CN116139861B - Catalyst applicable to storage reduction of nitrogen oxides of gas turbine as well as preparation and application thereof - Google Patents
Catalyst applicable to storage reduction of nitrogen oxides of gas turbine as well as preparation and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 125
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000007789 gas Substances 0.000 title claims abstract description 58
- 238000003860 storage Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000009467 reduction Effects 0.000 title claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 71
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000008367 deionised water Substances 0.000 claims abstract description 35
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 35
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 25
- 230000032683 aging Effects 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 17
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 13
- 238000006722 reduction reaction Methods 0.000 claims description 11
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 3
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 3
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 60
- 238000002474 experimental method Methods 0.000 description 42
- 230000000694 effects Effects 0.000 description 35
- 239000012159 carrier gas Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 28
- 238000011068 loading method Methods 0.000 description 26
- 229910001868 water Inorganic materials 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000843 powder Substances 0.000 description 17
- 238000000227 grinding Methods 0.000 description 14
- 238000012216 screening Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000000779 smoke Substances 0.000 description 6
- 239000010955 niobium Substances 0.000 description 5
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
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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
- B01D53/74—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
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
- B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives thereof
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- B01D2251/00—Reactants
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- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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Abstract
The invention discloses a catalyst suitable for nitrogen oxide storage reduction of a gas turbine, a preparation method and application thereof. In the catalyst, ag-M/CeO 2 is taken as a core, and the surface of the catalyst is coated with an amorphous TiO 2 layer; ag-M/CeO 2 represents the oxide loaded with Ag, ag 2 O and acid additive M on the surface of CeO 2; the acid auxiliary agent M is at least one of W, sb, mo, nb. The preparation method comprises the following steps: dispersing CeO 2, silver nitrate and a precursor of an acid auxiliary agent M in deionized water, uniformly mixing, drying and roasting to obtain Ag-M/CeO 2; dissolving tetrabutyl titanate in ethanol to obtain solution A, mixing nitric acid with deionized water and ethanol to obtain solution B, and adding the solution A into the solution B with continuous stirring to obtain TiO 2 sol; and adding Ag-M/CeO 2 into the TiO 2 sol, continuously stirring, aging and roasting to obtain the Ag-M/CeO 2@TiO2 catalyst suitable for the storage and reduction of nitrogen oxides of the gas turbine.
Description
Technical Field
The invention relates to the technical field of nitrogen oxide reduction of gas turbines, in particular to a catalyst suitable for nitrogen oxide storage reduction of gas turbines, a preparation method and application thereof.
Background
Because of the optimized adjustment of the energy structure in China, the scale of the gas power plant is continuously enlarged, and the emission problem of nitrogen oxides (NO x) is increasingly serious.
The power demand difference between day and night and the instability of new energy power generation require frequent peak shaving of a power grid, and a gas turbine (hereinafter referred to as a "gas turbine") has the characteristic of quick start and stop, so that the peak shaving task of the power grid is borne. However, frequent start and stop of the combustion engine easily causes the problems of exceeding standard emission of NO x and yellow smoke emission of tail gas (high NO 2/NOx). Compared with NO, NO 2 has stronger toxicity, can cause diseases such as bronchitis, even lung cancer and the like on human and animals, and can also bring serious disaster problems such as photochemical smog, acid rain and the like. Therefore, how to solve the problem of yellow smoke in the starting stage of the gas turbine becomes the key point of controlling NO x in the gas power plant in China at present.
The denitration catalyst is the key for treating the tail end of the NO x in the gas fume. The Selective Catalytic Reduction (SCR) technology is the most widely applied fixed source denitration technology at present, and the representative catalyst is a V 2O5/TiO2 -based catalyst, which has good middle-high Wen Tuoxiao performance (300-420 ℃), but poor adaptability to the low temperature and high NO 2/NOx flue gas environment at the starting stage of the combustion engine, and insufficient removal capability of nitrogen oxides.
For the removal of nitrogen oxides at low temperatures, adsorption storage technology is a suitable choice. The Passive nitrogen oxide adsorption (PNA) technology represented by Pd/ZSM-5 is mainly used in the cold start stage of the motor vehicle, has a better low-temperature NO x adsorption effect, but usually needs to be matched with post-treatment to remove NO x. The technology of nitrogen oxide Storage Reduction (NSR) represented by Pt-Ba/Al utilizes the lean-rich phase switching of an engine of a motor vehicle to realize the Storage Reduction of nitrogen oxides, but has the defects of higher noble metal cost, smaller Storage capacity of NO x and the like, and is not suitable for the application of large smoke volume of a gas power plant.
Cerium oxide (CeO 2) has been widely studied and applied in the SCR denitration field as a main catalyst or a co-catalyst by virtue of its excellent oxygen storage and release properties. Meanwhile, the oxygen vacancies rich in the CeO 2 surface have strong chemical adsorption effect on NO x. Therefore, based on CeO 2, aiming at the characteristic of frequent start and stop of the gas engine, a cerium-based denitration catalyst with low-temperature NO 2 adsorption and medium-high-temperature NO x catalytic reduction functions is developed, and the cerium-based denitration catalyst has very important practical significance for realizing full-time emission control of NO x of a gas power plant.
The patent specification with publication number CN 108993471A discloses a supported nano cerium oxide particle catalyst for NO x catalytic purification, which takes a titanium dioxide carrier as a main component, ag as a cocatalyst, the mass fraction of cerium oxide is only 0.5% -15%, the catalyst structure is simple supported on the surface of titanium dioxide, and the patent technology does not relate to the adsorption storage and reduction process of NO 2.
Disclosure of Invention
The invention provides a catalyst suitable for nitrogen oxide storage reduction of a gas turbine, which is a cerium-based catalyst with low cost and better activity and stability, can be used for storage reduction of NO x in a gas turbine starting and low-load (Start Up and Low Loading, SULL) operation stage, has good SCR denitration activity in a gas turbine high-load (High Loading, HL) operation stage, and can effectively solve the problem of yellow smoke emission of tail gas caused by frequent start and stop of a gas turbine in a current gas power plant.
A catalyst suitable for the nitrogen oxide storage reduction of a gas turbine, wherein Ag-M/CeO 2 is taken as a core, and the surface of the catalyst is coated with an amorphous TiO 2 layer;
Ag-M/CeO 2 represents the oxide of the surface loaded Ag, ag 2 O and acid auxiliary agent M of CeO 2;
the acid auxiliary M is at least one of W, sb, mo, nb, preferably W.
The temperature of the smoke in the SULL stage of the gas engine is low, the water content is high, NO x in the smoke is mainly NO 2, and the adaptability of the traditional vanadium-tungsten-titanium catalyst is poor. The CeO 2 has rich oxygen vacancies and certain alkalinity on the surface so as to ensure that the CeO 2 has excellent low-temperature NO 2 adsorption performance, but the weak surface acidity also ensures that the SCR denitration reaction cannot be effectively completed. Therefore, the invention is based on CeO 2, and the addition of the acid auxiliary agent M, ag and Ag 2 O respectively improves the surface acidity and redox performance, improves the adsorption and activation capacity of NH 3, and greatly improves the SCR performance. Meanwhile, the strong interaction between CeO 2 and the acid auxiliary agent M promotes the formation of more oxygen vacancies, ag and Ag 2 O can induce the oxygen vacancies of the CeO 2 bulk phase to migrate to the surface, and the two effects jointly improve the adsorption performance of the catalyst on NO 2. Finally, amorphous TiO 2 is used for wrapping the catalyst, so that the agglomeration of CeO 2 is avoided, acid sites are added, and the denitration performance of the catalyst is further improved. In addition, the inventor also researches and discovers that the nitrogen oxides, especially the low-temperature storage effect and the denitration performance of NO 2, of the invention cannot be obtained if the simple supported catalyst such as cerium oxide, ag, acid auxiliary agent M and the like is carried by titanium dioxide instead of the Ag-M/CeO 2 core and TiO 2 shell structure of the invention.
In the SULL stage of the gas turbine, the catalyst can efficiently adsorb NO 2; in the stage of the combustion engine HL, the surface of the catalyst can be subjected to SCR reaction in an in-situ NH 3 spraying mode, NO 2 adsorbed and stored on the surface of the catalyst can be reduced to N 2 for desorption, and the regeneration of the adsorption site of NO 2 on the surface of the catalyst is realized while the denitration is completed.
Preferably, the catalyst takes CeO 2 as a main component, wherein the mass ratio of CeO 2 to TiO 2 is preferably 100:5-20, more preferably 100:10, and the catalyst can show higher adsorption capacity to NO 2 and better SCR catalytic performance under the preferable condition.
Too high of Ag, ag 2 O and acid auxiliary agent M loading can reduce the adsorption of CeO 2 on NO 2, while too low of loading can make the SCR performance improvement effect not large. Preferably, in the Ag-M/CeO 2, the mass ratio of the sum of the masses of Ag and Ag 2 O to the mass ratio of the oxide of the acid auxiliary M to CeO 2 is 0.02-0.2 (more preferably 0.1) to 0.5-2 (more preferably 1) to 100; wherein the sum of the masses of Ag and Ag 2 O is calculated by the mass of Ag and Ag 2 O converted into Ag 2 O, and the mass of the oxide of the acid auxiliary agent M is calculated by WO 3、Sb2O3、MoO3、Nb2O5.
On one hand, ceO 2 serves as a main NO 2 low-temperature adsorption and storage site, NO 2 can be efficiently adsorbed and stored in the form of nitrate/nitrite species in a SULL stage, and on the other hand, the excellent oxygen storage and release performance plays an important role in the SCR function in an HL stage; the acid auxiliary agent M and the TiO 2 wrapped outside provide a large number of surface acid sites for the catalyst, which is favorable for the adsorption of the reducing agent NH 3 in the denitration process, thereby greatly improving the SCR performance of CeO 2; the addition of the acid auxiliary agent M, ag and Ag 2 O can generate good interaction with CeO 2, and promote more generation of surface oxygen vacancies, so that the adsorption performance of the catalyst on NO 2 is enhanced, and meanwhile, the oxidation-reduction performance of the catalyst is further improved, and the denitration efficiency is improved.
In the catalyst, ceO 2 is preferably obtained by roasting cerium nitrate hexahydrate at 400-450 ℃ for 4-5 hours.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
(1) Preparation of Ag-M/CeO 2: dispersing CeO 2, silver nitrate and a precursor of an acid auxiliary agent M in deionized water, uniformly mixing, drying and roasting to obtain Ag-M/CeO 2;
(2) Preparation of TiO 2 sol: dissolving tetrabutyl titanate in ethanol to obtain solution A, mixing nitric acid with deionized water and ethanol to obtain solution B, and adding the solution A into the solution B with continuous stirring to obtain TiO 2 sol;
(3) Preparation of Ag-M/CeO 2@TiO2 catalyst: and (3) adding the Ag-M/CeO 2 in the step (1) into the TiO 2 sol in the step (2), continuously stirring, aging and roasting to obtain the Ag-M/CeO 2@TiO2 catalyst suitable for the nitrogen oxide storage reduction of the gas turbine.
In the step (1), the precursor of the acid promoter M is preferably at least one of ammonium metatungstate, antimony acetate, ammonium molybdate and niobium oxalate.
Preferably, in the step (1), the roasting temperature is 400-450 ℃ and the time is 4-5 h.
Preferably, in the step (3), the aging temperature is 75-85 ℃ and the aging time is 40-56 h.
Preferably, in the step (3), the roasting temperature is 400-450 ℃ and the time is 3-4 h.
The invention also provides application of the catalyst in the catalytic reduction of nitrogen oxides in a gas turbine as a general inventive concept.
Compared with the prior art, the invention has the beneficial effects that:
1. The CeO 2 is used as a main NO 2 adsorption storage site, and each additive component greatly improves the surface oxygen vacancy content, and simultaneously improves the surface acidity and the oxidation-reduction capability of the catalyst, so that the catalyst has the dual functions of low-temperature NO 2 adsorption and medium-high-temperature NO x catalytic reduction.
2. The outer layer of Ag-M/CeO 2 is coated by amorphous TiO 2, so that the agglomeration of CeO 2 can be avoided, rich acid sites are provided, and the medium-high temperature denitration performance and stability of the catalyst are further ensured.
3. The invention has better circulation stability, the NO 2 adsorption performance of the catalyst can be regenerated by in-situ spraying NH 3 to match with SCR reaction at medium and high temperature, and the NO x control in the start-stop circulation process of the combustion engine can be realized in a longer time.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
And (3) preparing a catalyst: (1) Roasting cerium nitrate hexahydrate at 450 ℃ for 4 hours to obtain CeO 2, grinding and screening, taking 8g of 40-60 mesh CeO 2, dispersing in 100mL of deionized water, adding a certain amount of silver nitrate and ammonium metatungstate, uniformly mixing, drying at 120 ℃ for 12 hours, roasting at 450 ℃ for 4 hours to obtain Ag-W/CeO 2 powder, controlling the total loading of Ag and Ag 2 O to be about 0.1wt% (calculated by the mass of Ag and Ag 2 O to be Ag 2 O and taking the mass of CeO 2 as a reference), and the loading of W to be about 1wt% (calculated by the mass of WO 3 and taking the mass of CeO 2 as a reference);
(2) Dissolving a certain amount of tetrabutyl titanate in 40mL of absolute ethyl alcohol to serve as a solution A, mixing 5mL of 68wt% concentrated nitric acid with 20mL of absolute ethyl alcohol and 20mL of deionized water to serve as a solution B, and then dropwise adding the solution A into the stirred solution B to obtain TiO 2 sol;
(3) Adding Ag-W/CeO 2 powder into the fresh TiO 2 sol prepared in the step (2), continuously stirring for 6 hours, aging at 80 ℃ for 48 hours, and finally roasting at 450 ℃ for 3 hours to obtain the Ag-W/CeO 2@TiO2 catalyst, wherein the content of the outer layer TiO 2 is controlled to be about 10wt% (based on the mass of CeO 2).
Catalyst activity test: the activity experiment is carried out on a fixed bed reactor, the catalyst dosage is 3.0g, and the granularity is 40-60 meshes. In the NO 2 adsorption experiment, the composition of the mixed gas is as follows: [ NO 2]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV =30,000 ml g- 1h-1; in the SCR experiment, the composition of the mixed gas is as follows: [ NO ] = [ NH 3]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV = 30,000ml g- 1h-1. The catalyst has an adsorption capacity of 12.8mg/g of NO 2 at 150 ℃, a conversion rate of 98.6% of NO x at 350 ℃ and a selectivity of 99.4% of N 2, and shows good stability, and the adsorption performance of NO 2 after 3 cycles is similar to that of a fresh sample.
Example 2
And (3) preparing a catalyst: (1) Roasting cerium nitrate hexahydrate at 450 ℃ for 4 hours to obtain CeO 2, grinding and screening, taking 8g of 40-60 mesh CeO 2, dispersing in 100mL of deionized water, adding a certain amount of silver nitrate and ammonium meta-tungstate, uniformly mixing, drying at 120 ℃ for 12 hours, roasting at 450 ℃ for 4 hours to obtain Ag-W/CeO 2, controlling the total loading of Ag and Ag 2 O to be about 0.05wt% (calculated by the mass of Ag and Ag 2 O converted to Ag 2 O and taking the mass of CeO 2 as a reference), and the loading of W to be about 1wt% (calculated by the mass of WO 3 and taking the mass of CeO 2 as a reference);
(2) Dissolving a certain amount of tetrabutyl titanate in 40mL of absolute ethyl alcohol to serve as a solution A, mixing 5mL of 68wt% concentrated nitric acid with 20mL of absolute ethyl alcohol and 20mL of deionized water to serve as a solution B, and then dropwise adding the solution A into the stirred solution B to obtain TiO 2 sol;
(3) Adding Ag-W/CeO 2 powder into the fresh TiO 2 sol prepared in the step (2), continuously stirring for 6 hours, aging at 80 ℃ for 48 hours, and finally roasting at 450 ℃ for 3 hours to obtain the Ag-W/CeO 2@TiO2 catalyst, wherein the content of the outer layer TiO 2 is controlled to be about 10wt% (based on the mass of CeO 2).
Catalyst activity test: the activity experiment is carried out on a fixed bed reactor, the catalyst dosage is 3.0g, and the granularity is 40-60 meshes. In the NO 2 adsorption experiment, the composition of the mixed gas is as follows: [ NO 2]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV (mass space velocity) =30,000 ml g- 1h-1; in the SCR experiment, the composition of the mixed gas is as follows: [ NO ] = [ NH 3]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV = 30,000ml g- 1h-1. The adsorption capacity of NO 2 of the catalyst at 150 ℃ is 11.9mg/g; the conversion of NO x at 300℃was 97.2% and the N 2 selectivity was 97.9%; the conversion of NO x at 350 ℃ was 97.3%, the selectivity of N 2 was 98.4%, and good stability was exhibited, and the adsorption performance of NO 2 after 3 cycles was similar to that of fresh samples.
Example 3
And (3) preparing a catalyst: (1) Roasting cerium nitrate hexahydrate at 450 ℃ for 4 hours to obtain CeO 2, grinding and screening, taking 8g of 40-60 mesh CeO 2, dispersing in 100mL of deionized water, adding a certain amount of silver nitrate and ammonium meta-tungstate, uniformly mixing, drying at 120 ℃ for 12 hours, roasting at 450 ℃ for 4 hours to obtain Ag-W/CeO 2, controlling the total loading of Ag and Ag 2 O to be about 0.2wt% (calculated by the mass of Ag and Ag 2 O converted to Ag 2 O and taking the mass of CeO 2 as a reference), and the loading of W to be about 1wt% (calculated by the mass of WO 3 and taking the mass of CeO 2 as a reference);
(2) Dissolving a certain amount of tetrabutyl titanate in 40mL of absolute ethyl alcohol to serve as a solution A, mixing 5mL of 68wt% concentrated nitric acid with 20mL of absolute ethyl alcohol and 20mL of deionized water to serve as a solution B, and then dropwise adding the solution A into the stirred solution B to obtain TiO 2 sol;
(3) Adding Ag-W/CeO 2 powder into the fresh TiO 2 sol prepared in the step (2), continuously stirring for 6 hours, aging at 80 ℃ for 48 hours, and finally roasting at 450 ℃ for 3 hours to obtain the Ag-W/CeO 2@TiO2 catalyst, wherein the content of the outer layer TiO 2 is controlled to be about 10wt% (based on the mass of CeO 2).
Catalyst activity test: the activity experiment is carried out on a fixed bed reactor, the catalyst dosage is 3.0g, and the granularity is 40-60 meshes. In the NO 2 adsorption experiment, the composition of the mixed gas is as follows: [ NO 2]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV =30,000 ml g- 1h-1; in the SCR experiment, the composition of the mixed gas is as follows: [ NO ] = [ NH 3]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV = 30,000ml g- 1h-1. The catalyst has an adsorption capacity of 12.2mg/g of NO 2 at 150 ℃, a conversion rate of NO x at 350 ℃ of 100%, a selectivity of N 2 of 97.9%, and good stability, and the adsorption performance of NO 2 after 3 cycles is similar to that of a fresh sample.
Example 4
And (3) preparing a catalyst: (1) Roasting cerium nitrate hexahydrate at 450 ℃ for 4 hours to obtain CeO 2, grinding and screening, taking 8g of 40-60 mesh CeO 2, dispersing in 100mL of deionized water, adding a certain amount of silver nitrate and ammonium metatungstate, uniformly mixing, drying at 120 ℃ for 12 hours, roasting at 450 ℃ for 4 hours to obtain Ag-W/CeO 2, controlling the total load of Ag and Ag 2 O to be about 0.1wt% (calculated by the mass of Ag and Ag 2 O converted to Ag 2 O and based on CeO 2) and the load of W to be about 0.5wt% (calculated by the mass of WO 3 and based on CeO 2);
(2) Dissolving a certain amount of tetrabutyl titanate in 40mL of absolute ethyl alcohol to serve as a solution A, mixing 5mL of 68wt% concentrated nitric acid with 20mL of absolute ethyl alcohol and 20mL of deionized water to serve as a solution B, and then dropwise adding the solution A into the stirred solution B to obtain TiO 2 sol;
(3) Adding Ag-W/CeO 2 powder into the fresh TiO 2 sol prepared in the step (2), continuously stirring for 6 hours, aging at 80 ℃ for 48 hours, and finally roasting at 450 ℃ for 3 hours to obtain the Ag-W/CeO 2@TiO2 catalyst, wherein the content of the outer layer TiO 2 is controlled to be about 10wt% (based on the mass of CeO 2).
Catalyst activity test: the activity experiment is carried out on a fixed bed reactor, the catalyst dosage is 3.0g, and the granularity is 40-60 meshes. In the NO 2 adsorption experiment, the composition of the mixed gas is as follows: [ NO 2]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV =30,000 ml g- 1h-1; in the SCR experiment, the composition of the mixed gas is as follows: [ NO ] = [ NH 3]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV = 30,000ml g- 1h-1. The catalyst has an adsorption capacity of 11.1mg/g of NO 2 at 150 ℃, a conversion rate of 86.7% of NO x at 350 ℃ and a selectivity of 97.1% of N 2, and shows good stability, and the adsorption performance of NO 2 after 3 cycles is similar to that of a fresh sample.
Example 5
And (3) preparing a catalyst: (1) Roasting cerium nitrate hexahydrate at 450 ℃ for 4 hours to obtain CeO 2, grinding and screening, taking 8g of 40-60 mesh CeO 2, dispersing in 100mL of deionized water, adding a certain amount of silver nitrate and ammonium meta-tungstate, uniformly mixing, drying at 120 ℃ for 12 hours, roasting at 450 ℃ for 4 hours to obtain Ag-W/CeO 2, controlling the total loading of Ag and Ag 2 O to be about 0.1wt% (calculated by the mass of Ag and Ag 2 O converted to Ag 2 O and taking the mass of CeO 2 as a reference), and the loading of W to be about 2wt% (calculated by the mass of WO 3 and taking the mass of CeO 2 as a reference);
(2) Dissolving a certain amount of tetrabutyl titanate in 40mL of absolute ethyl alcohol to serve as a solution A, mixing 5mL of 68wt% concentrated nitric acid with 20mL of absolute ethyl alcohol and 20mL of deionized water to serve as a solution B, and then dropwise adding the solution A into the stirred solution B to obtain TiO 2 sol;
(3) Adding Ag-W/CeO 2 powder into the fresh TiO 2 sol prepared in the step (2), continuously stirring for 6 hours, aging at 80 ℃ for 48 hours, and finally roasting at 450 ℃ for 3 hours to obtain the Ag-W/CeO 2@TiO2 catalyst, wherein the content of the outer layer TiO 2 is controlled to be about 10wt% (based on the mass of CeO 2).
Catalyst activity test: the activity experiment is carried out on a fixed bed reactor, the catalyst dosage is 3.0g, and the granularity is 40-60 meshes. In the NO 2 adsorption experiment, the composition of the mixed gas is as follows: [ NO 2]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV =30,000 ml g- 1h-1; in the SCR experiment, the composition of the mixed gas is as follows: [ NO ] = [ NH 3]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV = 30,000ml g- 1h-1. The catalyst has an adsorption capacity of 10.8mg/g of NO 2 at 150 ℃, a conversion rate of 98.7% of NO x at 350 ℃ and a selectivity of 98.4% of N 2, and shows good stability, and the adsorption performance of NO 2 after 3 cycles is similar to that of a fresh sample.
Example 6
And (3) preparing a catalyst: (1) Roasting cerium nitrate hexahydrate at 450 ℃ for 4 hours to obtain CeO 2, grinding and screening, taking 8g of 40-60 mesh CeO 2, dispersing in 100mL of deionized water, adding a certain amount of silver nitrate and ammonium meta-tungstate, uniformly mixing, drying at 120 ℃ for 12 hours, roasting at 450 ℃ for 4 hours to obtain Ag-W/CeO 2, controlling the total loading of Ag and Ag 2 O to be about 0.1wt% (calculated by the mass of Ag and Ag 2 O converted to Ag 2 O and based on the mass of CeO 2), and the loading of W to be about 1wt% (calculated by the mass of WO 3 and based on the mass of CeO 2);
(2) Dissolving a certain amount of tetrabutyl titanate in 40mL of absolute ethyl alcohol to serve as a solution A, mixing 5mL of 68wt% concentrated nitric acid with 20mL of absolute ethyl alcohol and 20mL of deionized water to serve as a solution B, and then dropwise adding the solution A into the stirred solution B to obtain TiO 2 sol;
(3) Adding Ag-W/CeO 2 powder into the fresh TiO 2 sol prepared in the step (2), continuously stirring for 6 hours, aging at 80 ℃ for 48 hours, and finally roasting at 450 ℃ for 3 hours to obtain the Ag-W/CeO 2@TiO2 catalyst, wherein the content of the outer layer TiO 2 is controlled to be about 5wt% (based on the mass of CeO 2).
Catalyst activity test: the activity experiment is carried out on a fixed bed reactor, the catalyst dosage is 3.0g, and the granularity is 40-60 meshes. In the NO 2 adsorption experiment, the composition of the mixed gas is as follows: [ NO 2]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV =30,000 ml g- 1h-1; in the SCR experiment, the composition of the mixed gas is as follows: [ NO ] = [ NH 3]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV = 30,000ml g- 1h-1. The catalyst has an adsorption capacity of 10.3mg/g of NO 2 at 150 ℃, a conversion rate of 92.5% of NO x at 350 ℃ and a selectivity of 99.0% of N 2, and shows good stability, and the adsorption performance of NO 2 after 3 cycles is similar to that of a fresh sample.
Example 7
And (3) preparing a catalyst: (1) Roasting cerium nitrate hexahydrate at 450 ℃ for 4 hours to obtain CeO 2, grinding and screening, taking 8g of 40-60 mesh CeO 2, dispersing in 100mL of deionized water, adding a certain amount of silver nitrate and ammonium meta-tungstate, uniformly mixing, drying at 120 ℃ for 12 hours, roasting at 450 ℃ for 4 hours to obtain Ag-W/CeO 2, controlling the total loading of Ag and Ag 2 O to be about 0.1wt% (calculated by the mass of Ag and Ag 2 O converted to Ag 2 O and based on the mass of CeO 2), and the loading of W to be about 1wt% (calculated by the mass of WO 3 and based on the mass of CeO 2);
(2) Dissolving a certain amount of tetrabutyl titanate in 40mL of absolute ethyl alcohol to serve as a solution A, mixing 5mL of 68wt% concentrated nitric acid with 20mL of absolute ethyl alcohol and 20mL of deionized water to serve as a solution B, and then dropwise adding the solution A into the stirred solution B to obtain TiO 2 sol;
(3) Adding Ag-W/CeO 2 powder into the fresh TiO 2 sol prepared in the step (2), continuously stirring for 6 hours, aging at 80 ℃ for 48 hours, and finally roasting at 450 ℃ for 3 hours to obtain the Ag-W/CeO 2@TiO2 catalyst, wherein the content of the outer layer TiO 2 is controlled to be about 20wt% (based on the mass of CeO 2).
Catalyst activity test: the activity experiment is carried out on a fixed bed reactor, the catalyst dosage is 3.0g, and the granularity is 40-60 meshes. In the NO 2 adsorption experiment, the composition of the mixed gas is as follows: [ NO 2]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV =30,000 ml g- 1h-1; in the SCR experiment, the composition of the mixed gas is as follows: [ NO ] = [ NH 3]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV = 30,000ml g- 1h-1. The catalyst has an adsorption capacity of 10.8mg/g of NO 2 at 150 ℃, a conversion rate of 93.7% of NO x at 350 ℃ and a selectivity of 99.1% of N 2, and shows good stability, and the adsorption performance of NO 2 after 3 cycles is similar to that of a fresh sample.
Example 8
And (3) preparing a catalyst: (1) Roasting cerium nitrate hexahydrate at 450 ℃ for 4 hours to obtain CeO 2, grinding and screening, dispersing 8g of 40-60 mesh CeO 2 in 100mL of deionized water, adding a certain amount of silver nitrate and antimony acetate, uniformly mixing, drying at 120 ℃ for 12 hours, roasting at 450 ℃ for 4 hours to obtain Ag-Sb/CeO 2, controlling the total loading of Ag and Ag 2 O to be about 0.1wt% (calculated by the mass of Ag and Ag 2 O to be Ag 2 O and calculated by the mass of CeO 2) and the loading of Sb to be about 1wt% (calculated by the mass of Sb 2O3 and calculated by the mass of CeO 2);
(2) Dissolving a certain amount of tetrabutyl titanate in 40mL of absolute ethyl alcohol to serve as a solution A, mixing 5mL of 68wt% concentrated nitric acid with 20mL of absolute ethyl alcohol and 20mL of deionized water to serve as a solution B, and then dropwise adding the solution A into the stirred solution B to obtain TiO 2 sol;
(3) Adding Ag-Sb/CeO 2 powder into the fresh TiO 2 sol prepared in the step (2), continuously stirring for 6 hours, aging at 80 ℃ for 48 hours, and finally roasting at 450 ℃ for 3 hours to obtain the Ag-Sb/CeO 2@TiO2 catalyst, wherein the content of the outer layer TiO 2 is controlled to be about 10wt% (based on the mass of CeO 2).
Catalyst activity test: the activity experiment is carried out on a fixed bed reactor, the catalyst dosage is 3.0g, and the granularity is 40-60 meshes. In the NO 2 adsorption experiment, the composition of the mixed gas is as follows: [ NO 2 ] = 200ppm,
[ H 2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV =30,000 ml g- 1h-1; in the SCR experiment, the composition of the mixed gas is as follows: [ NO ] = [ NH 3]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV = 30,000ml g- 1h-1. The catalyst has an adsorption capacity of 9.9mg/g of NO 2 at 150 ℃, a conversion rate of NO x at 350 ℃ of 91.1%, a selectivity of N 2 of 98.3%, and good stability, and the adsorption performance of NO 2 after 3 cycles is similar to that of a fresh sample.
Example 9
And (3) preparing a catalyst: (1) Roasting cerium nitrate hexahydrate at 450 ℃ for 4 hours to obtain CeO 2, grinding and screening, taking 8g of 40-60 mesh CeO 2, dispersing in 100mL of deionized water, adding a certain amount of silver nitrate and ammonium molybdate, uniformly mixing, drying at 120 ℃ for 12 hours, roasting at 450 ℃ for 4 hours to obtain Ag-Mo/CeO 2, controlling the total loading of Ag and Ag 2 O to be about 0.1wt% (calculated by the mass of Ag and Ag 2 O converted to Ag 2 O and based on CeO 2) and the loading of Mo to be about 1wt% (calculated by the mass of MoO 3 and based on CeO 2);
(2) Dissolving a certain amount of tetrabutyl titanate in 40mL of absolute ethyl alcohol to serve as a solution A, mixing 5mL of 68wt% concentrated nitric acid with 20mL of absolute ethyl alcohol and 20mL of deionized water to serve as a solution B, and then dropwise adding the solution A into the stirred solution B to obtain TiO 2 sol;
(3) Adding Ag-Mo/CeO 2 powder into the fresh TiO 2 sol prepared in the step (2), continuously stirring for 6 hours, aging at 80 ℃ for 48 hours, and finally roasting at 450 ℃ for 3 hours to obtain the Ag-Mo/CeO 2@TiO2 catalyst, wherein the content of the outer layer TiO 2 is controlled to be about 10wt% (based on the mass of CeO 2).
Catalyst activity test: the activity experiment is carried out on a fixed bed reactor, the catalyst dosage is 3.0g, and the granularity is 40-60 meshes. In the NO 2 adsorption experiment, the composition of the mixed gas is as follows: [ NO 2 ] = 200ppm,
[ H 2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV =30,000 ml g- 1h-1; in the SCR experiment, the composition of the mixed gas is as follows: [ NO ] = [ NH 3]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV = 30,000ml g- 1h-1. The catalyst has an adsorption capacity of 11.5mg/g of NO 2 at 150 ℃, a conversion rate of 98.2% of NO x at 350 ℃ and a selectivity of 99.2% of N 2, and shows good stability, and the adsorption performance of NO 2 after 3 cycles is similar to that of a fresh sample.
Example 10
And (3) preparing a catalyst: (1) Roasting cerium nitrate hexahydrate at 450 ℃ for 4 hours to obtain CeO 2, grinding and screening, dispersing 8g of 40-60 mesh CeO 2 in 100mL of deionized water, adding a certain amount of silver nitrate and niobium oxalate, uniformly mixing, drying at 120 ℃ for 12 hours, roasting at 450 ℃ for 4 hours to obtain Ag-Nb/CeO 2, controlling the total loading of Ag and Ag 2 O to be about 0.1wt% (calculated by the mass of Ag and Ag 2 O to be Ag 2 O and calculated by the mass of CeO 2), and controlling the loading of Nb to be about 1wt% (calculated by the mass of Nb 2O5 and calculated by the mass of CeO 2);
(2) Dissolving a certain amount of tetrabutyl titanate in 40mL of absolute ethyl alcohol to serve as a solution A, mixing 5mL of 68wt% concentrated nitric acid with 20mL of absolute ethyl alcohol and 20mL of deionized water to serve as a solution B, and then dropwise adding the solution A into the stirred solution B to obtain TiO 2 sol;
(3) Adding Ag-Nb/CeO 2 powder into the fresh TiO 2 sol prepared in the step (2), continuously stirring for 6 hours, aging at 80 ℃ for 48 hours, and finally roasting at 450 ℃ for 3 hours to obtain the Ag-Nb/CeO 2@TiO2 catalyst, wherein the content of the outer layer TiO 2 is controlled to be about 10wt% (based on the mass of CeO 2).
Catalyst activity test: the activity experiment is carried out on a fixed bed reactor, the catalyst dosage is 3.0g, and the granularity is 40-60 meshes. In the NO 2 adsorption experiment, the composition of the mixed gas is as follows: [ NO 2]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV =30,000 ml g- 1h-1; in the SCR experiment, the composition of the mixed gas is as follows: [ NO ] = [ NH 3]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV = 30,000ml g- 1h-1. The catalyst has an adsorption capacity of 10.7mg/g of NO 2 at 150 ℃, a conversion rate of 95.8% of NO x at 350 ℃ and a selectivity of 98.9% of N 2, and shows good stability, and the adsorption performance of NO 2 after 3 cycles is similar to that of a fresh sample.
Example 11
And (3) preparing a catalyst: (1) Roasting cerium nitrate hexahydrate at 450 ℃ for 4 hours to obtain CeO 2, grinding and screening, taking 8g of 40-60 mesh CeO 2, dispersing in 100mL of deionized water, adding a certain amount of silver nitrate and ammonium metatungstate, uniformly mixing, drying at 120 ℃ for 12 hours, roasting at 400 ℃ for 4 hours to obtain Ag-W/CeO 2 powder, controlling the total loading of Ag and Ag 2 O to be about 0.1wt% (calculated by the mass of Ag and Ag 2 O to be Ag 2 O and taking the mass of CeO 2 as a reference), and the loading of W to be about 1wt% (calculated by the mass of WO 3 and taking the mass of CeO 2 as a reference);
(2) Dissolving a certain amount of tetrabutyl titanate in 40mL of absolute ethyl alcohol to serve as a solution A, mixing 5mL of 68wt% concentrated nitric acid with 20mL of absolute ethyl alcohol and 20mL of deionized water to serve as a solution B, and then dropwise adding the solution A into the stirred solution B to obtain TiO 2 sol;
(3) Adding Ag-W/CeO 2 powder into the fresh TiO 2 sol prepared in the step (2), continuously stirring for 6 hours, aging at 80 ℃ for 48 hours, and finally roasting at 450 ℃ for 3 hours to obtain the Ag-W/CeO 2@TiO2 catalyst, wherein the content of the outer layer TiO 2 is controlled to be about 10wt% (based on the mass of CeO 2).
Catalyst activity test: the activity experiment is carried out on a fixed bed reactor, the catalyst dosage is 3.0g, and the granularity is 40-60 meshes. In the NO 2 adsorption experiment, the composition of the mixed gas is as follows: [ NO 2]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV =30,000 ml g- 1h-1; in the SCR experiment, the composition of the mixed gas is as follows: [ NO ] = [ NH 3]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV = 30,000ml g- 1h-1. The catalyst has an adsorption capacity of 12.0mg/g of NO 2 at 150 ℃, a conversion rate of NO x at 350 ℃ of 97.8%, a selectivity of N 2 of 99.5%, and good stability, and the adsorption performance of NO 2 after 3 cycles is similar to that of a fresh sample.
Example 12
And (3) preparing a catalyst: (1) Roasting cerium nitrate hexahydrate at 450 ℃ for 4 hours to obtain CeO 2, grinding and screening, taking 8g of 40-60 mesh CeO 2, dispersing in 100mL of deionized water, adding a certain amount of silver nitrate and ammonium metatungstate, uniformly mixing, drying at 120 ℃ for 12 hours, roasting at 450 ℃ for 4 hours to obtain Ag-W/CeO 2 powder, controlling the total loading of Ag and Ag 2 O to be about 0.1wt% (calculated by the mass of Ag and Ag 2 O to be Ag 2 O and taking the mass of CeO 2 as a reference), and the loading of W to be about 1wt% (calculated by the mass of WO 3 and taking the mass of CeO 2 as a reference);
(2) Dissolving a certain amount of tetrabutyl titanate in 40mL of absolute ethyl alcohol to serve as a solution A, mixing 5mL of 68wt% concentrated nitric acid with 20mL of absolute ethyl alcohol and 20mL of deionized water to serve as a solution B, and then dropwise adding the solution A into the stirred solution B to obtain TiO 2 sol;
(3) Adding Ag-W/CeO 2 powder into the fresh TiO 2 sol prepared in the step (2), continuously stirring for 6 hours, aging at 80 ℃ for 48 hours, and finally roasting at 400 ℃ for 3 hours to obtain the Ag-W/CeO 2@TiO2 catalyst, wherein the content of the outer layer TiO 2 is controlled to be about 10wt% (based on the mass of CeO 2).
Catalyst activity test: the activity experiment is carried out on a fixed bed reactor, the catalyst dosage is 3.0g, and the granularity is 40-60 meshes. In the NO 2 adsorption experiment, the composition of the mixed gas is as follows: [ NO 2 ] = 200ppm,
[ H 2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV =30,000 ml g- 1h-1; in the SCR experiment, the composition of the mixed gas is as follows: [ NO ] = [ NH 3]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV = 30,000ml g- 1h-1. The catalyst has an adsorption capacity of 12.1mg/g of NO 2 at 150 ℃, a conversion rate of 96.6% of NO x at 350 ℃ and a selectivity of 99.6% of N 2, and shows good stability, and the adsorption performance of NO 2 after 3 cycles is similar to that of a fresh sample.
Comparative example 1
And (3) preparing a catalyst: (1) Roasting cerium nitrate hexahydrate for 4 hours at 450 ℃ to obtain CeO 2, grinding and screening, taking 8g of 40-60 mesh CeO 2, dispersing in 100mL of deionized water, adding a certain amount of ammonium metatungstate, uniformly mixing, drying at 120 ℃ for 12 hours, roasting at 450 ℃ for 4 hours to obtain W/CeO 2 powder, and controlling the W load to be about 1wt% (based on the mass of WO 3 and the mass of CeO 2);
(2) Dissolving a certain amount of tetrabutyl titanate in 40mL of absolute ethyl alcohol to serve as a solution A, mixing 5mL of 68wt% concentrated nitric acid with 20mL of absolute ethyl alcohol and 20mL of deionized water to serve as a solution B, and then dropwise adding the solution A into the stirred solution B to obtain TiO 2 sol;
(3) The W/CeO 2 powder is added into the fresh TiO 2 sol prepared in the step (2), stirring is continued for 6 hours, then aging is carried out at 80 ℃ for 48 hours, finally roasting is carried out at 450 ℃ for 3 hours, the W/CeO 2@TiO2 catalyst is obtained, and the content of the outer layer TiO 2 is controlled to be about 10wt% (based on the mass of CeO 2).
Catalyst activity test: the activity experiment is carried out on a fixed bed reactor, the catalyst dosage is 3.0g, and the granularity is 40-60 meshes. In the NO 2 adsorption experiment, the composition of the mixed gas is as follows: [ NO 2]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV =30,000 ml g- 1h-1; in the SCR experiment, the composition of the mixed gas is as follows: [ NO ] = [ NH 3]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV = 30,000ml g- 1h-1. The catalyst has an adsorption capacity of 6.9mg/g of NO 2 at 150 ℃, a conversion rate of 92.2% of NO x at 350 ℃ and a selectivity of 97.4% of N 2, and shows good stability, and the adsorption performance of NO 2 after 3 cycles is similar to that of a fresh sample.
Comparative example 2
And (3) preparing a catalyst: roasting cerium nitrate hexahydrate for 4 hours at 450 ℃ to obtain CeO 2, grinding and screening, dispersing 8g of 40-60 mesh CeO 2 in 100mL of deionized water, adding a certain amount of silver nitrate, ammonium metatungstate and P25 titanium dioxide, uniformly mixing, drying at 120 ℃ for 12 hours, roasting at 450 ℃ for 4 hours to obtain the Ag-W-TiO 2/CeO2 catalyst, controlling the total load of Ag and Ag 2 O to be about 0.1wt% (calculated by the mass of Ag and Ag 2 O to be Ag 2 O and based on CeO 2), the load of W to be about 1wt% (calculated by the mass of WO 3 and based on CeO 2), and the content of TiO 2 to be about 10wt% (based on CeO 2).
Catalyst activity test: the activity experiment is carried out on a fixed bed reactor, the catalyst dosage is 3.0g, and the granularity is 40-60 meshes. In the NO 2 adsorption experiment, the composition of the mixed gas is as follows: [ NO 2]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV =30,000 ml g- 1h-1; in the SCR experiment, the composition of the mixed gas is as follows: [ NO ] = [ NH 3]＝200ppm,[H2O]＝10vol％,[O2]＝15vol％,N2 carrier gas, MHSV = 30,000ml g- 1h-1. The catalyst has an adsorption capacity of 9.3mg/g of NO 2 at 150 ℃, a conversion rate of 95.7% of NO x at 350 ℃ and a selectivity of 99.4% of N 2, and shows good stability, and the adsorption performance of NO 2 after 3 cycles is similar to that of a fresh sample.
Further, it is to be understood that various changes and modifications of the present application may be made by those skilled in the art after reading the above description of the application, and that such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (6)
1. The catalyst is characterized in that Ag-M/CeO 2 is taken as a core in the catalyst, and an amorphous TiO 2 layer is coated on the surface of the catalyst;
Ag-M/CeO 2 represents the oxide of the surface loaded Ag, ag 2 O and acid auxiliary agent M of CeO 2;
the acid auxiliary agent M is at least one of W, sb, mo, nb;
in the Ag-M/CeO 2, the mass ratio of the sum of the masses of Ag and Ag 2 O to the mass ratio of the oxide of the acid auxiliary agent M to the mass ratio of CeO 2 is 0.02-0.2:0.5-2:100; wherein the sum of the masses of Ag and Ag 2 O is calculated by the mass of Ag and Ag 2 O converted into Ag 2 O, and the mass of the oxide of the acid auxiliary agent M is calculated by WO 3、Sb2O3、MoO3、Nb2O5;
the preparation method of the catalyst comprises the following steps:
(1) Preparation of Ag-M/CeO 2: dispersing CeO 2, silver nitrate and a precursor of an acid auxiliary agent M in deionized water, uniformly mixing, drying and roasting to obtain Ag-M/CeO 2; the roasting temperature is 400-450 ℃ and the roasting time is 4-5 h;
(2) Preparation of TiO 2 sol: dissolving tetrabutyl titanate in ethanol to obtain solution A, mixing nitric acid with deionized water and ethanol to obtain solution B, and adding the solution A into the solution B with continuous stirring to obtain TiO 2 sol;
(3) Preparation of Ag-M/CeO 2@TiO2 catalyst: adding Ag-M/CeO 2 in the step (1) into the TiO 2 sol in the step (2), continuously stirring, and then aging and roasting to obtain an Ag-M/CeO 2@TiO2 catalyst suitable for nitrogen oxide storage reduction of a gas turbine; the aging temperature is 75-85 ℃ and the aging time is 40-56 h; the roasting temperature is 400-450 ℃ and the roasting time is 3-4 h.
2. The catalyst according to claim 1, wherein the mass ratio of CeO 2 to TiO 2 in the catalyst is 100:5-20.
3. The catalyst according to claim 1, wherein CeO 2 is obtained by calcination of cerium nitrate hexahydrate at 400-450 ℃ for 4-5 hours.
4. A method for preparing a catalyst according to any one of claims 1 to 3, characterized in that the method comprises the steps of:
(1) Preparation of Ag-M/CeO 2: dispersing CeO 2, silver nitrate and a precursor of an acid auxiliary agent M in deionized water, uniformly mixing, drying and roasting to obtain Ag-M/CeO 2; the roasting temperature is 400-450 ℃ and the roasting time is 4-5 h;
(2) Preparation of TiO 2 sol: dissolving tetrabutyl titanate in ethanol to obtain solution A, mixing nitric acid with deionized water and ethanol to obtain solution B, and adding the solution A into the solution B with continuous stirring to obtain TiO 2 sol;
(3) Preparation of Ag-M/CeO 2@TiO2 catalyst: adding Ag-M/CeO 2 in the step (1) into the TiO 2 sol in the step (2), continuously stirring, and then aging and roasting to obtain an Ag-M/CeO 2@TiO2 catalyst suitable for nitrogen oxide storage reduction of a gas turbine; the aging temperature is 75-85 ℃ and the aging time is 40-56 h; the roasting temperature is 400-450 ℃ and the roasting time is 3-4 h.
5. The method according to claim 4, wherein in the step (1), the precursor of the acid promoter M is at least one of ammonium metatungstate, antimony acetate, ammonium molybdate and niobium oxalate.
6. Use of a catalyst according to any one of claims 1-3 in gas turbine nitrogen oxide storage catalytic reduction.
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