be caused to affect NH 3 And NO x Contact with active centers on the core results in a catalyst with too low denitration activity.
In addition, the invention coats SiO by sol-gel method 2 Intermediate layer and porous TiO 2 /SiO 2 In the process of the composite shell, no acid ring is adoptedIn addition, the corrosion of the denitration active core in an acidic solution can be avoided.
Preferably, in step (1): the volume ratio of the ethanol aqueous solution is 3.0-4.5: 1, wherein the mass volume ratio of the denitration active kernel to the ethanol water solution is 1 g:20-25 mL; the volume ratio of the tetraethoxysilane to the ethanol solution is 1: 10-15 of a mixture of ethyl orthosilicate and ethanol, wherein the volume ratio of the ethanol aqueous solution to the ethyl orthosilicate/ethanol solution is 1:0.6 to 0.9.
Preferably, the dispersant is cetyl trimethylammonium bromide; the volume ratio of the dispersing agent to the ethanol water solution is 1:60 to 80 percent.
Preferably, in step (2): in the preparation of TiO 2 In the sol process, the volume ratio of the ethanol aqueous solution is 3.0-4.5: 1, wherein the volume ratio of the tetrabutyl titanate, the diethanolamine, the ethanol and the ethanol aqueous solution is 1:1.3 to 1.8: 20-30: 2.8 to 3.5; in the preparation of SiO 2 In the sol process, the volume ratio of the ethanol aqueous solution is 3.0-4.5: 1, wherein the volume ratio of the tetraethoxysilane to the ethanol water solution is 1: 25-30 parts; the product A, tiO 2 Sol and SiO 2 The mass volume ratio of the sol is 1g: 15-20 mL: 1-3 mL.
Preferably, in steps (1) and (2): the calcination temperature is 500-600 ℃ and the time is 2-3 h.
An exhaust gas treatment agent for treating exhaust gas containing nitrogen oxides, wherein the exhaust gas treatment agent is a filter material loaded with the sulfur dioxide poisoning resistant catalyst.
Preferably, the filter material is a fiber filter material, a porous ceramic filter material or a needled felt filter material.
The sulfur dioxide poisoning resistant catalyst or the exhaust gas treatment agent is applied to the treatment of exhaust gas containing nitrogen oxides.
Compared with the prior art, the invention has the following advantages:
(1) The catalyst of the invention has better SO resistance 2 Poisoning ability, and simultaneously, denitration activity thereofThe hollow layer between the inner core and the titanium dioxide shell and the porous structure of the titanium dioxide shell are beneficial to NH 3 And NO x Contact with the active center, so that the denitration activity of the catalyst can be better improved;
(2) In the preparation process of the catalyst, the method comprises the steps of coating TiO 2 /SiO 2 The shell is treated by sodium hydroxide solution after being compounded, so that the porosity of the shell can be improved, and the catalyst has better denitration activity.
Detailed Description
The invention is further described below with reference to examples. The following examples are only intended to illustrate the invention in detail and do not limit the scope of the invention in any way.
Example 1
A sulfur dioxide poisoning resistant catalyst for treating nitrogen oxide-containing waste gas is prepared by the following steps:
(1) Coating SiO 2 : according to 3.2g:1mL:80mL ratio of MnO with particle diameter of 100-150 nm x -CeO 2 Adding a composite denitration catalyst (the mol ratio of Mn to Ce is 4:1) and hexadecyl trimethyl ammonium bromide into an ethanol water solution (the volume ratio of ethanol to water is 3:1), after fully dispersing, regulating the pH to 8 by using ammonia water, dropwise adding an tetraethoxysilane/ethanol solution (the volume ratio of tetraethoxysilane to ethanol is 1:15 and the volume ratio of the tetraethoxysilane to the ethanol water solution is 0.9:1) under stirring, continuing stirring for 6h after the dropwise adding is completed, and obtaining a product A with the particle size of 150-200 nm after suction filtration, drying, calcining at 500 ℃ for 3h, crushing and sieving;
(2) Coating TiO 2 /SiO 2 : according to the following steps of 1:1.3:30, mixing tetrabutyl titanate, diethanolamine and ethanol, dropwise adding ethanol water solution (the volume ratio of ethanol to water is 3:1 and the volume ratio of tetrabutyl titanate to tetrabutyl titanate is 2.8:1), and uniformly mixing to prepare TiO 2 Sol; the volume ratio is 1:30 ethyl orthosilicate and ethanol water solution (the volume ratio of ethanol to water is 3:1) are evenly mixed to prepare SiO 2 Sol; the volume ratio is 15: tiO 1 2 Sol and SiO 2 Mixing the sol uniformly, addingIn and TiO 2 The mass volume ratio of the sol is 1g:15mL of the product A is fully dispersed, then is stood for 12 hours, and is subjected to suction filtration, drying, calcination at 500 ℃ for 3 hours, crushing and sieving to prepare a product B with the particle size of 230-280 nm;
(3) SiO removal 2 : according to 1g: dispersing the product B into a 6wt% sodium hydroxide solution in a proportion of 10mL, stirring and reacting for 1.5h, and carrying out suction filtration, washing and drying to obtain the sulfur dioxide poisoning resistant catalyst.
The sulfur dioxide poisoning resistant catalyst obtained by the steps comprises MnO from inside to outside x -CeO 2 The composite denitration active core, the hollow layer and the titanium dioxide shell with a porous structure.
Example 2
A sulfur dioxide poisoning resistant catalyst for treating nitrogen oxide-containing waste gas is prepared by the following steps:
(1) Coating SiO 2 : according to 1g:0.3mL:20mL of MnO having a particle diameter of 100 to 150nm x -CeO 2 Adding a composite denitration catalyst (the same as that of the embodiment 1) and hexadecyl trimethyl ammonium bromide into an ethanol water solution (the volume ratio of ethanol to water is 4:1), fully dispersing, regulating the pH to 8.5 by using ammonia water, dropwise adding tetraethoxysilane/ethanol solution (the volume ratio of tetraethoxysilane to ethanol is 1:12.5 and the volume ratio of the tetraethoxysilane to the ethanol water solution is 0.7:1) under stirring, continuously stirring for 6.5h after the dropwise adding is finished, and carrying out suction filtration, drying, calcining at 550 ℃ for 2.5h, crushing and sieving to obtain a product A with the particle size of 150-200 nm;
(2) Coating TiO 2 /SiO 2 : according to the following steps of 1:1.5: mixing tetrabutyl titanate, diethanolamine and ethanol in a volume ratio of 25, dropwise adding an ethanol water solution (the volume ratio of ethanol to water is 4:1 and the volume ratio of tetrabutyl titanate is 3.2:1), and uniformly mixing to prepare TiO 2 Sol; the volume ratio is 1:30 ethyl orthosilicate and ethanol water solution (the volume ratio of ethanol to water is 4:1) are evenly mixed to prepare SiO 2 Sol; the volume ratio is 15: tiO 2 2 Sol and SiO 2 Mixing the sol uniformly, adding the sol and TiO 2 The mass-volume ratio of the sol is1g:15mL of the product A is fully dispersed, then is kept stand for 13h, and is subjected to suction filtration, drying, calcining at 550 ℃ for 2.5h, crushing and sieving to prepare a product B with the particle size of 230-280 nm;
(3) SiO removal 2 : according to 1g:15mL of the product B is dispersed into 4.5wt% sodium hydroxide solution, stirred and reacted for 1.75h, and the sulfur dioxide poisoning resistant catalyst is prepared after suction filtration, washing and drying.
The sulfur dioxide poisoning resistant catalyst obtained by the steps comprises MnO from inside to outside x -CeO 2 The composite denitration active core, the hollow layer and the titanium dioxide shell with a porous structure.
Example 3
A sulfur dioxide poisoning resistant catalyst for treating nitrogen oxide-containing waste gas is prepared by the following steps:
(1) Coating SiO 2 : according to 3g:1mL:60mL of MnO having a particle diameter of 100 to 150nm x -CeO 2 Adding a composite denitration catalyst (the same as that of the embodiment 1) and hexadecyl trimethyl ammonium bromide into an ethanol water solution (the volume ratio of ethanol to water is 4.5:1), fully dispersing, regulating the pH to 9 by using ammonia water, dropwise adding tetraethoxysilane/ethanol solution (the volume ratio of tetraethoxysilane to ethanol is 1:10 and the volume ratio of the tetraethoxysilane to the ethanol water solution is 0.6:1) under stirring, continuously stirring for 7h after the dropwise adding is finished, and carrying out suction filtration, drying, calcining at 600 ℃ for 2h, crushing and sieving to obtain a product A with the particle size of 150-200 nm;
(2) Coating TiO 2 /SiO 2 : according to the following steps of 1:1.8:20, mixing tetrabutyl titanate, diethanolamine and ethanol, dropwise adding ethanol water solution (the volume ratio of ethanol to water is 4.5:1, and the volume ratio of tetrabutyl titanate to ethanol is 3.5:1), and uniformly mixing to obtain TiO 2 Sol; the volume ratio is 1:25 ethyl orthosilicate and ethanol water solution (the volume ratio of ethanol to water is 4.5:1) are evenly mixed to prepare SiO 2 Sol; the volume ratio is 20: tiO 3 2 Sol and SiO 2 Mixing the sol uniformly, adding the sol and TiO 2 The mass volume ratio of the sol is 1g:20mL of product A was sufficiently dispersed and allowed to stand14h, carrying out suction filtration, drying, calcining at 600 ℃ for 2h, crushing and sieving to obtain a product B with the particle size of 230-280 nm;
(3) SiO removal 2 : according to 1g: and dispersing the product B into a 4wt% sodium hydroxide solution according to the proportion of 20mL, stirring and reacting for 2.0h, and carrying out suction filtration, washing and drying to obtain the sulfur dioxide poisoning resistant catalyst.
The sulfur dioxide poisoning resistant catalyst obtained by the steps comprises MnO from inside to outside x -CeO 2 The composite denitration active core, the hollow layer and the titanium dioxide shell with a porous structure.
Comparative example 1
The catalyst of this comparative example is MnO having a particle size of 100 to 150nm x -CeO 2 Composite denitration catalyst (same as example 1).
Comparative example 2
A catalyst for the treatment of exhaust gas containing nitrogen oxides is prepared by:
according to the following steps of 1:1.5: mixing tetrabutyl titanate, diethanolamine and ethanol in a volume ratio of 25, dropwise adding an ethanol water solution (the volume ratio of ethanol to water is 4:1 and the volume ratio of tetrabutyl titanate is 3.2:1), and uniformly mixing to prepare TiO 2 Sol; according to 15mL:1g of TiO 2 Adding MnO with the particle size of 100-150 nm into the sol x -CeO 2 The composite denitration catalyst (the same as that of example 1) is fully dispersed, and then is stood for 13 hours, and after suction filtration, drying, calcination at 550 ℃ for 2.5 hours, crushing and sieving, the catalyst with the particle size of 170-230 nm is prepared.
The sulfur dioxide poisoning resistant catalyst obtained by the steps comprises MnO from inside to outside x -CeO 2 A composite denitration active core and a titanium dioxide shell with a porous structure.
Comparative example 3
The product B obtained in example 3 was taken at 1g: the product B is dispersed into a 4wt% sodium hydroxide solution according to the proportion of 20mL, stirred and reacted for 2.5h, and the catalyst is prepared after suction filtration, washing and drying.
Comparative example 4
The product B obtained in example 1 was taken at a rate of 1g: the product B is dispersed into 6wt% sodium hydroxide solution in the proportion of 10mL, stirred and reacted for 1h, and the catalyst is prepared after suction filtration, washing and drying.
Comparative example 5
A catalyst for the treatment of exhaust gas containing nitrogen oxides is prepared by:
(1) Coating TiO 2 : according to the following steps of 1:1.5: mixing tetrabutyl titanate, diethanolamine and ethanol in a volume ratio of 25, dropwise adding an ethanol water solution (the volume ratio of ethanol to water is 4:1 and the volume ratio of tetrabutyl titanate is 3.2:1), and uniformly mixing to prepare TiO 2 Sol; according to 15mL:1g of TiO 2 Adding the product A prepared in the example 2 into the sol, fully dispersing, standing for 13h, carrying out suction filtration, drying, calcining at 550 ℃ for 2.5h, crushing and sieving to obtain a product B with the particle size of 230-280 nm;
(3) SiO removal 2 : according to 1g:15mL of the product B is dispersed into 4.5wt% sodium hydroxide solution, stirred and reacted for 1.75h, and the sulfur dioxide poisoning resistant catalyst is prepared after suction filtration, washing and drying.
The sulfur dioxide poisoning resistant catalyst obtained by the steps comprises MnO from inside to outside x -CeO 2 The composite denitration active core, the hollow layer and the titanium dioxide shell with a porous structure.
The catalysts of examples 1 to 3 and comparative examples 1 to 5 were tested for denitration activity and sulfur dioxide poisoning resistance, respectively, using a flue gas denitration experimental device. The following mixed gas was used to simulate exhaust gas containing nitrogen oxides: NO 500ppm, NH 3 500ppm，SO 2 150ppm，O 2 5vol% of carrier gas N 2 The method comprises the steps of carrying out a first treatment on the surface of the The flow rate was 250mL/min and the temperature was 100 ℃. After the catalyst was used for 0h, 2h and 5h, NO removal rates were detected, respectively, and NO removal rate decrease rates at 0h were calculated as follows:
comparative example 1 MnO was used x /CeO 2 Composite denitration catalyst, comparative example 2 uses TiO 2 Directly to MnO x /CeO 2 The composite denitration catalyst was coated, examples 1 to 3 were prepared by the method of the present invention, and the catalyst was prepared in MnO x /CeO 2 A hollow layer is arranged between the composite denitration catalyst and the titanium dioxide shell. As can be seen from the above table, the catalysts of comparative example 2 and examples 1 to 3 are significantly higher in sulfur poisoning resistance than comparative example 1 because SO can be blocked by coating the titania shell outside the denitration-active core 2 Contact with denitration active core to reduce SO 2 With NH 3 And NO x Competitive adsorption on the catalyst, inhibiting the formation of ammonium sulfate and ammonium bisulfate and sulfation of active centers on the core, thereby improving SO resistance of the catalyst 2 Poisoning ability; moreover, the denitration ability of the catalysts of examples 1 to 3 was significantly higher than that of comparative example 2, because the catalyst was obtained by forming a catalyst having a denitration active core (MnO x /CeO 2 Composite denitration catalyst) and the titanium dioxide shell, can prevent the titanium dioxide from covering the active center of the denitration active core, and is favorable for NH 3 And NO x Contact with the active center can thus enhance the denitration activity of the catalyst.
The time for the sodium hydroxide solution treatment in example 3 and comparative example 3 was 2h and 2.5h, respectively. As can be seen from the above table, the catalyst of example 3 has higher sulfur poisoning resistance than that of comparative example 3 because the excessive removal of silica in the shell and the intermediate layer caused by the excessively long treatment time of the sodium hydroxide solution causes the shell of the catalyst to collapse easily during use to affect SO resistance 2 Poisoning ability.
The treatment time with sodium hydroxide solution in example 1 and comparative example 4 was 1.5h and 1h, respectively. As can be seen from the above table, the catalyst of example 1 has a significantly higher denitration activity than that of comparative example 4, because too short treatment time of sodium hydroxide solution results in excessive silica residue in the outer shell and the intermediate layer, affecting NH 3 And NO x Contact with active centers on the core results in a catalyst with too low denitration activity.
Comparative example 5 in the coating of the outer shell, only TiO was used 2 Sol, not TiO 2 Sol and SiO 2 A mixture of sols. As can be seen from the above table, the catalyst of example 2 has significantly higher denitration activity than that of comparative example 5, because when TiO is used 2 Sol and SiO 2 When the mixture of sol coats the shell, tiO is in the process of subsequent sodium hydroxide solution treatment 2 /SiO 2 The silicon dioxide in the composite shell is partially removed, the porosity in the outer layer can be improved, and NH is facilitated 3 And NO x Contacts with active center on the inner core, thereby improving denitration activity of the catalyst.
Although the present invention has been described in detail with reference to the embodiments, those skilled in the art will recognize that changes and modifications may be made to the embodiments described above without departing from the spirit of the invention, and within the scope of the appended claims.

Claims (8)

1. The sulfur dioxide poisoning resistant catalyst for treating the nitrogen oxide-containing waste gas is characterized by sequentially comprising a denitration active core, a hollow layer and a titanium dioxide shell from inside to outside; the titanium dioxide shell has a porous structure; the denitration active core comprises MnO x 、CeO 2 And Fe (Fe) 2 O 3 At least one of (a) and (b); the preparation method of the sulfur dioxide poisoning resistant catalyst comprises the following steps:
(1) Coating SiO 2 : adding the denitration active kernel and the dispersing agent into an ethanol water solution, fully dispersing, regulating the pH to 8-9 by ammonia water, dropwise adding an ethyl orthosilicate/ethanol solution under stirring, continuously stirring for 6-7 h after the dropwise adding is finished, and obtaining a product A after suction filtration, drying, calcination, crushing and sieving;
(2) Coating TiO 2 /SiO 2 : mixing tetrabutyl titanate, diethanolamine and ethanol, dripping ethanol water solution, mixing uniformly, and preparing TiO 2 Sol; mixing tetraethoxysilane with ethanol water solution to obtain SiO 2 Sol; will beTiO 2 Sol and SiO 2 Mixing the sol uniformly, adding the product A into the mixture, fully dispersing the mixture, standing the mixture for 12 to 14 hours, and carrying out suction filtration, drying, calcination, crushing and sieving to obtain the product B;
(3) SiO removal 2 : dispersing the product B into a sodium hydroxide solution with the concentration of 4-6wt%, stirring and reacting for 1.5-2.0 h, and carrying out suction filtration, washing and drying to obtain the sulfur dioxide poisoning resistant catalyst.
2. The sulfur dioxide poisoning resistant catalyst according to claim 1, wherein the diameter of the denitration active core is 100-200 nm, the thickness of the hollow layer is 40-60 nm, and the thickness of the titanium dioxide shell is 60-100 nm.
3. The sulfur dioxide poisoning resistant catalyst of claim 1, wherein in step (1): the volume ratio of the ethanol aqueous solution is 3.0-4.5: 1, wherein the mass volume ratio of the denitration active kernel to the ethanol water solution is 1 g:20-25 mL; the volume ratio of the tetraethoxysilane to the ethanol solution is 1: 10-15 of a mixture of ethyl orthosilicate and ethanol, wherein the volume ratio of the ethanol aqueous solution to the ethyl orthosilicate/ethanol solution is 1:0.6 to 0.9.
4. The sulfur dioxide poisoning resistant catalyst of claim 1, wherein in step (2): in the preparation of TiO 2 In the process of sol, the volume ratio of the ethanol aqueous solution is 3.0-4.5: 1, wherein the volume ratio of the tetrabutyl titanate, the diethanolamine, the ethanol and the ethanol aqueous solution is 1: 1.3-1.8: 20-30: 2.8-3.5; in the preparation of SiO 2 In the process of sol, the volume ratio of the ethanol aqueous solution is 3.0-4.5: 1, wherein the volume ratio of the tetraethoxysilane to the ethanol water solution is 1: 25-30 parts of a base; the product A, tiO 2 Sol and SiO 2 The mass volume ratio of the sol is 1g: 15-20 mL: 1-3 mL.
5. The sulfur dioxide poisoning resistant catalyst of claim 1, wherein in steps (1) and (2): the calcination temperature is 500-600 ℃ and the time is 2-3 h.
6. An exhaust gas treatment agent for treating exhaust gas containing nitrogen oxides, characterized in that the exhaust gas treatment agent is a filter material loaded with the sulfur dioxide poisoning resistant catalyst according to one of claims 1 to 5.
7. The exhaust gas treatment agent according to claim 6, wherein the filter material is a fibrous filter material, a porous ceramic filter material, or a needled felt filter material.
8. Use of the sulfur dioxide poisoning resistant catalyst according to one of claims 1 to 5 or the exhaust gas treatment agent according to claim 6 or 7 in the treatment of exhaust gas containing nitrogen oxides.
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