CN117599800A - Ni-MnOx doped oxide catalyst and preparation method and application thereof - Google Patents
Ni-MnOx doped oxide catalyst and preparation method and application thereof Download PDFInfo
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- CN117599800A CN117599800A CN202311409597.0A CN202311409597A CN117599800A CN 117599800 A CN117599800 A CN 117599800A CN 202311409597 A CN202311409597 A CN 202311409597A CN 117599800 A CN117599800 A CN 117599800A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 229910016978 MnOx Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000011572 manganese Substances 0.000 claims abstract description 44
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000197 pyrolysis Methods 0.000 claims abstract description 13
- 239000000443 aerosol Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 239000003595 mist Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000002803 fossil fuel Substances 0.000 claims description 2
- 150000002697 manganese compounds Chemical class 0.000 claims description 2
- 150000002816 nickel compounds Chemical class 0.000 claims description 2
- 238000006213 oxygenation reaction Methods 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 44
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 6
- 239000010953 base metal Substances 0.000 abstract description 5
- 238000002309 gasification Methods 0.000 abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 77
- 229910002091 carbon monoxide Inorganic materials 0.000 description 77
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000012159 carrier gas Substances 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910018565 CuAl Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910002668 Pd-Cu Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
-
- 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
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0233—Chemical processing only
- C01B13/0237—Chemical processing only by oxidation
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of CO removal by catalytic oxidation, and provides a Ni-MnOx doped oxide catalyst. The Ni-MnOx doped oxide catalyst is prepared by an aerosol pyrolysis method of a nickel-containing compound and a manganese-containing compound. The invention adopts base metal doping, high temperature reaction, nano engineering and interface reaction to realize low temperature gasification of carbonate on the surface of the catalyst, release active sites and achieve 100 percent conversion of CO into CO at 25-800 DEG C 2 At-20℃also 82% conversion to CO 2 。
Description
Technical Field
The invention belongs to the field of CO removal by catalytic oxidation, and particularly relates to a Ni-MnOx doped oxide catalyst, and a preparation method and application thereof.
Background
The purification treatment of CO-containing gas is generally carried out by oxidizing CO to CO at room temperature or low temperature using a noble metal catalyst 2 。
The document CN107519871B provides "an auag@siof which catalyzes the oxidation of CO 2 The preparation method of the nano catalyst adopts noble metals Au and Ag to prepare Au-Ag alloy particle cores and SiO 2 Is a shell catalyst which can fully convert CO into CO at 70 DEG C 2 。
The document CN113117693a provides "a Pd-Cu/TiO for the catalytic oxidation of CO 2 Bimetallic catalyst and preparation method and application thereof, pd-Cu/TiO 2 The catalytic temperature of the bimetallic catalyst for catalytic oxidation of CO is 20-120 ℃.
The patent No. CN108126708A provides a CO normal-temperature oxidation catalyst, the active component of the catalyst is nano gold, and the auxiliary agent is Fe 2 O 3 、MnO 2 、CuO、Co 2 O 3 、CeO 2 And one or more of NiO, and the carrier is gamma-Al 2 O 3 CO can be 100% oxidized at 55deg.C.
The patent No. CN 111266116A provides a supported nano multi-metal catalyst, a preparation method and application thereof to CO oxidation, and the catalyst is prepared by the following steps of 1-x-y-z Pt x Ru y Pd z O 3 /SiO 2 Under the catalysis of the supported nano multi-metal catalyst, the CO conversion rate is 80% at 350 ℃ and 100% at 400 ℃.
The patent number CN 110876943A provides an oxide modified Pt-Co bimetallic catalyst, a preparation method and application thereof to CO oxidation, and the oxide modified Pt-Co bimetallic catalyst is adopted to catalyze the CO oxidation. LaCo at 380 ℃ 0.99 Pt 0.01 O 3 The catalytic CO conversion was 100%.
The document CN 113597339A provides a "low temperature CO oxidation catalyst" and relates to a (LT-CO) oxidation catalyst composition for reducing low temperature carbon monoxide from exhaust emissions of lean burn engines. The LT-CO oxidation catalyst composition includes an Oxygen Storage Component (OSC), a first Platinum Group Metal (PGM) component, and a promoter metal, wherein the OSC is impregnated with the first PGM component and the promoter metal, and the LT-CO oxidation catalyst composition is effective to oxidize carbon monoxide (CO) and Hydrocarbons (HC) under cold start conditions.
The document CN 113877605A provides a catalyst for low-temperature oxidation of CO and a method for preparing the same. The catalyst comprises Pt element as an active component, transition metal element M2 oxide and alkali metal element M1, wherein M2 is one or more selected from Mn, mo, fe, ni elements, the Pt element accounts for 0.1-2wt% of the total mass of the catalyst, and the M1 element accounts for 1-10wt% of the total mass of the catalyst. First by M1OH or M1 2 CO 3 The Pt/M1-M2 catalyst is prepared by preparing a basic mixture of Pt-M1-M2 by a coprecipitation method for a precipitant and then performing high-temperature treatment. The catalyst has high CO catalytic oxidation activity and stability in various characteristic atmospheres (such as hydrogen-rich, carbon dioxide-rich and sulfur-containing), and can be used in fuel cells, automobile exhaust and low levelsThe method has good application potential in CO elimination scenes such as tail gas washing by warm methanol. The evaluation conditions of the catalyst were: the reaction pressure is normal pressure, and the reaction raw material gas is 85 percent CO 2+ 、14.6％He + 、0.1％CO + 、0.3％H 2 (80 mL/min) and air (5 mL/min), the catalyst loading volume was 1mL, and the space velocity was 5000h –1 . The temperature at which the CO catalytic oxidation conversion of the catalyst reaches 99% is 50 ℃.
The development of highly effective base metal catalysts is necessary due to the disadvantages of scarce precious metal resources and high costs.
The document CN1554480a provides "CuO/CeO 2 Preparation of catalyst and application thereof in CO oxidation, cuO/CeO 2 The catalyst is prepared by a process combining a sol-gel method and an impregnation method, wherein the mass ratio of CuO is 3.78% -15.12%, and the CO conversion rate is 100% above 140 ℃.
The patent No. CN105396587A provides a composite copper oxide catalyst for removing trace CO, a preparation method and application thereof, and the catalyst is used in CuO/CuAl 2 Under the action of a catalyst/C, the temperature of 90 ℃ is 5000h –1 At space velocity, 2.2ppm CO can be reduced to 16ppb.
The document CN114345357a provides a "method for preparing an isothermal methanation catalyst". Preparing a modified mesoporous alumina carrier by adopting a hydrothermal treatment process under the synergistic effect of a plurality of metal components such as Cu, zn, ce, zr, mo, mn, la, and obtaining a precursor with good specific surface area, pore diameter, heat and mass transfer performance by means of drying, roasting, tabletting and the like; the bimetallic Ni-Ce is used as an active ingredient to prepare the catalyst. The CO conversion rate reaches more than 99.0 percent under the condition of 250-400 ℃.
Patent No. CN115704097A 'preparation method and application of a diatomic catalyst with M1M 2-carrier structure'. The active center of the diatomic catalyst contains two metal M1 and M2 atoms with a distance L, the metal M1 and M2 are the same or different and are independently selected from one of Mg, V, cr, mn, fe, co, ni, cu, zn, sn, ru, rh, pd, ir, pt, ag, au, and the carrier is a carbon-based carrier or a metal oxide. The preparation method of the catalyst comprises the steps of loading a binuclear complex serving as a precursor on a carrier, and carrying out pyrolysis under an inert atmosphere.
The document CN114206781a provides a "nickel composite hydroxide, a positive electrode active material containing a nickel composite hydroxide as a precursor, and a method for producing the same", wherein the nickel composite hydroxide contains Ni, co and 1 or more additive metal elements M selected from the group consisting of Mn, al, fe, and Ti, and the nickel composite hydroxide is a precursor of the positive electrode active material of a nonaqueous electrolyte secondary battery, and the method for producing the same comprises the steps of: and a neutralization reaction step in which an aqueous solution containing at least a Ni salt, a Co salt, and a salt of the added metal element, an aqueous solution containing an ammonium ion donor, and a pH adjuster are mixed in a reaction tank, and a coprecipitation reaction is performed in the mixed liquid to obtain a crude nickel composite hydroxide.
In the prior art, the CO oxidation conversion temperature is high, the catalyst preparation process is complex, and the cost is high.
Disclosure of Invention
The invention provides a method for realizing 100 percent conversion of CO at 25 ℃ to 800 ℃ and 82 percent conversion of CO at-20 DEG C 2 Is a catalyst of (a).
The Ni-MnOx doped oxide catalyst is prepared by an aerosol pyrolysis method of a nickel-containing compound and a manganese-containing compound.
Further, the nickel Ni/(nickel Ni+manganese Mn) atomic ratio is 0.01 or more and 2 or less.
Further, the nickel Ni/(nickel Ni+manganese Mn) atomic ratio is 0.3 or more and 1 or less.
Further, the Ni-MnOx doped oxide catalyst is a hollow spherical shell formed by 10-100 nanometer sphere arrangement, the shell can be open or closed, and the outer diameter of the shell is between 100 nanometers and 10 micrometers.
An object of the present invention is to provide a method for preparing a Ni-MnOx doped oxide catalyst.
The preparation method of the Ni-MnOx doped oxide catalyst comprises the following steps:
s1: atomizing an aqueous solution containing a nickel compound and a manganese compound, introducing the mist into a heat-preserving pipeline through inert gas, and vaporizing the mist to generate aerosol containing small solid particles of nickel nitrate and manganese nitrate;
s2: the aerosol is introduced into a pyrolysis tube along with the inert gas to be decomposed into nickel and manganese oxide, wherein the nickel is doped into manganese oxide crystal lattice to form a Ni-MnOx doped oxide solid product which is partially or completely doped;
s3: the Ni-MnOx doped oxide solid product enters a water absorption bottle along with the inert gas, is absorbed by water, is subjected to high-speed centrifugal separation, and is dried to obtain the Ni-MnOx doped oxide catalyst.
Further, the temperature of the heat preservation pipeline is 60-70 ℃, and the temperature of the pyrolysis tube is 500-800 ℃.
Further, the temperature of the heat-preserving pipe is 70 ℃, and the temperature of the pyrolysis tube is 600 ℃.
Further, the drying temperature was 80℃and the drying period was 12 hours.
It is an object of the present invention to provide the use of a Ni-MnOx doped oxide catalyst as described above in CO oxidation.
Further, the applications include purification of CO-containing gases, production of high purity oxygen, and oxidation of CO produced by burning fossil fuels.
The invention adopts base metal doping, high temperature, nano engineering and interfaces to realize the low temperature gasification of the carbonate on the surface of the catalyst, release active sites and reach the conversion of CO into CO at the temperature of 25-800 ℃ of 100 percent 2 At-20℃also 82% conversion to CO 2 。
Drawings
FIG. 1 is a schematic illustration of a method for preparing a Ni-MnOx doped oxide catalyst according to the present invention;
FIG. 2 example 1 provides an apparatus for preparing a Ni-MnOx doped oxide catalyst;
FIG. 3 is an electron micrograph of a Ni-MnOx doped oxide catalyst at 0.5 of Nickel Ni/(Nickel Ni+manganese Mn) provided in example 1;
FIG. 4 is a transmission electron microscope image of a Ni-MnOx doped oxide catalyst at 0.5 Ni/(Ni Ni+Mn) provided in example 1;
FIG. 5 is an XRD spectrum for a Ni-MnOx doped oxide catalyst at 0.5 of Nickel Ni/(Nickel Ni+manganese Mn) provided in example 1;
FIG. 6 is a graph showing the relationship between CO conversion and reaction temperature for Ni-MnOx doped oxide catalysts with different Ni/(Ni Ni+Mn) atomic ratios provided in effect example 1;
FIG. 7 is a graph of the CO90% conversion versus the atomic ratio for Ni-MnOx doped oxide catalysts with different Ni/(Ni Ni+Mn) atomic ratios provided in effect example 1.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments that are illustrated in the appended drawings, but are not to be construed as limiting the scope of the invention.
The chemical reaction temperature is controlled by desorption of carbonate on the surface of the catalyst. The invention adopts base metal doping, high temperature reaction, nano engineering and interface reaction to realize low temperature gasification of surface carbonate, release active site and reach the conversion of CO from 25 ℃ to 800 ℃ to CO100 percent 2 。
The invention provides a preparation device of a Ni-MnOx doped oxide catalyst.
The preparation device of the Ni-MnOx doped oxide catalyst comprises an ultrasonic atomization assembly, a carrier gas assembly, a heating assembly, a water absorption bottle and a conveying assembly. The ultrasonic atomization assembly comprises a glass bottle and an ultrasonic atomizer arranged in the glass bottle, and the ultrasonic atomizer atomizes liquid contained in the glass bottle. The carrier gas assembly includes a rotameter for introducing carrier gas into the glass bottle at a set flow rate. The heating assembly comprises a tube furnace and an electric furnace temperature controller, and the electric furnace temperature controller is used for controlling the reaction temperature in the tube furnace. The water absorption bottle contains water for absorbing the product carried by the carrier gas. And (3) carrying out high-speed centrifugal separation on the mixture of water and the product to obtain a solid product, and drying in a drying oven to obtain the Ni-MnOx doped oxide catalyst product. The conveying component comprises a heat preservation pipe, a heat preservation temperature controller, a pyrolysis pipe and an exhaust pipe. The heat preservation pipe conveys the carrier gas and the atomized liquid to a pyrolysis pipe of the tubular furnace, and after the reaction is finished, the carrier gas and the product are introduced into a water absorption bottle through an exhaust pipe. The water absorption bottle contains water, the product is absorbed in the water absorption bottle, and the carrier gas is discharged again through the exhaust pipe. The heat-preserving temperature controller is used for maintaining the temperature of the heat-preserving pipe.
Based on the above device, referring to fig. 1, the present invention provides a method for preparing a Ni-MnOx doped oxide catalyst.
S1: the aqueous solution of nickel nitrate and manganese nitrate is atomized by an ultrasonic atomizer, the mist is brought into a heat preservation (60-70 ℃) pipeline through nitrogen, and the liquid in the mist is vaporized in the heat preservation pipeline to generate aerosol containing solid small particles of nickel nitrate and manganese nitrate.
S2: the aerosol is introduced into a high temperature (500-800 ℃) decomposition tube along with nitrogen, and is decomposed into nickel and manganese oxide therein, and further, the nickel is doped into manganese oxide crystal lattice to form a partially or fully doped Ni-MnOx doped oxide solid product.
S3: the Ni-MnOx doped oxide solid product and nitrogen gas enter a water absorption bottle, the Ni-MnOx doped oxide solid product is absorbed by water and is subjected to high-speed centrifugal separation, and the Ni-MnOx doped oxide catalyst is obtained after drying in a drying box.
The nitrogen may be replaced with other inert gases.
The chemical reaction temperature is controlled by desorption of carbonate on the surface of the catalyst. The invention adopts base metal doping, high temperature reaction, nano engineering and interface reaction to realize the low temperature gasification of the carbonate on the surface of the catalyst, release active sites and reach the conversion of CO into CO at 25 ℃ and 100 percent 2 At-20℃also 82% conversion to CO 2 。
Example 1
As shown in fig. 2, a preparation apparatus 1 of a Ni-MnOx doped oxide catalyst includes an ultrasonic atomizing assembly, a carrier gas assembly, a heating assembly, a water absorbing bottle 31, and a transport assembly. The ultrasonic atomizing assembly includes a glass bottle 11 and an ultrasonic atomizer 12 disposed in the glass bottle 11. The carrier gas assembly includes a rotameter. The heating assembly includes a tube furnace 21 and an electric furnace temperature controller. The transport assembly includes a thermal insulation tube 41, a quartz tube 42 (pyrolysis tube), a thermal insulation controller, and a discharge tube.
The parameters of the above meter are shown in the following table:
TABLE 1
Based on the apparatus 1 for preparing the Ni-MnOx doped oxide catalyst and the method for preparing the Ni-MnOx doped oxide catalyst provided above, a series of Ni-MnOx doped oxide catalysts with different Ni/(Ni ni+mn) atomic ratios are prepared.
The experimental parameters are as follows: n (N) 2 Flow rate: 0.8L/min; water: 50mL; temperature of the heat preservation pipe: 70 ℃; tube furnace temperature: 600 ℃; and (3) centrifugal separation: 100000rpm, 5 minutes; drying temperature: and 80 ℃ for 12 hours.
Ex-purchased manganese nitrate liquid (50% wtMn (NO) 3 ) 3 ) And nickel nitrate solids (Ni (NO) 3 ) 2 ·6H 2 O) was used as a raw material to prepare catalysts with different doping ratios according to the addition amounts of Table 2.
TABLE 2
The morphology and composition of the Ni-MnOx doped oxide catalyst at Ni/(NiNi+Mn) 0.5 was characterized.
1. The picture of the Ni-MnOx doped oxide catalyst at 0.5 of Ni/(Ni Ni+Mn) is shown in FIG. 3.
Analysis of results:
the catalyst is open and non-open hollow spheres with the particle size of 10 nanometers to 5 micrometers. The sphere wall is composed of solid spheres of several nanometers to tens of nanometers.
2. The photograph of the Ni-MnOx doped oxide catalyst obtained by the transmission electron microscope at the time of 0.5 of Ni/(Ni+Mn) is shown in FIG. 4.
Analysis of results:
from FIG. 4, it is clear that the crystal stripes A and Mn of NiO 2 O 3 Is a crystal streak B of (a). The electron micrograph also shows that there are lattice defects in the crystal streak blurred spots C.
3. XRD analysis of Ni-MnOx doped oxide catalyst at 0.5 Ni/(Ni Ni+Mn) is shown in FIG. 5.
Nickel Ni/(Nickel Ni+manganese Mn) 0.5 catalyst showed a major peak of nickel oxide, indicating that manganese smaller than nickel atoms was doped into the nickel oxide skeleton, and a major peak of nickel oxide, indicating that manganese smaller than nickel atoms was doped into the nickel oxide skeleton.
The above results demonstrate that the nickel Ni/(nickel Ni+manganese Mn) 0.5Ni-MnOx doped oxide catalyst is NiO, mn 2 O 3 And Mn doped NiO, and lattice defects. These mixtures consist of hollow spheres of a few hundred nanometers to 5 microns in nanoparticles.
Effect example 1
The performance of the series of Ni-MnOx doped oxide catalysts of varying doping ratios prepared by the apparatus and method of example 1 for the catalytic oxidation of CO was evaluated using a flow-through fixed bed reactor.
Reaction conditions: 1% CO,10% O 2 ，N 2 Balance gas, ni-MnOx doped oxide catalyst dosage is 0.2g, total flow is 100mL/min, and space velocity per unit mass is 30000 mL/(g.h).
The relationship between the CO conversion and the reaction temperature of the Ni-MnOx doped oxide catalysts of different nickel Ni/(nickel ni+manganese Mn) atomic ratios is shown in fig. 6.
Analysis of results: the CO conversion of ni—mnox doped oxides with nickel Ni/(nickel ni+manganese Mn) atomic ratios from 0.33 to 0.5 were 100% from room temperature 25 ℃ to 800 ℃. The CO conversion rate of the Ni-MnOx doped oxide with other nickel Ni/(nickel Ni+manganese Mn) atomic ratio reaches 100 percent at the temperature of more than 150 ℃. The CO conversion was 82% at-20 ℃.
Ni-MnOx doped oxide catalysts prepared with the apparatus and method of example 1 having Ni/(Nickel Ni+manganese Mn) atomic ratios of 0, 0.15, 0.25, 0.33, 0.4, 0.5, 0.7, 0.75 reached temperatures (T) at 90% CO conversion 90 ) And the atomic ratio of Ni/(Ni+Mn) is plotted as shown in FIG. 7.
Analysis of results:
the atomic ratio of nickel Ni/(nickel Ni+manganese Mn) is in the range of 0.25-0.71, which can obviously reduce the CO oxidation temperature. The atomic ratio of 0.33-0.5 is lower than room temperature at 25deg.C to oxidize more than 90% of CO into CO 2 In particular, when Ni/(Ni+Mn) is 0.5, T 90 Is-10 ℃. At-20℃also 82% conversion to CO 2
As the Ni-MnOx doped oxide catalyst provided by the invention catalyzes CO to be efficiently oxidized into CO in the temperature range of-20-800 ℃ under the condition of oxygen 2 . The present invention therefore provides the use of a Ni-MnOx doped oxide catalyst in the oxidation of CO, in particular in three aspects:
(1) Purifying CO-containing air at room temperature (25deg.C) or below zero. The combustion of hydrocarbons produces CO. The method converts toxic and harmful CO into nontoxic and harmless CO by carrying out catalytic oxidation treatment on the gas in the indoor space 2 。
(2) And (3) preparing high-purity oxygen. The pure oxygen contains a trace amount of CO and is difficult to remove. The Ni-MnOx doped oxide catalyst provided by the invention converts CO in oxygen into CO 2 After that, CO is used 2 Adsorption materials such as alumina can be used for removing CO from oxygen and preparing high-purity oxygen.
(3) Oxidation of CO in the products of hydrocarbon fuel combustion (e.g., gasoline engines, diesel engines, etc.).
The use of a Ni-MnOx doped oxide catalyst to catalyze CO oxidation can achieve 100% CO conversion under different conditions. When the gas is anhydrous, the gas temperature is in the range of 25 ℃ to 800 ℃, and 100% conversion of CO into CO can be realized 2 At-20There is also 82% conversion to CO at C 2 . When the gas contains water, the gas temperature is 150-800 ℃, and 100% conversion of CO into CO can be realized 2 。
Claims (10)
1. A Ni-MnOx doped oxide catalyst, characterized by being prepared by an aerosol pyrolysis process of a nickel-containing compound and a manganese-containing compound.
2. The Ni-MnOx doped oxide catalyst of claim 1, wherein the nickel Ni/(nickel ni+manganese Mn) atomic ratio is 0.01 or greater and 2 or less.
3. The Ni-MnOx doped oxide catalyst of claim 2, wherein the nickel Ni/(nickel ni+manganese Mn) atomic ratio is 0.3 or greater and 1 or less.
4. The Ni-MnOx doped oxide catalyst of claim 2, wherein said Ni-MnOx doped oxide catalyst is a hollow sphere shell comprised of an arrangement of 10 nm-100 nm spheres, said shell being either open or closed, said shell having an outer diameter between 100 nm and 10 microns.
5. The preparation method of the Ni-MnOx doped oxide catalyst is characterized by comprising the following steps of:
s1: atomizing an aqueous solution containing a nickel compound and a manganese compound, introducing the mist into a heat-preserving pipeline through inert gas, and vaporizing the mist to generate aerosol containing small solid particles of nickel nitrate and manganese nitrate;
s2: the aerosol is introduced into a pyrolysis tube along with the inert gas to be decomposed into nickel and manganese oxide, wherein the nickel is doped into manganese oxide crystal lattice to form a Ni-MnOx doped oxide solid product which is partially or completely doped;
s3: the Ni-MnOx doped oxide solid product enters a water absorption bottle along with the inert gas, is absorbed by water, is subjected to high-speed centrifugal separation, and is dried to obtain the Ni-MnOx doped oxide catalyst.
6. The method for preparing a Ni-MnOx doped oxide catalyst according to claim 1, wherein the temperature of the thermal insulation pipe is 60-70 ℃ and the temperature of the pyrolysis tube is 500-800 ℃.
7. The method for preparing a Ni-MnOx doped oxide catalyst according to claim 1, wherein the temperature of the insulated pipe is 70 ℃ and the temperature of the pyrolysis tube is 600 ℃.
8. The method for preparing a Ni-MnOx doped oxide catalyst according to claim 1, wherein the drying temperature is 80 ℃ and the drying time is 12 hours.
9. Use of the Ni-MnOx doped oxide catalyst of claim 1 in CO oxidation.
10. The use of the Ni-MnOx doped oxide catalyst of claim 9 for CO oxidation, including CO purification in CO-containing gases, production of high purity oxygen, and oxidation of CO from combustion of fossil fuels.
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