CN113289616A - Catalyst for NO oxidation and preparation method thereof - Google Patents
Catalyst for NO oxidation and preparation method thereof Download PDFInfo
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- CN113289616A CN113289616A CN202110670571.6A CN202110670571A CN113289616A CN 113289616 A CN113289616 A CN 113289616A CN 202110670571 A CN202110670571 A CN 202110670571A CN 113289616 A CN113289616 A CN 113289616A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 230000003647 oxidation Effects 0.000 title claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 239000011651 chromium Substances 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 15
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 13
- 239000012495 reaction gas Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 229940071125 manganese acetate Drugs 0.000 description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000010412 oxide-supported catalyst Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 229910002520 CoCu Inorganic materials 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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Classifications
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- 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
- 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
- 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
- B01J23/75—Cobalt
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/647—
-
- 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
- B01J37/0201—Impregnation
-
- 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
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The present invention relates to a catalyst for the oxidation of NO, characterized in that it comprises: the carrier is gamma-alumina, and the active component is one or more of oxides of manganese, iron, copper, cobalt, chromium or cerium; the active component loading mass is 10-25% of the carrier mass. The active component is loaded on the carrier by a simple impregnation method to obtain the NO oxidation catalyst. The catalyst has NO conversion rate up to 98.5% in the presence of oxygen in 275 deg.c lower temperature window and excellent sulfur resistance. The catalyst prepared by the method has wide sources, low price and good industrial application potential.
Description
Technical Field
The invention belongs to the technical field of industrial catalysts and environmental protection, and particularly relates to a NO oxidation catalyst and a preparation method thereof, in particular to a preparation method and property research of a metal oxide supported catalyst for selectively oxidizing NO at low temperature.
Background
A large amount of nitrogen oxides, including nitrogen monoxide, nitrogen dioxide, and nitrous oxide, are emitted during the combustion of fossil fuels, which can cause environmental problems such as acid rain and photochemical smog. Of which 90% is nitric oxide, and removal of which has become a hot problem.
The denitration method of NO mainly comprises two methods, one method is to reduce NO into nitrogen, and the most widely applied method in the current thermal power plant is selective catalytic reduction (NH)3-SCR) technique, but NH3SCRs are low in safety, high in cost, and have a strict temperature window. The other method is to oxidize NO into high-valence nitrogen oxide, then to absorb the nitrogen oxide by using alkaline, oxidizing or reducing liquid, and is suitable for small and medium-sized enterprises. The method for removing NO by using an oxidation method has low cost and can achieve higher removal efficiency in a low temperature range.
The core of the NO oxidation method is a catalyst which can be divided into two main types of noble metal catalysts and non-noble metal catalysts according to the difference of active components. Among them, noble metal catalysts such as Pt, Pd, and Ag have been widely studied and have a good denitration efficiency, but such catalysts have a problem of high price and are difficult to be widely used in industry. The non-noble metal has variable valence, relatively low price and better catalytic activity, and the preparation of the catalyst draws wide attention in the industry.
Chinese patent document CN107824192B discloses Sr for flue gas denitration2FeTaO6Aluminum oxideThe composite catalyst is prepared by mainly using strontium carbonate, tantalum pentoxide and iron particles as raw materials2FeTaO6And then coating the carrier on the surface of the alumina globule to obtain the product. The catalyst has the advantages of wide reaction window, environmental friendliness, good low-temperature activity and the like. But the denitration method is NH3SCR process, low safety, high cost and the generation of NH3The problem of leakage. Chinese patent CN107376913A discloses a gamma-alumina-based copper oxide nano material for high-efficiency catalytic purification of NO and a preparation method thereof. The material is composed of gamma-phase Al2O3The foam ceramic and the CuO nano particles growing on the surface thereof in situ. The catalyst has the advantages of low preparation cost, good catalytic effect, simple and convenient steps and higher conversion temperature. Therefore, the development of the NO oxidation catalyst with low temperature, high efficiency and low cost is of great significance.
Disclosure of Invention
The present invention has been made in an effort to provide a multi-oxide supported catalyst for NO oxidation, which has a high NO conversion at a relatively low temperature, and can solve the problem of low conversion at a low temperature in the related art, and a method for preparing the same.
The technical scheme of the invention is as follows: a catalyst for the oxidation of NO, the catalyst comprising: the carrier is gamma-alumina, and the active component is one or more of oxides of manganese, iron, copper, cobalt, chromium or cerium; the active component loading mass is 10-25% of the carrier mass.
Preferably, the average pore diameter of the gamma-alumina carrier is 9-12nm, and the pore volume is 0.30-0.50cm3A specific surface area of 130-2/g。
The invention also provides a method for preparing the NO oxidation catalyst, which comprises the following steps:
(1) preparing an active component solution, dissolving soluble salt of the active component in a solvent to prepare the active component solution; wherein the concentration of soluble salt in the active component solution is 0.1-0.3 mol/L; the active component is one or more of acetate, nitrate or chloride of manganese, iron, copper, cobalt, chromium and cerium;
(2) adding the active component solution prepared in the step (1) into a gamma-alumina carrier, and carrying out ultrasonic treatment to obtain a mixed solution;
(3) putting the mixed solution obtained in the step (2) into rotary evaporation, heating and evaporating to obtain a mixture;
(4) and (4) drying and roasting the mixture obtained in the step (3) to obtain the NO oxidation catalyst.
Preferably, the solvent in step (1) is ethanol or water.
Preferably, the ultrasonic frequency in the step (2) is 20-60Hz, and the ultrasonic time is 1-1.5 h.
Preferably, the rotary evaporation temperature in the step (3) is 40-80 ℃.
Preferably, the drying temperature in the step (4) is 100-120 ℃, and the drying time is 4-6 h; the roasting temperature is 400-500 ℃, and the roasting time is 3-4 h.
The application method of the NO oxidation catalyst comprises the following steps: in the temperature range of the flue gas of 150 ℃ and 400 ℃, the reaction gas comprises the following components: 300ppmNO, 5% O2The balance gas is N2The total flow rate of the gas is 100mL/min, and the space velocity is 3.0-6.0h-1Under the conditions of (1), oxidizing NO with an NO oxidation catalyst.
The application method of the NO oxidation catalyst prepared by the invention comprises the following steps: at a flue gas temperature range of 275 ℃, the reaction gas composition is: 300ppmNO, 20ppmSO2，5％O2The balance gas is N2The total flow rate of the gas is 100mL/min, and the space velocity is 6.0h-1NO was tested for sulfur resistance using a NO oxidation catalyst under the conditions of (1).
The invention has the beneficial effects that the catalyst uses transition metal oxide and rare earth metal oxide with relatively low price as main components of the catalyst, and is prepared by a simple and easily repeated dipping method, and the prepared catalyst has good NO conversion rate at a lower temperature window; the catalyst has the characteristics of excellent stability and long service life, so that the catalyst has good industrial application potential.
Drawings
FIG. 1 shows XRD patterns of catalysts prepared in examples 1-5 of the present invention;
FIG. 2 is a graph showing the NO oxidation performance of the catalyst prepared in example 5 of the present invention;
FIG. 3 is a graph showing the sulfur resistance of the catalyst prepared in example 5 of the present invention.
Detailed Description
The solution according to the invention is further described in detail below with reference to the figures and examples.
Example 1
Measuring 18.4mL of manganese acetate solution with the concentration of 0.2mol/L, taking water as a solvent, adding 1g of gamma-alumina carrier which is not treated by other materials, treating the obtained mixture by using ultrasonic for 1h, setting the ultrasonic frequency to be 20Hz, placing the mixture in rotary evaporation at 80 ℃ to dry the water, then drying the mixture in an oven at 120 ℃ for 4h, and finally roasting the mixture at 400 ℃ for 4h in an air atmosphere. The mass fraction of the active component content in the obtained catalyst relative to the carrier is 20%, and the mass fraction is recorded as Mn/Al2O3A catalyst. Wherein the average pore diameter of the alumina carrier is 11.6nm, and the pore volume is 0.45cm3Per g, specific surface area 149.2m3(ii) in terms of/g. The XRD pattern of the catalyst is shown in FIG. 1.
The activity evaluation of the catalyst was carried out in a fixed bed reactor with a reaction gas composition of: 300ppmNO, 5% O2The balance gas is N2The total flow of gas is 100mL/min, and the reaction space velocity is 3.0h-1The temperature range tested was 150 ℃ and 400 ℃ and at 300 ℃ the maximum NO conversion of 78.3% was achieved.
Example 2
Weighing 18.4mL of manganese acetate solution with the concentration of 0.1mol/L and 16.8mL of cobalt chloride solution with the concentration of 0.1mol/L, wherein all solvents are water, adding 2g of gamma-alumina carrier which is not treated, treating the obtained mixture by using ultrasonic waves for 1h, wherein the ultrasonic frequency is 40Hz, placing the mixture in rotary evaporation at 70 ℃ to dry the water, then drying the mixture in an oven at 100 ℃ for 6h, and finally roasting the mixture at 450 ℃ for 4h in an air atmosphere. The mass fraction of the active component content in the obtained catalyst relative to the carrier is 10 percent and is recorded as MnCo/Al2O3A catalyst. Wherein the average pore diameter of the alumina carrier is 11.2nm, and the pore volume is 0.42cm3Per g, specific surface area of 145.3m3(ii) in terms of/g. The XRD pattern of the catalyst is shown in FIG. 1.
The activity evaluation of the catalyst was carried out in a fixed bed reactor with a reaction gas composition of: 300ppmNO, 5% O2The balance gas is N2The total flow of gas is 100mL/min, and the reaction space velocity is 6.0h-1The temperature range tested was 150-400 ℃ and at 300 ℃ the maximum NO conversion of 86.3% was achieved.
Example 3
Weighing 18.2mL of manganese acetate solution with the concentration of 0.3mol/L and 19.3mL of chromium nitrate solution with the concentration of 0.2mol/L, wherein the solvents are all ethanol, adding 2g of gamma-alumina carrier which is not treated, treating the obtained mixture by using ultrasonic waves for 1h, wherein the ultrasonic frequency is 50Hz, placing the mixture in rotary evaporation, drying the mixture at 40 ℃ to remove water, and then drying the mixture in an oven at 110 ℃ for 5 h. Finally, roasting the catalyst for 3 hours at 400 ℃ in air atmosphere, wherein the mass fraction of the active component in the obtained catalyst relative to the carrier is 25 percent and is marked as MnCr/Al2O3A catalyst. Wherein the average pore diameter of the alumina carrier is 9.3nm, and the pore volume is 0.32cm3Per g, specific surface area 135.4m3(ii) in terms of/g. The XRD pattern of the catalyst is shown in FIG. 1.
The activity evaluation of the catalyst was carried out in a fixed bed reactor with a reaction gas composition of: 300ppmNO, 5% O2The balance gas is N2The total flow of gas is 100mL/min, and the reaction space velocity is 3.0h-1The temperature range tested was 150-400 ℃ and at 290 ℃ the highest NO conversion of 82.6% was achieved.
Example 4
11.7mL of copper chloride solution with the concentration of 0.2mol/L and 6.3mL of cobalt chloride solution with the concentration of 0.2mol/L are measured, the solvents are all ethanol, 1.5g of gamma-alumina carrier which is not treated by other materials is added, the obtained mixture is treated by ultrasonic for 1.5h, the ultrasonic frequency is 30Hz, the mixture is placed in rotary evaporation, the moisture is evaporated to dryness at 55 ℃, then the mixture is dried in an oven at 100 ℃ for 6h, and finally the mixture is roasted at 500 ℃ for 3h in the air atmosphere. The mass fraction of the active component content in the obtained catalyst relative to the carrier is 15%, and the active component content is recorded as CoCu/Al2O3CatalysisAnd (3) preparing. Wherein the average pore diameter of the alumina carrier is 10.8nm, and the pore volume is 0.40cm3Per g, specific surface area 138.4m3(ii) in terms of/g. The XRD pattern of the catalyst is shown in FIG. 1.
The activity evaluation of the catalyst was carried out in a fixed bed reactor with a reaction gas composition of: 300ppmNO, 5% O2The balance gas is N2The total flow of gas is 100mL/min, and the reaction space velocity is 5.0h-1The temperature range tested was 150-400 ℃ and the maximum NO conversion of 81.5% was reached at 310 ℃.
Example 5
12.4mL of manganese acetate solution with the concentration of 0.3mol/L, 3.5mL of cerium nitrate solution with the concentration of 0.1mol/L and 7.5mL of ferric nitrate solution with the concentration of 0.2mol/L are weighed, ethanol is added into 2g of gamma-alumina carrier which is not treated, the obtained mixture is treated by ultrasonic for 1.5h with the ultrasonic frequency of 60Hz, the mixture is placed in rotary evaporation at 50 ℃ to be dried, then the mixture is dried in an oven at 120 ℃ for 4h, and finally the mixture is roasted at 400 ℃ for 3h in the air atmosphere. The mass fraction of the active component in the obtained catalyst relative to the carrier is 16%, and the active component is recorded as MnCeFe/Al2O3A catalyst. Wherein the average pore diameter of the alumina carrier is 11.6nm, and the pore volume is 0.45cm3Per g, specific surface area 149.2m3(ii) in terms of/g. The XRD pattern of the catalyst is shown in FIG. 1.
The activity evaluation of the catalyst was carried out in a fixed bed reactor with a reaction gas composition of: 300ppmNO, 5% O2The balance gas is N2The total flow of gas is 100mL/min, and the reaction space velocity is 6.0h-1The temperature range tested was 150-400 ℃ and at 290 ℃ the highest NO conversion of 82.6% was achieved. The results are shown in FIG. 2.
The evaluation of the sulfur resistance of the catalyst was carried out in a fixed reactor, the amount of catalyst used was 0.1g, and the composition of the reaction gas was: 300ppmNO, 5% O2，20ppmSO2The balance gas is N2The total flow of reaction gas is 100mL/min, and the reaction space velocity is 6.0h-1The test temperature was 275 ℃ and the test time was 10 h. The results are shown in FIG. 3.
Claims (7)
1. The catalyst for NO oxidation is characterized by comprising a carrier and an active component loaded on the carrier, wherein the carrier is gamma-alumina, and the active component is one or more of oxides of manganese, iron, copper, cobalt, chromium or cerium; the active component loading mass is 10-25% of the carrier mass.
2. The catalyst for the oxidation of NO as claimed in claim 1, wherein the γ -alumina support has an average pore diameter of 9 to 12nm and a pore volume of 0.30 to 0.50cm3A specific surface area of 130-2/g。
3. A method of preparing a catalyst for the oxidation of NO as claimed in claim 1, comprising the steps of:
(1) preparing an active component solution, dissolving soluble salt of the active component in a solvent to prepare the active component solution; wherein the concentration of soluble salt in the active component solution is 0.1-0.3 mol/L; the active component is one or more of acetate, nitrate or chloride of manganese, iron, copper, cobalt, chromium and cerium;
(2) adding the active component solution prepared in the step (1) into a gamma-alumina carrier, and carrying out ultrasonic treatment to obtain a mixed solution;
(3) putting the mixed solution obtained in the step (2) into rotary evaporation, heating and evaporating to obtain a mixture;
(4) and (4) drying and roasting the mixture obtained in the step (3) to obtain the NO oxidation catalyst.
4. The method according to claim 3, wherein the solvent in step (1) is ethanol or water.
5. The method according to claim 3, wherein the ultrasonic frequency in step (2) is 20-60Hz, and the ultrasonic time is 1-1.5 h.
6. The method of claim 3, wherein the rotary evaporation temperature in step (3) is 40-80 ℃.
7. The method as claimed in claim 3, wherein the drying temperature in step (4) is 100-120 ℃, and the drying time is 4-6 h; the roasting temperature is 400-500 ℃, and the roasting time is 3-4 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103263925A (en) * | 2013-05-08 | 2013-08-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Cerium-zirconium base nitric oxide common temperature catalyst preparation method |
| CN103566946A (en) * | 2012-07-24 | 2014-02-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Copper/manganese composited nitric oxide normal-temperature catalyst and preparation method thereof |
| CN103801286A (en) * | 2012-11-14 | 2014-05-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Supported chromic oxide catalyst as well as preparation and application thereof |
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| CN103566946A (en) * | 2012-07-24 | 2014-02-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Copper/manganese composited nitric oxide normal-temperature catalyst and preparation method thereof |
| CN103801286A (en) * | 2012-11-14 | 2014-05-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Supported chromic oxide catalyst as well as preparation and application thereof |
| CN103263925A (en) * | 2013-05-08 | 2013-08-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Cerium-zirconium base nitric oxide common temperature catalyst preparation method |
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