CN110052287B - Core-shell structure molecular sieve catalyst for cooperatively controlling NO and toluene and preparation method thereof - Google Patents
Core-shell structure molecular sieve catalyst for cooperatively controlling NO and toluene and preparation method thereof Download PDFInfo
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 125
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 58
- 239000011258 core-shell material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005342 ion exchange Methods 0.000 claims abstract description 9
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 238000001338 self-assembly Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 14
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 7
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- 229960004011 methenamine Drugs 0.000 claims description 7
- 238000009423 ventilation Methods 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims 1
- 229940076286 cupric acetate Drugs 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- 231100000572 poisoning Toxicity 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 65
- 239000007789 gas Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000011257 shell material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
-
- 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
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a core-shell structure molecular sieve catalyst for cooperatively controlling NO and toluene and a preparation method thereof, wherein the molecular sieve catalyst comprises a Cu-SAPO-34 molecular sieve core formed by loading CuO on an SAPO-34 molecular sieve and CeO self-assembled on the surface of the Cu-SAPO-34 molecular sieve core 2 A housing. The catalyst is specifically composed of the following components in percentage by mass: 1 to 3 percent of CuO and CeO 2 15.0% -30% of the total weight of the SAPO-34. The preparation method comprises the following steps: after Cu-SAPO-34 is prepared by an ion exchange method, ceO is used by adopting a self-assembly method 2 Coating a molecular sieve, drying, introducing nitrogen into the inert gas, and calcining to obtain the catalyst. The catalyst can better disperse active components, improve the hydrothermal stability of the catalyst, effectively prevent sulfur poisoning of the catalyst, cooperatively control toluene during denitration, and improve the carbon-hydrogen poisoning resistance of the catalyst.
Description
Technical Field
The invention belongs to the field of environmental protection, relates to a core-shell structure molecular sieve catalyst for cooperatively controlling NO and toluene and a preparation method thereof, and particularly relates to a core-shell structure Cu-SAPO-34@ CeO 2 Molecular sieve catalysts and methods for their preparation.
Background
NO x The environment-friendly type organic fertilizer has great damage effect on the natural environment and human health, can cause serious environmental problems such as photochemical smog, acid rain, greenhouse effect, ozone layer cavity effect and the like, and has serious pollution; toluene is a serious hazard to the environment, can cause pollution to the air, water environment and water source, and has strong toxicity and serious harm to human health.
At present, the problem of motor vehicle moving source pollution in China is increasingly prominent, and the motor vehicle moving source pollution becomes an important source of air pollution. Nitrogen Oxides (NO) emitted by motor vehicles x ) And Volatile Organic Compounds (VOCs) are important precursors for causing atmospheric pollution problems such as dust haze and near-ground ozone, and the VOCs with strong activity and NO are mixed under certain conditions x A photochemical reaction takes place to cause O 3 The volume increases and photochemical smog is formed, thus generating a wider range of pollution. With the development of the times, the diesel vehicle has become a machineMotor car NO x And a major contributor to toluene emissions. NO in tail gas of diesel vehicle x And toluene are a great hazard to the ecological environment and human health. Therefore, there is an urgent need to develop NO in the exhaust gas of diesel vehicles x And emission reduction studies of toluene.
NO emitted from diesel vehicle x Mainly N in the combustion process of diesel oil 2 And O 2 About 90% NO produced by reaction at elevated temperature x Is NO. The diesel vehicle adopts the thin combustion technology to improve the fuel efficiency and simultaneously increases the oxygen content of tail gas, and the traditional three-way catalyst can not effectively treat NO in the oxygen-enriched environment x . Thus, highly efficient selective catalytic reduction (NH) 3 SCR) Simultaneous Oxidation of toluene with Nitric Oxide (NO) to control NO in Diesel exhaust x And toluene contamination. In practical application, the Cu/SAPO-34 molecular sieve catalyst has high NH 3 SCR catalytic Activity and N 2 Selectivity, good anti-carbon characteristics, a wider temperature window and excellent hydrothermal stability become the current very potential diesel vehicle SCR catalyst. However, the Cu-SAPO-34 molecular sieve catalyst still suffers from the following disadvantages: (1) poor sulfur resistance; and (2) the catalytic oxidation of toluene has poor activity. However, no relevant research is available to solve the above problems, which limits the better application of the Cu-SAPO-34 molecular sieve catalyst. Therefore, the high NH content of the Cu-SAPO-34 catalyst is kept 3 The improvement of the sulfur resistance and the catalytic oxidation of toluene of the catalyst while the SCR activity, the high hydrothermal stability and the good anti-carbon property are the problems which need to be solved urgently.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a core-shell structure molecular sieve catalyst for cooperatively controlling NO and toluene and a preparation method thereof.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the core-shell structure molecular sieve catalyst for cooperatively controlling NO and toluene comprises a Cu-SAPO-34 molecular sieve core formed by loading CuO on an SAPO-34 molecular sieve and CeO self-assembled on the surface of the Cu-SAPO-34 molecular sieve core 2 Housings with co-operating controlsNO and toluene properties.
Preferably, the molecular sieve catalyst contains CuO and CeO 2 And the SAPO-34 comprises the following components in percentage by mass: 1 to 3 percent of CuO and CeO 2 15-30% and the balance SAPO-34.
The preparation method of the core-shell structure molecular sieve catalyst for cooperatively controlling NO and toluene comprises the following steps:
(1) Taking the SAPO-34 molecular sieve as a carrier, and loading CuO on the carrier by using an ion exchange method to obtain the Cu-SAPO-34 molecular sieve;
(2) Taking a Cu-SAPO-34 molecular sieve as a core, and self-assembling a layer of CeO on the surface of the Cu-SAPO-34 molecular sieve by using a self-assembling method 2 A shell to obtain the core-shell structure molecular sieve catalyst for cooperatively controlling NO and toluene, i.e. the core-shell structure Cu-SAPO-34@ CeO 2 A molecular sieve catalyst.
Preferably, the ion exchange method in the step (1) is an aqueous solution ion exchange method, and the copper source of the CuO is copper acetate, copper nitrate and copper sulfate.
More preferably, the ion exchange method of the aqueous solution in the step (1) is to add SAPO-34 molecular sieve to the copper nitrate solution, wherein every 5g of SAPO-34 molecular sieve is added to 5-20 mL of copper nitrate solution with the concentration of 0.065-0.25 mol/L; stirring at normal temperature for 4-7 h, drying at 45-55 deg.C, preferably 50 deg.C for 20-28 h, and calcining at 500-600 deg.C under air atmosphere for 3-5 h, preferably 4h to obtain Cu-SAPO-34 molecular sieve.
Preferably, the self-assembly method in the step (2) is to disperse 100mg of Cu-SAPO-34 powder in 50-150 mL of ethanol aqueous solution and stir for 10-20 min, then add 1g of polyvinylpyrrolidone (PVP) powder, then add cerium nitrate and hexamethylenetetramine in sequence, stir at the constant temperature for 2-3 h under the condition of 60-80 ℃ while carrying out condensation reflux, centrifuge at 6000-8000 r, wash with deionized water and absolute ethyl alcohol, dry at 45-55 ℃, preferably at 50 ℃ for 20-28 h, and finally calcine at 400-600 ℃ for 3-5 h under the inert ventilation environment to obtain the core-shell structure Cu-SAPO-34@ CeO 2 A molecular sieve catalyst.
Preferably, the volume ratio of water to ethanol in the ethanol aqueous solution is 1; the addition amount of the cerium nitrate is 0.04-0.08 g; the addition amount of the hexamethylene tetramine is 0.04-0.08 g.
The present invention is further described below.
The invention adopts an impregnation method to prepare Cu-SAPO-34, and adopts a self-assembly method to prepare Cu-SAPO-34@ CeO with a core-shell structure 2 Molecular sieve catalyst, ceO 2 Can well coat Cu-SAPO-34.CeO (CeO) 2 As a shell structure, the catalytic activity and the sulfur resistance of the catalyst can be obviously improved; at the same time, ceO 2 Has strong oxygen storage capacity and special Ce 3+ /Ce 4+ Oxidation-reduction of p-toluene to promote the catalytic oxidation of toluene to CO 2 And H 2 O, and the like.
The core-shell structure Cu-SAPO-34@ CeO 2 The molecular sieve catalyst has high specific surface area, so that active components can be better dispersed; secondly, the temperature range of the catalyst is widened, and the hydrothermal stability of the catalyst is improved; again, the catalyst was formed with CeO 2 The Cu-SAPO-34 is coated on the shell, so that the sulfur poisoning of the catalyst can be effectively prevented, the toluene can be synergistically controlled during denitration, and the hydrocarbon poisoning resistance of the catalyst is improved. The catalyst has excellent application prospect in treating the tail gas of the diesel vehicle.
Compared with the existing SCR catalyst, the invention has the following advantages:
(1) CeO is used in the invention 2 The Cu-SAPO-34 molecular sieve is coated by the shell material, SO that the original characteristics of the molecular sieve can be maintained, and the core active site is prevented from being subjected to SO 2 Influence and ability to retain CeO 2 The performance characteristics, the sulfur resistance of the catalyst and the activity of catalytic oxidation of toluene are improved.
（2）CeO 2 CeO can be realized under oxidation and reduction conditions respectively 2 With CeO 3 Ce of conversion between 3+ /Ce 4+ Redox couple and highly reactive, unstable oxygen vacancies during conversion, thus favoring O more 2 And (4) activating molecules to promote the catalytic oxidation of the toluene.
Detailed Description
Example 1:
the preparation method of the core-shell structure molecular sieve catalyst for cooperatively controlling NO and toluene comprises the following steps:
(1) Soaking 5g of SAPO-34 molecular sieve in 10mL of 0.065mol/L copper nitrate solution, and magnetically stirring for 5 hours at normal temperature; then drying at 50 ℃ for 24h, calcining at 550 ℃ for 4h under an air atmosphere, and grinding and sieving to obtain Cu-SAPO-34;
(2) Dispersing 100mg of Cu-SAPO-34 powder in 100mL of ethanol water (50 mL of deionized water and 50mL of absolute ethyl alcohol), and stirring for 10min;
(4) Adding 1g of polyvinylpyrrolidone (PVP) powder, stirring until the PVP powder is completely dissolved, then sequentially adding 0.04g of cerium nitrate and 0.06g of hexamethylenetetramine, and continuing to stir for 10min;
(5) Condensing and refluxing at 60 ℃ and stirring at constant temperature for 2h, centrifuging at 8000r, washing with deionized water and absolute ethyl alcohol, drying at 50 ℃ for 12h, and calcining at 500 ℃ for 3h in an inert ventilation environment to obtain the final product Cu-SAPO-34@ CeO 2 。
Example 2:
the preparation method of the core-shell structure molecular sieve catalyst for cooperatively controlling NO and toluene comprises the following steps:
(1) Soaking 5g of SAPO-34 molecular sieve in 10mL of 0.158mol/L copper nitrate solution, and magnetically stirring for 5 hours at normal temperature; then drying at 50 ℃ for 24h, calcining at 550 ℃ for 4h under an air atmosphere, and grinding and sieving to obtain Cu-SAPO-34;
(2) Dispersing 100mg of Cu-SAPO-34 powder in 100mL of ethanol water (50 mL of deionized water and 50mL of absolute ethyl alcohol), and stirring for 10min;
(4) Adding 1g of polyvinylpyrrolidone (PVP) powder, stirring until the PVP powder is completely dissolved, then sequentially adding 0.08g of cerium nitrate and 0.06g of hexamethylenetetramine, and continuing stirring for 10min;
(5) Condensing and refluxing at 60 ℃ and stirring at constant temperature for 2h, centrifuging at 8000r, washing with deionized water and absolute ethyl alcohol, drying at 50 ℃ for 12h, and calcining at 500 ℃ for 3h in an inert ventilation environment to obtain the final product Cu-SAPO-34@ CeO 2 。
Example 3:
the preparation method of the core-shell structure molecular sieve catalyst for cooperatively controlling NO and toluene comprises the following steps:
(1) Soaking 5g of SAPO-34 molecular sieve in 10mL of 0.25mol/L copper nitrate solution, and magnetically stirring for 5 hours at normal temperature; then drying at 50 ℃ for 24h, calcining at 550 ℃ for 4h under an air atmosphere, and grinding and sieving to obtain Cu-SAPO-34;
(2) Dispersing 100mg of Cu-SAPO-34 powder in 100mL of ethanol water (50 mL of deionized water and 50mL of absolute ethyl alcohol), and stirring for 10min;
(4) Adding 1g of polyvinylpyrrolidone (PVP) powder, stirring until the PVP powder is completely dissolved, then sequentially adding 0.08g of cerium nitrate and 0.06g of hexamethylenetetramine, and continuing stirring for 10min;
(5) Condensing and refluxing at 60 ℃ while stirring at constant temperature for 2h, centrifuging at 8000r, washing with deionized water and absolute ethyl alcohol, drying at 50 ℃ for 12h, calcining at 500 ℃ for 3h in an inert ventilation environment, and obtaining a final product expressed as Cu-SAPO-34@ CeO 2 。
Example 4:
the core-shell structure molecular sieve catalyst for cooperatively controlling NO and methylbenzene provided by the invention can be used for cooperatively controlling NO and methylbenzene performance test
The activity test of the NO and the toluene is carried out in a fixed bed reactor in a synergic control mode. The catalyst is loaded into a catalytic reactor, the gas flow is controlled to be 200ml/min, and the components of the tail gas of the simulated diesel vehicle are as follows: 3% vol.O 2 ，400ppmNO，200ppmSO 2 200ppm toluene, balance gas N 2 ，500ppm NH 3 As a reducing agent; at an airspeed of 50000h -1 And the reaction temperature is controlled at 100-600 ℃, and the performance of the catalyst for synergistically controlling NO and toluene is tested.
The results show that: in the temperature range of 200-400 ℃ and SO 2 Under the existing conditions, the conversion rate of NO can reach more than 80 percent, and the conversion rate of toluene can reach more than 80 percent.
Example 5
Sulfur resistance test of the catalyst of the invention
Using 0.50 g of the molecular sieve catalyst prepared in inventive example 3 as the baseChecking the object; the airspeed is as follows: 50000h -1 (ii) a The simulated flue gas comprises the following components: 3% vol.O 2 400ppmNO,200ppm toluene, equilibrium gas N 2 ，500ppm NH 3 As a reducing agent; the catalyst is tested at 300 ℃ to synergistically control the activity of NO and toluene, and 200ppm SO is introduced 2 Checking for Activity to pass in SO 2 The latter is the case.
The results show that: conversion of NO and toluene in the presence of SO 2 The change is small, so that the core-shell structure molecular sieve catalyst for synergistically controlling NO and toluene has stronger sulfur resistance.
Example 6
BET and SEM testing of the catalysts of the invention
The specific surface area and pore structure analysis of all catalysts in this invention was determined using a Micromeritics Tristar (Micrometrics Instrument Crop, USA) model number Micromeritics Tristar (1030). And (3) testing conditions are as follows: analysis gas and saturated pressure determination gas as N 2 And backfilling gas and measuring free space gas are He, the temperature is 77K, and a sample to be measured is degassed for 5 hours at 180 ℃. The specific surface area is the pore volume and pore diameter calculated by the BET (Brunauer-Emmett-Teller) formula under the condition of 0.05-0.35 gas partial pressure, and is calculated by BJH (Barrett-Joyner-Halenda) from a desorption curve; furthermore, transmission Electron Microscopy (TEM) analysis of the catalyst of the present invention was carried out by using a JEM-2010 TEM instrument from Hitachi.
The results show that: the prepared molecular sieve catalyst has large specific surface area and is beneficial to the catalytic reaction. Meanwhile, as can be seen from TEM images, the catalyst is a molecular sieve catalyst with a core-shell structure and used for synergistically controlling NO and toluene.
Claims (5)
1. The application of the core-shell structure molecular sieve catalyst in the cooperative control of NO and toluene is characterized in that the molecular sieve catalyst comprises a Cu-SAPO-34 molecular sieve core formed by loading CuO on an SAPO-34 molecular sieve and CeO self-assembled on the surface of the Cu-SAPO-34 molecular sieve core 2 A housing; the molecular sieveCuO and CeO in catalyst 2 And the SAPO-34 comprises the following components in percentage by mass: 1 to 3 percent of CuO and CeO 2 15-30% of SAPO-34 as the rest; the core-shell structure molecular sieve catalyst for synergistically controlling NO and toluene is prepared by the following method: (1) Taking the SAPO-34 molecular sieve as a carrier, and loading CuO on the carrier by using an ion exchange method to obtain the Cu-SAPO-34 molecular sieve; (2) Taking a Cu-SAPO-34 molecular sieve as a core, and self-assembling a layer of CeO on the surface of the Cu-SAPO-34 molecular sieve by using a self-assembling method 2 The shell is used for obtaining Cu-SAPO-34@ CeO with a core-shell structure 2 A molecular sieve catalyst.
2. The application of the core-shell structure molecular sieve catalyst in the cooperative control of NO and toluene as claimed in claim 1, wherein the ion exchange method in step (1) is an aqueous solution ion exchange method, and the copper source of CuO is cupric acetate, cupric nitrate, and cupric sulfate.
3. The use of the core-shell structure molecular sieve catalyst in the synergistic control of NO and toluene according to claim 2, wherein the aqueous solution ion exchange method in step (1) is to add SAPO-34 molecular sieve into copper nitrate solution, wherein every 5g of SAPO-34 molecular sieve is added into 5-20 mL of copper nitrate solution with concentration of 0.065-0.25 mol/L; stirring for 4-7 h at normal temperature, drying at 45-55 ℃ for 20-28 h, and finally calcining at 500-600 ℃ for 3-5 h in an air atmosphere to obtain the Cu-SAPO-34 molecular sieve.
4. The application of the core-shell structure molecular sieve catalyst in the cooperative control of NO and toluene according to claim 1, wherein the self-assembly method in step (2) is to disperse every 100mg of Cu-SAPO-34 powder in 50-150 mL of ethanol water solution and stir for 10-20 min, then add 1g of polyvinylpyrrolidone powder, then add cerium nitrate and hexamethylenetetramine in sequence, stir at a constant temperature for 2-3 h under the condition of 60-80 ℃, after centrifugation at 6000-8000 r, wash with deionized water and absolute ethanol, dry at 45-55 ℃ for 20-28 h, and finally calcine at 400-600 ℃ for 3-5 h under an inert ventilation environment to obtain the core-shell structure Cu-SAPO-34 CeO @ 2 A molecular sieve catalyst.
5. The application of the core-shell structure molecular sieve based catalyst in the cooperative control of NO and toluene as claimed in claim 4, wherein the volume ratio of water to ethanol in the ethanol aqueous solution is 1; the addition amount of the cerium nitrate is 0.04-0.08 g; the addition amount of the hexamethylene tetramine is 0.04-0.08 g.
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