CN114042449A - Sulfur dioxide poisoning resistant catalyst for treating waste gas containing nitrogen oxide, waste gas treating agent and application of catalyst and waste gas treating agent - Google Patents

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

Info

Publication number
CN114042449A
CN114042449A CN202111428987.3A CN202111428987A CN114042449A CN 114042449 A CN114042449 A CN 114042449A CN 202111428987 A CN202111428987 A CN 202111428987A CN 114042449 A CN114042449 A CN 114042449A
Authority
CN
China
Prior art keywords
catalyst
ethanol
sol
volume ratio
sio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111428987.3A
Other languages
Chinese (zh)
Other versions
CN114042449B (en
Inventor
胡晨鸣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanxi Shuangling Chemical Joint Stock Co ltd
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN202111428987.3A priority Critical patent/CN114042449B/en
Publication of CN114042449A publication Critical patent/CN114042449A/en
Application granted granted Critical
Publication of CN114042449B publication Critical patent/CN114042449B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/02—Loose filtering material, e.g. loose fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • 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
    • B01J37/0215—Coating
    • 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
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0407—Additives and treatments of the filtering material comprising particulate additives, e.g. adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the technical field of waste gas treatment, and discloses a waste gas containing nitrogen oxidesA sulfur dioxide poisoning resistant catalyst for gas treatment, a waste gas treating agent and application thereof. The sulfur dioxide poisoning resisting catalyst sequentially comprises 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 catalyst of the invention has better SO resistance2The poisoning capability is utilized, and simultaneously, the hollow layer between the denitration active core and the titanium dioxide shell and the porous structure of the titanium dioxide shell are utilized to facilitate NH3And NOxContact with the active center, and thus the denitration activity of the catalyst can be improved more effectively.

Description

Sulfur dioxide poisoning resistant catalyst for treating waste gas containing nitrogen oxide, waste gas treating agent and application of catalyst and waste gas treating agent
Technical Field
The invention relates to the technical field of waste gas treatment, in particular to a sulfur dioxide poisoning resistant catalyst for treating waste gas containing nitrogen oxides, a waste gas treating agent and application thereof.
Background
Nitrogen Oxides (NO)x) Mainly comprises Nitric Oxide (NO) and nitrogen dioxide (NO)2) Dinitrogen monoxide (N)2O) and dinitrogen pentoxide (N)2O5) And the like, which are one of the main atmospheric pollutants, can cause acid rain, ozone cavities, photochemical smog and the like, and seriously harm the ecological environment and the human health. Currently, ammonia selective catalytic reduction of NOxTechnique (NH)3SCR) is considered to be one of the most effective denitration methods, in which denitration catalysts play an important role, and currently NH3The hot and difficult points of research on SCR processes. NH can be adjusted according to the different use temperature of the catalyst3SCR separation into high-temperature NH3SCR and low temperature NH3-SCR。
Low temperature NH3Catalysts commonly used in SCR processes include MnOx、Fe2O3、CeO2、CuO、CrOxEtc. with an active temperature below 300 ℃ compared to high temperature NH3SCR catalyst has wider application prospect, but at the same time, NH is at low temperature3SCR catalysts are faced with SO resistance2The problem of poor poisoning capacity limits its large-scale industrial application. Low temperature NH3SO of SCR catalyst2The poisoning mechanism mainly comprises three aspects: (1) SO (SO)2And NH3And NOxCompetitive adsorption on the catalyst, which hinders the reaction; (2) SO (SO)2Is easily oxidized into SO3Subsequently with NH3The reaction generates ammonium sulfate and ammonium bisulfate to cover the catalytic active sites, which leads to the inactivation of the catalyst; (3) SO (SO)2Or SO3Directly contact with active metal on the surface of the catalyst to react, so that active sites of the metal are sulfated, and the oxidation-reduction cycle process of active components of the catalyst is hindered.
Disclosure of Invention
In order to solve the technical problems, the invention provides a sulfur dioxide poisoning resistant catalyst for treating waste gas containing nitrogen oxides, 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 core, so that the denitration catalyst can be effectively improvedHigh catalyst SO resistance2Poisoning ability and denitration activity.
The specific technical scheme of the invention is as follows:
the sulfur dioxide poisoning resisting catalyst for treating the waste gas containing the nitrogen oxide sequentially comprises 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 inner core is coated with the titanium dioxide shell to block SO2Contact with denitration active core to reduce SO2And NH3And NOxCompetitive adsorption on the catalyst, inhibition of ammonium sulfate and ammonium bisulfate formation and sulfation of active centers on the inner core, thereby improving SO resistance of the catalyst2And meanwhile, the titanium dioxide shell can also increase acid sites on the surface of the catalyst, so that the denitration activity of the catalyst is improved.
However, when the denitration active core is directly coated with titanium dioxide, the active sites of the denitration active core are covered, and the effect of the titanium dioxide coating on the improvement of the denitration activity of the catalyst is limited. Therefore, the hollow layer is arranged between the denitration active core and the titanium dioxide shell, and the titanium dioxide shell with the porous structure is adopted, so that the titanium dioxide can be prevented from covering the active center of the denitration active core, and NH is facilitated3And NOxContact with the active center, and thus the denitration activity of the catalyst can be improved more effectively.
Preferably, the denitration active core comprises MnOx、CeO2And Fe2O3At least one of (1).
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.
A preparation method of the catalyst for resisting sulfur dioxide poisoning comprises the following steps:
(1) coated SiO2: adding the denitration active core and a dispersant into an ethanol water solution, fully dispersing, and adjusting the pH value to be equal to8-9, dropwise adding an ethyl orthosilicate/ethanol solution under stirring, continuing stirring for 6-7 hours after dropwise adding, and performing suction filtration, drying, calcination, crushing and sieving to obtain a product A;
(2) coated TiO2/SiO2: mixing tetrabutyl titanate, diethanol amine and ethanol, dripping ethanol water solution, and mixing uniformly to prepare TiO2Sol; mixing ethyl orthosilicate and ethanol water solution to prepare SiO2Sol; adding TiO into the mixture2Sol and SiO2Uniformly mixing the sol, adding the product A into the sol, fully dispersing, standing for 12-14 h, and performing suction filtration, drying, calcining, crushing and sieving to obtain a product B;
(3) removal of SiO2: and dispersing the product B into a 4-6 wt% sodium hydroxide solution, stirring for reaction for 1.5-2.0 h, and performing suction filtration, washing and drying to obtain the sulfur dioxide poisoning resistant catalyst.
The invention sequentially coats SiO outside the denitration active core by a sol-gel method2Intermediate layer and porous TiO2/SiO2Compounding the shell, and then partially removing TiO by using a sodium hydroxide solution2/SiO2Silica and SiO in composite housing2An intermediate layer, thereby forming a hollow layer (but still leaving a suitable amount of SiO) between the outer shell and the denitration active core2Act as a support) and increase the porosity in the outer layer, favoring NH3And NOxAnd the catalyst is contacted with the active center on the inner core, so that the denitration activity of the catalyst is improved.
In the step (3), the finally obtained catalyst has higher denitration activity and structural strength by controlling the time of the treatment of the sodium hydroxide solution. When the sodium hydroxide solution is treated for too long time, the silicon dioxide in the shell and the intermediate layer is removed too much, SO that the shell of the catalyst is easy to collapse during the use process to influence the SO resistance of the catalyst2The ability to be poisoned; when the treatment time of the sodium hydroxide solution is too short, excessive silica remains in the shell and the intermediate layer, affecting NH3And NOxContact with the active center on the core causes the denitrification activity of the catalyst to be too low.
In addition, the invention coats SiO by sol-gel method2Intermediate layer and porous TiO2/SiO2In the process of compounding the shell, an acid environment is not adopted, so that the denitration active core can be prevented from being corroded in an acid solution.
Preferably, in step (1): the ethanol water solution is prepared by mixing 3.0-4.5 by volume: 1, wherein the mass-volume ratio of the denitration active core to the ethanol water solution is 1g: 20-25 mL; the volume ratio of the ethyl orthosilicate/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 trimethyl ammonium bromide; the volume ratio of the dispersing agent to the ethanol aqueous solution is 1: 60-80.
Preferably, in step (2): in the preparation of TiO2In the sol process, the volume ratio of the ethanol water solution is 3.0-4.5: 1, wherein the volume ratio of the tetrabutyl titanate to the diethanol amine to the ethanol aqueous solution is 1: 1.3-1.8: 20-30: 2.8 to 3.5; in the preparation of SiO2In the sol process, the volume ratio of the ethanol water solution is 3.0-4.5: 1, wherein the volume ratio of the ethyl orthosilicate to the ethanol aqueous solution is 1: 25-30; said product A, TiO2Sol and SiO2The 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 calcination time is 2-3 h.
The waste gas treating agent is a filter material loaded with the sulfur dioxide poisoning resisting catalyst.
Preferably, the filter material is a fiber filter material, a porous ceramic filter material or a needle felt filter material.
The application of the catalyst for resisting sulfur dioxide poisoning or the waste gas treating agent in the treatment of waste gas containing nitrogen oxide.
Compared with the prior art, the invention has the following advantages:
(1) the catalyst of the invention has better SO resistance2The poisoning capability is utilized, and simultaneously, the hollow layer between the denitration active core and the titanium dioxide shell and the porous structure of the titanium dioxide shell are utilized to facilitate NH3And NOxThe catalyst is contacted with the active center, so that the denitration activity of the catalyst can be better improved;
(2) the invention coats TiO with the catalyst during the preparation process2/SiO2And the shell is compounded and then treated by a sodium hydroxide solution, so that the porosity of the shell can be improved, and the catalyst has better denitration activity.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are intended only to illustrate the invention in detail and are not intended to limit the scope of the invention in any way.
Example 1
A sulfur dioxide poisoning resistant catalyst for treating exhaust gas containing nitrogen oxides is prepared by the following steps:
(1) coated SiO2: according to the weight ratio of 3.2 g: 1mL of: 80mL of MnO with a particle size of 100-150 nmx-CeO2Adding a composite denitration catalyst (the molar 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), fully dispersing, adjusting the pH to 8 by using ammonia water, dropwise adding an ethyl orthosilicate/ethanol solution (the volume ratio of ethyl orthosilicate to ethanol is 1: 15 and the volume ratio of ethyl orthosilicate to ethanol is 0.9: 1) while stirring, continuously stirring for 6 hours after dropwise adding is finished, and preparing a product A with the particle size of 150-200 nm after suction filtration, drying, calcination at 500 ℃ for 3 hours, crushing and sieving;
(2) coated TiO2/SiO2: according to the following steps: 1.3: 30 volume ratio of tetrabutyl titanate, diethanol amine and ethanol, dropwise adding ethanol water (the volume ratio of ethanol to water is 3: 1, and the volume ratio of ethanol to tetrabutyl titanate is 2.8: 1), and uniformly mixing to prepare TiO2Sol; mixing the components in a volume ratio of 1: 30 of ortho silicic acidMixing ethyl ester and ethanol water solution (volume ratio of ethanol to water is 3: 1) to obtain SiO2Sol; mixing the components in a volume ratio of 15: 1 TiO2Sol and SiO2Mixing the sol uniformly, adding into the sol and TiO2The mass volume ratio of the sol is 1g: after fully dispersing 15mL of the product A, standing for 12h, performing suction filtration, drying, calcining at 500 ℃ for 3h, crushing and sieving to obtain a product B with the particle size of 230-280 nm;
(3) removal of SiO2: according to the weight ratio of 1g: and dispersing the product B into 6 wt% of sodium hydroxide solution according to the proportion of 10mL, stirring for reaction for 1.5h, and performing suction filtration, washing and drying to obtain the sulfur dioxide poisoning resistant catalyst.
The catalyst for resisting sulfur dioxide poisoning obtained by the steps sequentially comprises MnO from inside to outsidex-CeO2The composite denitration catalyst comprises a composite denitration active core, a hollow layer and a titanium dioxide shell with a porous structure.
Example 2
A sulfur dioxide poisoning resistant catalyst for treating exhaust gas containing nitrogen oxides is prepared by the following steps:
(1) coated SiO2: according to the weight ratio of 1g: 0.3 mL: 20mL of MnO having a particle size of 100 to 150nmx-CeO2Adding a composite denitration catalyst (same as that in example 1) and hexadecyl trimethyl ammonium bromide into an ethanol water solution (the volume ratio of ethanol to water is 4: 1), fully dispersing, adjusting the pH to 8.5 by using ammonia water, dropwise adding an ethyl orthosilicate/ethanol solution (the volume ratio of ethyl orthosilicate to ethanol is 1: 12.5, and the volume ratio of ethyl orthosilicate to ethanol is 0.7: 1) while stirring, continuously stirring for 6.5 hours after dropwise adding is finished, and preparing a product A with the particle size of 150-200 nm after suction filtration, drying, calcination at 550 ℃ for 2.5 hours, crushing and sieving;
(2) coated TiO2/SiO2: according to the following steps: 1.5: 25 volume ratio of tetrabutyl titanate, diethanol amine and ethanol, dropwise adding ethanol water (the volume ratio of ethanol to water is 4: 1, and the volume ratio of ethanol to tetrabutyl titanate is 3.2: 1), and uniformly mixing to prepare TiO2Sol; mixing the components in a volume ratio of 1: 30 parts by volume of ethyl orthosilicate and aqueous ethanol (volume ratio of ethanol to water)Is 4: 1) mixing to obtain SiO2Sol; mixing the components in a volume ratio of 15: 2 TiO 22Sol and SiO2Mixing the sol uniformly, adding into the sol and TiO2The mass volume ratio of the sol is 1g: after fully dispersing 15mL of the product A, 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) removal of SiO2: according to the weight ratio of 1g: dispersing the product B into 4.5 wt% sodium hydroxide solution according to the proportion of 15mL, stirring for reaction for 1.75h, and performing suction filtration, washing and drying to obtain the sulfur dioxide poisoning resistant catalyst.
The catalyst for resisting sulfur dioxide poisoning obtained by the steps sequentially comprises MnO from inside to outsidex-CeO2The composite denitration catalyst comprises a composite denitration active core, a hollow layer and a titanium dioxide shell with a porous structure.
Example 3
A sulfur dioxide poisoning resistant catalyst for treating exhaust gas containing nitrogen oxides is prepared by the following steps:
(1) coated SiO2: according to the weight ratio of 3 g: 1mL of: 60mL of MnO having a particle size of 100 to 150nmx-CeO2Adding a composite denitration catalyst (same as that in example 1) and hexadecyl trimethyl ammonium bromide into an ethanol water solution (the volume ratio of ethanol to water is 4.5: 1), fully dispersing, adjusting the pH to 9 by using ammonia water, dropwise adding an ethyl orthosilicate/ethanol solution (the volume ratio of ethyl orthosilicate to ethanol is 1: 10, and the volume ratio of ethyl orthosilicate to ethanol is 0.6: 1) while stirring, continuously stirring for 7 hours after dropwise adding is completed, and preparing a product A with the particle size of 150-200 nm after suction filtration, drying, calcination at 600 ℃ for 2 hours, crushing and sieving;
(2) coated TiO2/SiO2: according to the following steps: 1.8: 20 volume ratio of tetrabutyl titanate, diethanol amine and ethanol, dropwise adding ethanol water (the volume ratio of ethanol to water is 4.5: 1, and the volume ratio of ethanol to tetrabutyl titanate is 3.5: 1), and uniformly mixing to prepare TiO2Sol; mixing the components in a volume ratio of 1: 25 of ethyl orthosilicate and ethanol water solution (the volume ratio of ethanol to water is 4.5: 1) are mixed uniformly to prepare SiO2Sol gel(ii) a Mixing the components in a volume ratio of 20: 3 TiO 22Sol and SiO2Mixing the sol uniformly, adding into the sol and TiO2The mass volume ratio of the sol is 1g: after fully dispersing 20mL of the product A, standing for 14h, performing 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) removal of SiO2: according to the weight ratio of 1g: and dispersing the product B into a 4 wt% sodium hydroxide solution in a proportion of 20mL, stirring for reaction for 2.0h, and performing suction filtration, washing and drying to obtain the sulfur dioxide poisoning resistant catalyst.
The catalyst for resisting sulfur dioxide poisoning obtained by the steps sequentially comprises MnO from inside to outsidex-CeO2The composite denitration catalyst comprises a composite denitration active core, a hollow layer and a titanium dioxide shell with a porous structure.
Comparative example 1
The catalyst of the comparative example is MnO having a particle size of 100 to 150nmx-CeO2Composite denitration catalyst (same as example 1).
Comparative example 2
A catalyst for the treatment of exhaust gas containing nitrogen oxides is prepared by the steps of:
according to the following steps: 1.5: 25 volume ratio of tetrabutyl titanate, diethanol amine and ethanol, dropwise adding ethanol water (the volume ratio of ethanol to water is 4: 1, and the volume ratio of ethanol to tetrabutyl titanate is 3.2: 1), and uniformly mixing to prepare TiO2Sol; according to the volume ratio of 15 mL: 1g to TiO2MnO with the particle size of 100-150 nm is added into the solx-CeO2The composite denitration catalyst (same as the embodiment 1) is fully dispersed, then is kept stand for 13 hours, and is subjected to suction filtration, drying, calcination at 550 ℃ for 2.5 hours, crushing and sieving to prepare the catalyst with the particle size of 170-230 nm.
The catalyst for resisting sulfur dioxide poisoning obtained by the steps sequentially comprises MnO from inside to outsidex-CeO2The composite denitration active core and the titanium dioxide shell with a porous structure.
Comparative example 3
The product B obtained in example 3 was taken, and the molar ratio was 1g: and dispersing the product B into a 4 wt% sodium hydroxide solution in a ratio of 20mL, stirring for reaction for 2.5h, and carrying out suction filtration, washing and drying to obtain the catalyst.
Comparative example 4
The product B obtained in example 1 was taken, and the molar ratio was 1g: and dispersing the product B into 6 wt% of sodium hydroxide solution according to the proportion of 10mL, stirring for reaction for 1h, and carrying out suction filtration, washing and drying to obtain the catalyst.
Comparative example 5
A catalyst for the treatment of exhaust gas containing nitrogen oxides is prepared by the steps of:
(1) coated TiO2: according to the following steps: 1.5: 25 volume ratio of tetrabutyl titanate, diethanol amine and ethanol, dropwise adding ethanol water (the volume ratio of ethanol to water is 4: 1, and the volume ratio of ethanol to tetrabutyl titanate is 3.2: 1), and uniformly mixing to prepare TiO2Sol; according to the volume ratio of 15 mL: 1g to TiO2Adding the product A prepared in the example 2 into the sol, fully dispersing, standing for 13 hours, carrying out suction filtration, drying, calcining at 550 ℃ for 2.5 hours, crushing and sieving to obtain a product B with the particle size of 230-280 nm;
(3) removal of SiO2: according to the weight ratio of 1g: dispersing the product B into 4.5 wt% sodium hydroxide solution according to the proportion of 15mL, stirring for reaction for 1.75h, and performing suction filtration, washing and drying to obtain the sulfur dioxide poisoning resistant catalyst.
The catalyst for resisting sulfur dioxide poisoning obtained by the steps sequentially comprises MnO from inside to outsidex-CeO2The composite denitration catalyst comprises a composite denitration active core, a hollow layer and a titanium dioxide shell with a porous structure.
By using a flue gas denitration experimental device, the denitration activity and the sulfur dioxide poisoning resistance of the catalysts of the examples 1-3 and the comparative examples 1-5 are respectively tested. The following mixed gas was used to simulate an exhaust gas containing nitrogen oxides: NO 500ppm, NH3500ppm，SO2150ppm，O25 vol% of carrier gas N2(ii) a The flow rate was 250mL/min and the temperature was 100 ℃. After the catalyst was used for 0h, 2h and 5h, the NO removal rate was measured, and the NO removal rate decrease rate was calculated as compared to 0h, with the following results:
Figure BDA0003379522270000071
comparative example 1 Using MnOx/CeO2Composite denitration catalyst comparative example 2 using TiO2Directly to MnOx/CeO2Coating the composite denitration catalyst, and using the method of the invention in examples 1-3, in MnOx/CeO2A hollow layer is arranged between the composite denitration catalyst and the titanium dioxide shell. As can be seen from the above table, the sulfur poisoning resistance of the catalysts of comparative example 2 and examples 1 to 3 is significantly higher than that of comparative example 1, because SO can be blocked by coating the outer shell of titanium dioxide on the outer surface of the denitration active core2Contact with denitration active core to reduce SO2And NH3And NOxCompetitive adsorption on the catalyst, inhibition of ammonium sulfate and ammonium bisulfate formation and sulfation of active centers on the inner core, thereby improving SO resistance of the catalyst2The ability to be poisoned; also, the catalyst of examples 1 to 3 had a significantly higher denitration ability than that of comparative example 2 because the denitration activity was improved by adding a denitration active core (MnO)x/CeO2Composite denitration catalyst) and a titanium dioxide shell, can prevent the titanium dioxide from covering the active center of the denitration active core, and is favorable for NH3And NOxContact with the active sites, and thus the denitration activity of the catalyst can be improved.
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 sulfur poisoning resistance of the catalyst of example 3 is higher than that of comparative example 3, because when the treatment time of the NaOH solution is too long, the silica in the outer shell and the intermediate layer is removed too much, SO that the outer shell of the catalyst is easy to collapse during use to affect the SO resistance2The poisoning ability.
The time for the sodium hydroxide solution treatment in example 1 and comparative example 4 was 1.5h and 1h, respectively. As can be seen from the above table, the denitration activity of the catalyst of example 1 is significantly higher than that of comparative example 4 because when the treatment time of the sodium hydroxide solution is too short, it results in an out-gassingToo much silica remains in the shell and intermediate layers, affecting NH3And NOxContact with the active center on the core causes the denitrification activity of the catalyst to be too low.
Comparative example 5 in the process of coating the outer shell, only TiO was used2Sols other than TiO2Sol and SiO2A mixture of sols. As can be seen from the above table, the denitration activity of the catalyst of example 2 is significantly higher than that of comparative example 5 because when TiO is used2Sol and SiO2When the sol mixture is coated on the shell, TiO is coated in the subsequent sodium hydroxide solution treatment process2/SiO2The partial removal of silica from the composite shell can increase the porosity in the outer layer, which is beneficial to NH3And NOxAnd contact with the active center on the inner core, thereby improving the denitration activity of the catalyst.
Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that the embodiments may be modified or changed without departing from the spirit of the present invention within the scope of the appended claims.

Claims (10)

1. The sulfur dioxide poisoning resisting catalyst for treating the waste gas containing the nitrogen oxide is characterized by comprising a denitration active core, a hollow layer and a titanium dioxide shell from inside to outside in sequence; the titanium dioxide shell has a porous structure.
2. The sulfur dioxide poisoning resistant catalyst of claim 1, wherein the denitration active core comprises MnOx、CeO2And Fe2O3At least one of (1).
3. The sulfur dioxide poisoning resistant catalyst according to claim 1 or 2, wherein the denitration active core has a diameter of 100 to 200nm, the hollow layer has a thickness of 40 to 60nm, and the titanium dioxide shell has a thickness of 60 to 100 nm.
4. A method for preparing the catalyst for resisting sulfur dioxide poisoning according to any one of claims 1 to 3, comprising the steps of:
(1) coated SiO2: adding the denitration active core and a dispersing agent into an ethanol water solution, fully dispersing, adjusting the pH to 8-9 by using ammonia water, dropwise adding ethyl orthosilicate/ethanol solution under stirring, continuously stirring for 6-7 h after dropwise adding is completed, and performing suction filtration, drying, calcination, crushing and sieving to obtain a product A;
(2) coated TiO2/SiO2: mixing tetrabutyl titanate, diethanol amine and ethanol, dripping ethanol water solution, and mixing uniformly to prepare TiO2Sol; mixing ethyl orthosilicate and ethanol water solution to prepare SiO2Sol; adding TiO into the mixture2Sol and SiO2Uniformly mixing the sol, adding the product A into the sol, fully dispersing, standing for 12-14 h, and performing suction filtration, drying, calcining, crushing and sieving to obtain a product B;
(3) removal of SiO2: and dispersing the product B into a 4-6 wt% sodium hydroxide solution, stirring for reaction for 1.5-2.0 h, and performing suction filtration, washing and drying to obtain the sulfur dioxide poisoning resistant catalyst.
5. The production method according to claim 4, wherein in step (1): the ethanol water solution is prepared by mixing 3.0-4.5 by volume: 1, wherein the mass-volume ratio of the denitration active core to the ethanol water solution is 1g: 20-25 mL; the volume ratio of the ethyl orthosilicate/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.
6. The production method according to claim 4, wherein in step (2): in the preparation of TiO2In the sol process, the volume ratio of the ethanol water solution is 3.0-4.5: 1 mixture of ethanol and water, tetrabutyl titanate, diethanolamine, and water,The volume ratio of the ethanol to the ethanol aqueous solution is 1: 1.3-1.8: 20-30: 2.8 to 3.5; in the preparation of SiO2In the sol process, the volume ratio of the ethanol water solution is 3.0-4.5: 1, wherein the volume ratio of the ethyl orthosilicate to the ethanol aqueous solution is 1: 25-30; said product A, TiO2Sol and SiO2The mass volume ratio of the sol is 1g: 15-20 mL: 1-3 mL.
7. The production method according to claim 4, wherein in steps (1) and (2): the calcination temperature is 500-600 ℃, and the calcination time is 2-3 h.
8. An exhaust gas treating agent for treating exhaust gas containing nitrogen oxides, wherein the exhaust gas treating agent is a filter material loaded with the sulfur dioxide poisoning resistant catalyst according to any one of claims 1 to 3.
9. The exhaust gas treating agent according to claim 8, wherein the filter material is a fiber filter material, a porous ceramic filter material, or a needle felt filter material.
10. Use of the catalyst for sulfur dioxide poisoning resistance according to any one of claims 1 to 3 or the exhaust gas treating agent according to claim 8 or 9 for treating exhaust gas containing nitrogen oxides.
CN202111428987.3A 2021-11-28 2021-11-28 Sulfur dioxide poisoning resistant catalyst for treating nitrogen oxide-containing waste gas, waste gas treating agent and application thereof Active CN114042449B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111428987.3A CN114042449B (en) 2021-11-28 2021-11-28 Sulfur dioxide poisoning resistant catalyst for treating nitrogen oxide-containing waste gas, waste gas treating agent and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111428987.3A CN114042449B (en) 2021-11-28 2021-11-28 Sulfur dioxide poisoning resistant catalyst for treating nitrogen oxide-containing waste gas, waste gas treating agent and application thereof

Publications (2)

Publication Number Publication Date
CN114042449A true CN114042449A (en) 2022-02-15
CN114042449B CN114042449B (en) 2024-03-08

Family

ID=80211419

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111428987.3A Active CN114042449B (en) 2021-11-28 2021-11-28 Sulfur dioxide poisoning resistant catalyst for treating nitrogen oxide-containing waste gas, waste gas treating agent and application thereof

Country Status (1)

Country Link
CN (1) CN114042449B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116139861A (en) * 2023-01-31 2023-05-23 安庆市长三角未来产业研究院 Catalyst applicable to storage reduction of nitrogen oxides of gas turbine as well as preparation and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008284411A (en) * 2007-05-15 2008-11-27 Osaka Univ Photocatalyst included in hollow porous shell layer and its manufacturing method
CN102881881A (en) * 2012-10-25 2013-01-16 中国科学院宁波材料技术与工程研究所 Negative pole material of lithium ion battery, preparation method of material and lithium ion battery
CN104190408A (en) * 2014-08-19 2014-12-10 南京师范大学 Low-temperature SCR denitration catalyst with titanium-based core-shell structure and preparation method of catalyst
KR20150052652A (en) * 2013-11-06 2015-05-14 건국대학교 산학협력단 Preparation method of yolk-shell structured material by spray drying and yolk-shell structured materials prepared thereby
CN108579732A (en) * 2018-04-04 2018-09-28 中山大学 A kind of Pt ZrO of hollow nucleocapsid meso-hole structure2Photo-thermal catalyst and the preparation method and application thereof
CN111545193A (en) * 2020-05-30 2020-08-18 西安交通大学 Hollow core-shell structure catalyst for catalytic oxidation of nitrogen oxide and preparation method thereof
CN114191981A (en) * 2021-12-26 2022-03-18 胡晨鸣 Harmless treatment method for industrial waste gas

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008284411A (en) * 2007-05-15 2008-11-27 Osaka Univ Photocatalyst included in hollow porous shell layer and its manufacturing method
CN102881881A (en) * 2012-10-25 2013-01-16 中国科学院宁波材料技术与工程研究所 Negative pole material of lithium ion battery, preparation method of material and lithium ion battery
KR20150052652A (en) * 2013-11-06 2015-05-14 건국대학교 산학협력단 Preparation method of yolk-shell structured material by spray drying and yolk-shell structured materials prepared thereby
CN104190408A (en) * 2014-08-19 2014-12-10 南京师范大学 Low-temperature SCR denitration catalyst with titanium-based core-shell structure and preparation method of catalyst
CN108579732A (en) * 2018-04-04 2018-09-28 中山大学 A kind of Pt ZrO of hollow nucleocapsid meso-hole structure2Photo-thermal catalyst and the preparation method and application thereof
CN111545193A (en) * 2020-05-30 2020-08-18 西安交通大学 Hollow core-shell structure catalyst for catalytic oxidation of nitrogen oxide and preparation method thereof
CN114191981A (en) * 2021-12-26 2022-03-18 胡晨鸣 Harmless treatment method for industrial waste gas

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BINGJIE HUANG ET AL.,: "Novel CeO2@TiO2 core–shell nanostructure catalyst for selective catalytic reduction of NOx with NH3", 《JOURNAL OF ENVIRONMENTAL SCIENCES》, vol. 55, pages 129 - 136 *
BOQIONG JIANG ET AL.,: "Low-temperature selective catalytic reduction of NO on MnOx/TiO2 prepared by different methods", 《JOURNAL OF HAZARDOUS MATERIALS》, vol. 162, pages 1249, XP025805127, DOI: 10.1016/j.jhazmat.2008.06.013 *
THANGAVEL MATHIMANI ET AL.,: "Biodiesel production and engine performance study using one-pot synthesised ZnO/MCM-41", 《FUEL》, vol. 336, pages 1 - 9 *
彭子青;谌伟庆;马洪波;黄思富;石秋杰;: "核壳结构纳米复合材料在催化中的应用", 化工进展, no. 08 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116139861A (en) * 2023-01-31 2023-05-23 安庆市长三角未来产业研究院 Catalyst applicable to storage reduction of nitrogen oxides of gas turbine as well as preparation and application thereof
CN116139861B (en) * 2023-01-31 2024-04-16 安庆市长三角未来产业研究院 Catalyst applicable to storage reduction of nitrogen oxides of gas turbine as well as preparation and application thereof

Also Published As

Publication number Publication date
CN114042449B (en) 2024-03-08

Similar Documents

Publication Publication Date Title
CN112076803B (en) Ammonia oxidation catalyst, preparation method and application
CN111450876A (en) Low-temperature SCR denitration catalyst using carriers with different particle sizes to load Mn and preparation method thereof
CN110182827B (en) Preparation method and application of CuM/SAPO-34 and Fe/Beta coupled molecular sieve
CN106890649A (en) A kind of support type ceramic honey comb catalysis material and preparation method
CN113042066B (en) Flue gas denitration catalyst and preparation method thereof
CN109603807B (en) Modified activated carbon Ce-Nb/TiO2@ AC low-temperature efficient desulfurization and denitrification catalyst and preparation method thereof
CN111346670B (en) High-temperature flue gas denitration catalyst and preparation method thereof
CN111001415A (en) Preparation method of composite oxide low-temperature denitration catalyst and catalyst
CN106824174A (en) A kind of coccoid catalyst of high-efficient purification nitrogen oxides and preparation method thereof
CN114042449A (en) Sulfur dioxide poisoning resistant catalyst for treating waste gas containing nitrogen oxide, waste gas treating agent and application of catalyst and waste gas treating agent
CN110354839B (en) Cerium-based composite metal oxide nanoflower material and preparation method and application thereof
CN105772028A (en) Regeneration method for SCR (Selective Catalytic Reduction) denitration catalyst V2O5-WO3/TiO2
CN110947416A (en) For NH3-SCR iron/molecular sieve catalyst, preparation method and application thereof
CN106881105A (en) A kind of board-like low temperature catalyst with the self-assembly porous spherical titanium dioxide of crosslinking nano chain as carrier and its preparation method and application
CN111905721B (en) Catalyst for low-temperature denitration and demercuration of titanium dioxide nano array and preparation method thereof
CN114191981B (en) Harmless treatment method for industrial waste gas
CN108176349B (en) Al (aluminum)2O3@TiO2Preparation method of core-shell structure simultaneous desulfurization and denitrification adsorbent
CN115364868B (en) Catalyst for catalytically decomposing ozone and preparation method thereof
CN116422352A (en) Preparation method and application of phosphotungstic acid modified iron-based MOF derivative material
CN113893844A (en) NH with ethane as auxiliary reducing agent3-SCR denitration catalyst and preparation method thereof
CN110479296B (en) Catalyst capable of reducing escape of denitrated ammonia and preparation method thereof
CN111250078B (en) MnOx @ Eu-CeOx low-temperature SCR flue gas denitration catalyst and preparation method and application thereof
CN114011379A (en) Nitrogen oxide adsorbent and preparation method thereof
CN108816257B (en) Sulfur-resistant and water-resistant alkaline earth metal doped cerium phosphate-based catalyst and preparation method and application thereof
CN111530453A (en) Ce-Mn composite catalyst for low-temperature SCR denitration reaction and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20240201

Address after: 721000 Jiangzheng Railway Station, Fufeng County, Baoji City, Shaanxi Province

Applicant after: SHANXI SHUANGLING CHEMICAL JOINT-STOCK CO.,LTD.

Country or region after: China

Address before: 114000 Room 301, building 7, intelligent equipment Industrial Park, Yushan Economic Development Zone, Anshan City, Liaoning Province

Applicant before: Hu Chenming

Country or region before: China

TA01 Transfer of patent application right
GR01 Patent grant
GR01 Patent grant