CN114653375A - Catalyst for removing CO in sintering flue gas and preparation method thereof - Google Patents
Catalyst for removing CO in sintering flue gas and preparation method thereof Download PDFInfo
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- CN114653375A CN114653375A CN202011538520.XA CN202011538520A CN114653375A CN 114653375 A CN114653375 A CN 114653375A CN 202011538520 A CN202011538520 A CN 202011538520A CN 114653375 A CN114653375 A CN 114653375A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 151
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003546 flue gas Substances 0.000 title claims abstract description 50
- 238000005245 sintering Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 49
- 229910016978 MnOx Inorganic materials 0.000 claims abstract description 65
- 229910016553 CuOx Inorganic materials 0.000 claims abstract description 44
- 239000004480 active ingredient Substances 0.000 claims abstract description 41
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000008188 pellet Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 25
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 34
- 229910003320 CeOx Inorganic materials 0.000 claims description 26
- 238000002390 rotary evaporation Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 16
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 16
- 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 16
- 238000011065 in-situ storage Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 11
- 238000001994 activation Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000011363 dried mixture Substances 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000011148 porous material Substances 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 abstract description 10
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 32
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 26
- 239000005751 Copper oxide Substances 0.000 description 26
- 229910000431 copper oxide Inorganic materials 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 16
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 239000010407 anodic oxide Substances 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 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 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention provides a catalyst for removing CO in sintering flue gas and a preparation method thereof, wherein the catalyst comprises 88-92 wt% of an alumina pellet carrier and 8-12 wt% of an active ingredient in percentage by weight; the active ingredient comprises an active component; the active component consists of CuOxAnd MnOxComposition is carried out; the CuOxAnd MnOxThe mass ratio of (1-2.5) to (1). On one hand, the catalyst adopts the spherical carrier, so that the mechanical strength of the catalyst is improved; on the other hand, the transition metal oxide is used as the main active component of the catalyst, so that the preparation cost is reduced, secondary pollution is avoided, the high-efficiency removal of CO in the sintering flue gas can be realized, and the industrial application prospect is good.
Description
Technical Field
The invention belongs to the technical field of metal catalysts, and particularly relates to a catalyst for removing CO in sintering flue gas and a preparation method thereof.
Background
CO, one of the major atmospheric pollutants, poses serious risks to human health and the ecological environment. And the sintering flue gas contains a large amount of CO, the concentration of the CO is generally in the range of 6000-12000 ppm, and even if the CO is reused by a flue gas recycling technology, a large amount of CO still remains in the sintering machine tail gas, so the problem of CO emission in the sintering flue gas needs to be solved urgently.
The removal of CO gas in industry relies mainly on catalytic oxidation processes, which are usedThe catalyst is mainly a supported catalyst containing noble metal. CN111203200A discloses a preparation method of a high-performance CO oxidation catalyst, which comprises the following processing steps: (1) selecting an aluminum alloy as an aluminum base material, wherein the aluminum base material is preferably a 5-series aluminum alloy, and the thickness of the aluminum alloy is less than 0.5 cm; (2) pretreating an aluminum substrate; (3) carrying out anodic oxidation treatment on the treated aluminum substrate to form an oxide film on the surface; (4) adsorbing a protective film on the surface of the porous layer of the anodic oxide film, wherein the protective film is not adsorbed on the shielding layer; (5) removing the shielding layer at the bottom of the anodic oxide film to expose the aluminum substrate; (6) removing the aluminum substrate to obtain Al containing only the porous layer of the anodic oxide film2O3A carrier; (7) al obtained in step (6)2O3Taking an aqueous solution of chloroplatinic acid as a precursor as a carrier, adopting an isovolumetric impregnation method, impregnating at room temperature, freezing, condensing and drying in vacuum to obtain Pt/Al2O3A catalyst.
CN110876943A discloses an oxide-modified Pt-Co bimetallic catalyst, a preparation method and application thereof in CO oxidation, wherein the structural formula of the catalyst is Pt-Co/La-Ce-O, and the molecular formula of a precursor is La1-yCeyCo1-xPtxO3Wherein the value range of x is 0.01-0.17, and the value range of y is 0-0.25; the preparation method of the catalyst comprises the following steps: (1) lanthanum nitrate according to the molar ratio: cerium nitrate: cobalt nitrate: platinum nitrate: citric acid: preparing a solution according to the proportion of (1-0.75): (0-0.25): (0.99-0.83): (0.01-0.17): 2.4: 0.48; (2) stirring the solution prepared in the step (1) in a water bath kettle at the temperature of 60-90 ℃ until sol is formed, and obtaining an intermediate product; (3) transferring the intermediate product obtained in the step (2) to a constant-temperature drying oven for drying to obtain a dried product; (4) roasting the product obtained in the step (3) at 250-350 ℃, and then roasting at 550-750 ℃ to obtain a catalyst precursor La1-yCeyCo1-xPtxO3Has a perovskite type composite oxide structure; (5) placing the catalyst precursor obtained in the step (4) into a reactor, introducing reduction reaction gas into the reactor, and reducing the catalyst precursor; the temperature is 550-650 ℃; to obtain catalystThe oxidant Pt-Co/La-Ce-O.
The method adopts precious metals to prepare the catalyst, but the precious metals have limited reserves and higher prices, so the use of the catalyst in large-flow industrial flue gas is limited in cost.
On the other hand, the research on non-noble metal catalysts mainly focuses on powder catalysts, and most researches do not consider NO and SO in flue gas2And the influence of impurity gases makes it unfavorable for industrial application.
In summary, it is an urgent need to provide a CO oxidation catalyst with high strength, NO influence from impurity gases such as NO, and low cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a catalyst for removing CO in sintering flue gas and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a catalyst for removing CO from sintering flue gas, wherein the catalyst comprises, by weight, 88-92 wt% of an alumina pellet carrier, such as 88 wt%, 89 wt%, 90 wt%, 91 wt%, or 92 wt%; 8 to 12 wt% of an active ingredient, for example, 8 wt%, 9 wt%, 10 wt%, 11 wt%, or 12 wt%; the above-mentioned amounts are not to be selected exclusively for the values listed, but other values not listed within the respective numerical ranges are equally applicable.
The active ingredient comprises an active component; the active component consists of CuOxAnd MnOxAnd (4) forming.
The CuOxAnd MnOxThe mass ratio of (1 to 2.5):1, for example, 1:1, 1.5:1, 2:1 or 2.5:1, but is not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
In the present invention, the catalyst has high strength and long service lifeThe spherical carrier improves the mechanical strength of the catalyst compared with the traditional powder carrier; in another aspect, the catalyst employs transition metal oxide CuOxAnd MnOxAs an active component, precious metals such as platinum and the like are replaced, the preparation cost is reduced, secondary pollution is avoided, and CO in the sintering flue gas can be efficiently removed; the catalyst is not influenced by NO in the flue gas, has partial capability of removing NO, can be widely applied to removing CO in the sintering flue gas, and has good industrial application prospect.
In the present invention, the content of the active ingredient needs to be controlled. If the content of the active ingredient is too high, on one hand, the active ingredient is accumulated on the surface of the carrier and cannot be well dispersed, so that the waste of the active ingredient which is not exposed on the surface is caused, and on the other hand, the excessive content of the active ingredient causes the falling of the active ingredient, so that the mechanical strength of the catalyst is reduced; if the content of the active component is too low, active sites on the surface of the catalyst for catalytic reaction are reduced, and the catalytic reaction is not facilitated, so that the catalytic activity is reduced.
In the present invention, CuOxAnd MnOxThe catalytic synergistic effect exists between the CuO and the CuO, and the electron transfer between different oxides promotes the catalytic reaction, thereby improving the catalytic activityxAnd MnOxWhen the catalyst exists alone, the catalyst has higher CO catalytic removal performance; wherein, MnOxHas higher low-temperature oxidation capability and is also a component of a low-temperature denitration catalyst, and MnO is loadedxThe influence of NO in the sintering flue gas on the catalyst can be avoided; CuO (copper oxide)xHas strong oxidation-reduction capability and is prepared by loading CuOxAnd the catalytic removal capability of CO at low temperature can be effectively improved.
In the present invention, CuO is an active ingredientxAnd MnOxCu and Mn in the alloy have multiple valence states, so that transition metal oxides are all mixtures, and CuO is calculatedxAnd MnOxRespectively CuO and Mn2O3Is standard and passes CuOxAnd MnOxThe mass ratio of the copper nitrate to the manganese nitrate in the solution containing the active metal precursor is calculated.
In the present invention, CuO is an active ingredient in the catalystxAnd MnOxThe quality of (2) needs to be controlled. Reactive metal oxide CuOxAnd MnOxThe catalytic synergy between the oxides requires a certain ratio range among the oxides, wherein CuOxAnd MnOxToo high or too low of the amount of the active component is not beneficial to the electron transfer and the synergistic effect between the active components and the enhancement of the catalytic reaction.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferred technical scheme of the invention, the spherical carrier comprises alumina balls.
Preferably, the spherical support has a diameter of 1 to 2mm, such as 1mm, 1.2mm, 1.4mm, 1.6mm, 1.8mm, or 2mm, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the active ingredient further comprises a co-agent.
Preferably, the coagent is a rare earth metal oxide, preferably CeOx。
Preferably, the mass ratio of the active ingredient to the coagent is (1.5-2): 1, for example 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1 or 2:1, but not limited to the recited values, and other values not recited within this range of values are equally applicable.
In the present invention, the coagent CeOxCe in the CeO has multiple valence states, and the metal oxides are mixtures, so the CeO is calculatedxIn mass of (C) is CeO2And calculating the ratio of cerium nitrate in the solution containing the active metal precursor by using the mass ratio of the active component to the active additive as a standard.
In the invention, the catalyst is modified by loading cerium SO as to improve the SO resistance of the catalyst2The poisoning ability of (c). CeO (CeO)xCan inhibit the active component CuOxAnd MnOxIs covered with SO2Sulfiding to sulfate (conversion of active oxides to sulfate results in disappearance of catalytically active sites, i.e. sulfur dioxide poisoning deactivation of the catalyst). If CeOxThe amount of the catalyst is too small, so that the activity of the catalyst in the sulfur dioxide-containing atmosphere is influenced, and the effect of inhibiting sulfur poisoning is not achieved; if CeOxToo large an amount of the catalyst will cover the CuO as an active ingredientxAnd MnOxThe active sites of (2) are not beneficial to improving the CO catalytic removal capability of the catalyst.
In another aspect, the present invention provides a method for preparing the catalyst, the method comprising the steps of:
(1) mixing the pretreated spherical carrier with a solution containing an active metal precursor, and performing rotary evaporation and calcination to obtain a catalyst sample;
(2) and (3) carrying out in-situ activation on the catalyst sample obtained in the step (2) to obtain a catalyst finished product.
In the preparation method, a rotary evaporation auxiliary excess impregnation method is adopted, the pretreated spherical carrier is immersed in a solution containing an active metal precursor, and the catalyst is prepared through rotary evaporation, drying, calcination and activation; the preparation method has the advantages of simple process flow, easily obtained raw materials, low cost and good industrial application prospect.
In the invention, the active ingredients can be reduced into low-valent oxides through the reduction site activation treatment, which is beneficial to the occurrence of catalytic reaction and simultaneously prevents the rapid inactivation of the catalyst.
As a preferred technical scheme of the invention, the spherical carrier in the step (1) comprises alumina pellets.
Preferably, the active metal in step (1) is a metal element included in the active component.
Preferably, the pretreatment of step (1) comprises washing and drying in sequence.
Preferably, the cleaning mode is ultrasonic cleaning.
Preferably, the washing time is 1 to 2 hours, such as 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, etc., but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the drying temperature is 120 to 130 ℃, for example, 120 ℃, 122 ℃, 124 ℃, 126 ℃, 128 ℃ or 130 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the drying time is not less than 12 hours, such as 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, and the like, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
In a preferred embodiment of the present invention, the solution containing the active metal precursor in the step (1) includes a nitrate solution containing an active metal.
Preferably, the nitrate solution includes a manganese nitrate solution and a copper nitrate solution.
Preferably, the nitrate solution further comprises a cerium nitrate solution.
As a preferable technical scheme of the invention, the water bath heating is carried out after the mixing in the step (1).
Preferably, the temperature of the water bath heating is 80 to 90 ℃, for example 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃ or 90 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the time for heating in the water bath is 3-4 h, such as 3h, 3.2h, 3.4h, 3.6h, 3.8h or 4h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the water bath heating is carried out in an electromagnetic stirrer.
Preferably, the rotary evaporation of step (1) is carried out in a rotary evaporator.
Preferably, the temperature of the rotary evaporation in the step (1) is 80 to 90 ℃, for example 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃ or 90 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the rotary evaporation time in step (1) is 3-4 h, such as 3h, 3.2h, 3.4h, 3.6h, 3.8h or 4h, but not limited to the recited values, and other values in the range of the recited values are also applicable.
In the invention, the rotary evaporation operation can ensure that the active ingredients are gradually and uniformly loaded on the surface of the alumina pellet, thereby improving the catalytic activity and the mechanical strength of the catalyst.
Preferably, drying is carried out after the rotary evaporation in the step (1).
Preferably, the drying mode is air blast drying.
Preferably, the drying temperature is 120 to 130 ℃, for example, 120 ℃, 122 ℃, 124 ℃, 126 ℃, 128 ℃ or 130 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the drying time is 12 to 15 hours, such as 12 hours, 13 hours, 14 hours, 15 hours, and the like, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the calcination of step (1) is carried out in a high temperature tube furnace.
Preferably, the temperature of the calcination in step (1) is 400 to 500 ℃, for example, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃ or 500 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the calcination time in step (1) is 6-8 h, such as 6h, 6.5h, 7h, 7.5h or 8h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical scheme of the invention, the components in the catalyst sample in the step (1) comprise CuOx、MnOxAnd CeOx。
Preferably, the CuOxAnd MnOxThe mass ratio of (1 to 2.5):1, for example, 1:1, 1.5:1, 2:1 or 2.5:1, but is not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
Preferably, the CuOxAnd MnOxTotal mass of (D) and CeOxThe mass ratio of (1.5-2): 1, exampleSuch as 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2:1, but not limited to the recited values, and other values not recited within the numerical range are equally applicable.
In a preferred embodiment of the present invention, the temperature of the in-situ activation in step (2) is 400 to 420 ℃, for example, 400 ℃, 402 ℃, 404 ℃, 406 ℃, 408 ℃, 410 ℃, 412 ℃, 414 ℃, 416 ℃, 418 ℃ or 420 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the in situ activation of step (2) is carried out under a non-oxidizing atmosphere.
Preferably, the non-oxidizing atmosphere comprises carbon monoxide and a protective gas.
Preferably, the protective gas comprises nitrogen and/or an inert gas.
Preferably, the amount of carbon monoxide in the non-oxidizing atmosphere is 8 to 12 vol.%, e.g., 8 vol.%, 9 vol.%, 10 vol.%, 11 vol.% or 12 vol.%, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the in-situ activation time in step (2) is 90-110 min, such as 90min, 95min, 100min, 105min or 110min, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) ultrasonically cleaning an aluminum oxide pellet with the diameter of 1-2 mm for 2-3 h, and drying at 120-130 ℃ for at least 12h after cleaning; mixing the dried small aluminum oxide balls with a solution containing manganese nitrate, copper nitrate and cerium nitrate, then placing the mixture in an electromagnetic stirrer to be heated in a water bath at the temperature of 80-90 ℃ for 3-4 h, placing the mixture in a rotary evaporator to be subjected to rotary evaporation at the temperature of 80-90 ℃ for 3-4 h after being heated in the water bath, blowing and drying the mixture for 12-15 h at the temperature of 120-130 ℃, and placing the dried mixture in a high-temperature tubular furnace to be calcined at the temperature of 400-500 ℃ for 6-8 h to obtain a catalyst sample; CuO in the catalyst samplexAnd MnOxThe mass ratio of (1-2.5) to (1) CuOxAnd MnOxTotal mass of (D) and CeOxThe mass ratio of (1.5-2) to (1);
(2) and (3) activating the catalyst sample obtained in the step (2) in situ for 90-110 min at 400-420 ℃ in an atmosphere containing carbon monoxide and protective gas to obtain a catalyst finished product, wherein the content of the carbon monoxide is 8-12 vol.%.
In the invention, the prepared catalyst is used for removing CO in sintering flue gas, and the components of the sintering flue gas comprise CO and O2、NO、SO2And N2(ii) a The content of each component of the sintering flue gas comprises 6000-12000 ppm of CO, such as 6000ppm, 7000ppm, 8000ppm, 9000ppm, 10000ppm, 11000ppm or 12000 ppm; o is212-18 vol.%, such as 12 vol.%, 13 vol.%, 14 vol.%, 15 vol.%, 16 vol.%, 17 vol.% or 18 vol.%; NO 0 to 550ppm, for example 0ppm, 50ppm, 100ppm, 200ppm, 300ppm, 400ppm, 500ppm or 550 ppm; SO (SO)20 to 200ppm, for example 0ppm, 50ppm, 100ppm, 150ppm or 200 ppm; the balance being N2The above-mentioned amounts are not to be selected exclusively for the values listed, but other values not listed within the respective numerical ranges are equally applicable.
In the invention, the reaction conditions of the catalytic reaction of the catalyst are as follows:
the reaction temperature is 120 to 200 ℃, for example, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃, etc.; the reaction pressure is normal pressure; the space velocity of the reaction is 9000-12000 h-1For example 9000h-1、9500h-1、10000h-1、10500h-1、11000h-1、11500h-1Or 12000h-1For example, the above numerical values are not limited to the listed numerical values, and other numerical values not listed in the respective numerical ranges are also applicable.
Compared with the prior art, the invention has the following beneficial effects:
(1) on one hand, the catalyst of the invention adopts the spherical carrier, thus improving the mechanical strength of the catalyst; on the other hand by using transition goldBelongs to oxides as the main active component of the catalyst, reduces the preparation cost, has no secondary pollution, can efficiently remove CO in the sintering flue gas, and does not contain SO2The average removal rate of CO in the sintering flue gas can reach 98.81 percent, and the sintering flue gas contains SO2The average removal rate of CO in the sintering flue gas reaches above 85.11%; and further loading cerium and further controlling the mass ratio between active ingredients to make the active ingredients contain SO2The average removal rate of CO in the sintering flue gas can reach above 92.19%;
(2) the preparation method has the advantages of simple process flow, easily obtained raw materials and low cost, and the prepared catalyst is not influenced by NO in the flue gas, has the capability of partially and synergistically removing NO, and has good industrial application prospect.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The invention provides a catalyst for removing CO in sintering flue gas and a preparation method thereof, and the catalyst comprises 88-92 wt% of an alumina pellet carrier and 8-12 wt% of an active component in percentage by weight;
the active ingredient comprises an active component; the active component consists of CuOxAnd MnOxComposition is carried out;
the CuOxAnd MnOxThe mass ratio of (1-2.5) to (1).
The preparation method comprises the following steps:
(1) mixing the pretreated spherical carrier with a solution containing an active metal precursor, and performing rotary evaporation and calcination to obtain a catalyst sample;
(2) and (3) carrying out in-situ activation on the catalyst sample obtained in the step (2) to obtain a catalyst finished product.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a catalyst for removing CO in sintering flue gas and a preparation method thereof, wherein the catalyst comprises 90 wt% of an alumina pellet carrier and 10 wt% of an active ingredient in percentage by weight;
the active ingredient comprises an active component; the active component consists of CuOxAnd MnOxComposition is carried out;
the CuOxAnd MnOxThe mass ratio of (A) to (B) is 1.5: 1.
The preparation method comprises the following steps:
(1) ultrasonically cleaning 90g of alumina pellets with the diameter of 1mm for 2h, and drying for 12h at the temperature of 120 ℃ after cleaning; mixing the dried alumina pellets with a solution containing 9.07g of manganese nitrate and 14.15g of copper nitrate, then placing the mixture in an electromagnetic stirrer to heat in a water bath at 80 ℃ for 3h, placing the mixture in a rotary evaporator to carry out rotary evaporation at 80 ℃ for 4h after heating in the water bath, carrying out forced air drying at 120 ℃ for 12h after rotary evaporation, and placing the dried mixture in a high-temperature tubular furnace to calcine at 450 ℃ for 6h to obtain a catalyst sample; CuO in the catalyst samplexAnd MnOxThe mass ratio of (A) to (B) is 1.5: 1;
(2) and (3) activating the catalyst sample obtained in the step (2) in situ for 90min at 400 ℃ in an atmosphere containing carbon monoxide and nitrogen to obtain a finished catalyst product, wherein the content of the carbon monoxide is 10 vol.%.
Example 2:
the embodiment provides a catalyst for removing CO in sintering flue gas and a preparation method thereof, wherein the catalyst comprises 92 wt% of an alumina pellet carrier and 8 wt% of an active ingredient by weight percentage;
the active ingredients comprise active components and active auxiliary agents; the active component consists of CuOxAnd MnOxForming; the active assistant is CeOx；
The CuOxAnd MnOxThe mass ratio of (A) to (B) is 1: 1.
The preparation method comprises the following steps:
(1) ultrasonic cleaning 92g of alumina pellets with the diameter of 2mm for 3hAfter cleaning, drying for 13h at 130 ℃; mixing the dried alumina pellets with a solution containing 5.44g of manganese nitrate, 5.66g of copper nitrate and 8.07g of cerium nitrate, then placing the mixture in an electromagnetic stirrer to heat in a water bath at 90 ℃ for 4h, placing the mixture in a rotary evaporator to carry out rotary evaporation at 90 ℃ for 3h after heating in the water bath, carrying out air blast drying at 130 ℃ for 15h after rotary evaporation, placing the mixture in a high-temperature tubular furnace to calcine at 400 ℃ for 8h after drying, wherein CuO in the catalyst samplexAnd MnOxIn a mass ratio of 1:1, CuOxAnd MnOxTotal mass of (D) and CeOxThe mass ratio of (A) to (B) is 1.5: 1;
(2) and (3) activating the catalyst sample obtained in the step (2) in situ at 420 ℃ for 100min in an atmosphere containing carbon monoxide and nitrogen to obtain a finished catalyst product, wherein the content of the carbon monoxide is 8 vol.%.
Example 3:
the embodiment provides a catalyst for removing CO in sintering flue gas and a preparation method thereof, wherein the catalyst comprises 88 wt% of an alumina pellet carrier and 12 wt% of an active ingredient by weight percentage;
the active ingredients comprise active components and active auxiliary agents; the active component consists of CuOxAnd MnOxComposition is carried out; the active assistant is CeOx；
The CuOxAnd MnOxThe mass ratio of (A) to (B) is 2.5: 1.
The preparation method comprises the following steps:
(1) ultrasonically cleaning 88g of alumina pellets with the diameter of 1.5mm for 2.5h, and drying at 125 ℃ for 14h after cleaning; mixing the dried alumina pellets with a solution containing 4.66g of manganese nitrate, 12.13g of copper nitrate and 12.11g of cerium nitrate, then placing the mixture in an electromagnetic stirrer to heat in a water bath for 3.5h at 85 ℃, placing the mixture in a rotary evaporator to carry out rotary evaporation for 3.5h at 85 ℃, carrying out air-blast drying for 13h at 125 ℃ after the rotary evaporation, placing the mixture in a high-temperature tubular furnace to calcine for 7h at 500 ℃ after the drying to obtain a catalyst sample, and obtaining CuO in the catalyst samplexAnd MnOxIn a mass ratio of 2.5:1, CuOxAnd MnOxTotal mass of (D) and CeOxThe mass ratio of (A) to (B) is 1.5: 1;
(2) and (3) activating the catalyst sample obtained in the step (2) in situ at 410 ℃ for 110min in an atmosphere containing carbon monoxide and argon to obtain a finished catalyst product, wherein the content of the carbon monoxide is 12 vol.%.
Example 4:
the embodiment provides a catalyst for removing CO in sintering flue gas and a preparation method thereof, wherein the catalyst comprises 90 wt% of an alumina pellet carrier and 10 wt% of an active ingredient in percentage by weight;
the active ingredients comprise active components and active auxiliaries; the active component consists of CuOxAnd MnOxForming; the active assistant is CeOx；
The CuOxAnd MnOxThe mass ratio of (A) to (B) is 2: 1.
The preparation method comprises the following steps:
(1) ultrasonically cleaning 90g of alumina pellets with the diameter of 1mm for 2h, and drying for 12h at the temperature of 122 ℃; mixing the dried alumina pellets with a solution containing 5.04g of manganese nitrate, 10.48g of copper nitrate and 8.41g of cerium nitrate, then placing the mixture in an electromagnetic stirrer to heat in a water bath for 3.5h at 85 ℃, placing the mixture in a rotary evaporator to carry out rotary evaporation for 3.5h at 80 ℃ after heating in the water bath, carrying out air blast drying for 14h at 120 ℃ after rotary evaporation, and placing the mixture in a high-temperature tubular furnace to calcine for 6.5h at 450 ℃ after drying to obtain a catalyst sample; CuO in the catalyst samplexAnd MnOxIn a mass ratio of 2:1, CuOxAnd MnOxTotal mass of (D) and CeOxThe mass ratio of (A) to (B) is 2: 1;
(2) and (3) activating the catalyst sample obtained in the step (2) in situ at 400 ℃ for 100min in an atmosphere containing carbon monoxide and nitrogen to obtain a finished catalyst product, wherein the content of the carbon monoxide is 10 vol.%.
Example 5:
the present embodiment provides a catalyst for removing CO from sintering flue gas and a preparation method thereof, wherein the catalyst is different from the catalyst in embodiment 2 only in that: CuO (copper oxide)xAnd MnOxThe mass ratio of (A) to (B) is 0.3: 1.
The preparation is referred to the preparation in example 2, differing only in that: in step (1), the dried alumina pellets were mixed with a solution containing 8.37g of manganese nitrate, 2.61g of copper nitrate and 8.07g of cerium nitrate, so that CuO was contained in the calcined catalyst samplexAnd MnOxIn a mass ratio of 0.3:1, CuOxAnd MnOxTotal mass of (D) and CeOxThe mass ratio of (a) is still 1.5: 1.
Example 6:
the present embodiment provides a catalyst for removing CO from sintering flue gas and a preparation method thereof, wherein the catalyst is the catalyst in example 3, and the difference is only that: CuO (copper oxide)xAnd MnOxThe mass ratio of (A) to (B) is 4: 1.
The preparation is referred to the preparation in example 3, differing only in that: in step (1), the dried alumina pellets were mixed with a solution containing 3.26g of manganese nitrate, 13.58g of copper nitrate and 12.11g of cerium nitrate, so that CuO was contained in the calcined catalyst samplexAnd MnOxIn a mass ratio of 4:1, CuOxAnd MnOxTotal mass of (D) and CeOxStill the mass ratio of (a) to (b) is 1.5: 1.
Example 7:
the embodiment provides a catalyst for removing CO in sintering flue gas and a preparation method thereof, and the catalyst refers to the catalyst in the embodiment 3.
The preparation process is referred to the preparation process in example 3, with the only difference that: in step (1), the dried alumina pellets were mixed with a solution containing 3.89g of manganese nitrate, 10.10g of copper nitrate and 15.14g of cerium nitrate, so that CuO was contained in the calcined catalyst samplexAnd MnOxIs still 2.5:1, and CuOxAnd MnOxTotal mass of (D) and CeOxThe mass ratio of (A) to (B) is 1: 1.
Example 8:
the embodiment provides a catalyst for removing CO in sintering flue gas and a preparation method thereof, and the catalyst refers to the catalyst in the embodiment 4.
The preparation methodReferring to the preparation method in example 4, the only difference is that: in step (1), the dried alumina pellets were mixed with a solution containing 5.67g of manganese nitrate, 11.79g of copper nitrate and 6.31g of cerium nitrate, so that CuO was contained in the calcined catalyst samplexAnd MnOxIs still 2:1, and CuOxAnd MnOxTotal mass of (D) and CeOxThe mass ratio of (A) to (B) is 3: 1.
Comparative example 1:
this comparative example provides a catalyst for removing CO from sintering flue gas and a method for preparing the same, the catalyst being comparable to the catalyst of example 2 except that: the catalyst comprises 97 wt% of alumina pellet carrier and 3 wt% of active ingredients by weight percentage;
the preparation process is referred to the preparation process in example 2, with the only difference that: in the step (1), the dried alumina pellets were mixed with a solution containing 2.04g of manganese nitrate, 2.12g of copper nitrate and 3.03g of cerium nitrate, and CuO was contained in the calcined catalyst samplexAnd MnOxIs still 1:1, CuOxAnd MnOxTotal mass of (D) and CeOxStill the mass ratio of (a) to (b) is 1.5: 1.
Comparative example 2:
this comparative example provides a catalyst for removing CO from sintering flue gas and a method for its preparation, said catalyst being comparable to the catalyst of example 3, except that: the catalyst comprises 80 wt% of alumina pellet carrier and 20 wt% of active ingredient by weight percentage;
the preparation process is referred to the preparation process in example 3, with the only difference that: in step (1), the dried alumina pellets were mixed with a solution containing 7.77g of manganese nitrate, 20.21g of copper nitrate and 20.18g of cerium nitrate, and CuO was contained in the calcined catalyst samplexAnd MnOxStill in a mass ratio of 2.5:1, CuOxAnd MnOxTotal mass of (D) and CeOxStill the mass ratio of (a) to (b) is 1.5: 1.
Comparative example 3:
the comparative example provides a catalyst for removing CO in sintering flue gas and a preparation method thereof, and the catalyst refers to the catalyst in example 2.
The preparation is referred to the method in example 2, with the only difference that: in step (1), the dried alumina pellets were mixed with a solution containing 10.88g of manganese nitrate and 8.07g of cerium nitrate.
Comparative example 4:
the comparative example provides a catalyst for removing CO in sintering flue gas and a preparation method thereof, and the catalyst refers to the catalyst in example 2.
The preparation is referred to the method in example 2, with the only difference that: in step (1), the dried alumina pellets were mixed with a solution containing 11.32g of copper nitrate and 8.07g of cerium nitrate.
The catalysts obtained in examples 1 to 8 and comparative examples 1 to 4 were used for removing CO from sintering flue gas, and the average removal rate of CO was measured for 1 hour, and the measurement results are shown in Table 1. The determination conditions include: placing the catalyst at the bottom of a U-shaped fixed bed reactor, arranging alumina heat accumulator balls with the diameter of 3mm on two sides of the catalyst, and performing catalytic reaction at 180 ℃, normal pressure and airspeed of 10000h-1The components in the sintering flue gas comprise CO 9000ppm and O2 16vol.％、NO 550ppm，SO2200ppm, the balance being N2。
In addition to the above measurements, the catalyst obtained in example 1 was used for removing SO-free compounds2The average removal rate of CO is measured, and the measurement time and the measurement conditions are determined by referring to the measurement time and the measurement conditions as described above, except that SO is not contained2. The measurement results are shown in table 1.
TABLE 1 average CO removal from sintering fumes with different composition content for catalysts obtained in examples 1-8 and comparative examples 1-4
| Average CO removal rate/％ | |
| Example 1 (no SO)2Time) | 98.81 |
| Example 1 | 90.76 |
| Example 2 | 95.46 |
| Example 3 | 93.97 |
| Example 4 | 92.19 |
| Example 5 | 85.39 |
| Example 6 | 89.21 |
| Example 7 | 85.11 |
| Example 8 | 87.37 |
| Comparative example 1 | 53.81 |
| Comparative example 2 | 76.56 |
| Comparative example 3 | 74.95 |
| Comparative example 4 | 81.83 |
Example 1 the catalyst prepared by reacting CuOxAnd MnOxTwo transition metal oxides are used as active components of the catalyst, and no SO is generated under test conditions2The average removal rate of CO in the sintering flue gas can reach 98.81 percent, and SO is contained2The average removal rate of CO in the sintering flue gas can reach 90.76%; examples 2-4 the SO resistance of the catalyst was improved by further loading cerium and controlling the mass ratio between the active ingredients2The poisoning capability enables the average removal rate of CO to reach above 92.19%; CuO in catalysts prepared in examples 5 and 6xAnd MnOxToo small or too large mass ratio of (A) results in CuOxAnd MnOxThe catalytic synergistic effect is weakened, and the catalytic activity is reduced; example 7 catalyst prepared in CuOxAnd MnOxTotal mass of (C) and CeOxToo small a mass ratio of (a) results in a decrease in the number of main active sites and a decrease in catalytic activity; example 8 preparation of the resulting catalyst in which CuO was presentxAnd MnOxTotal mass of (D) and CeOxToo large a mass ratio of (A) to (B), resulting in the coagent CeOxThe content is reduced and the sulfur resistance of the catalyst is weakened.
The content of the active ingredients of the catalyst prepared in the comparative example 1 is too low, so that the active sites on the surface of the catalyst for catalytic reaction are reduced, and the catalytic reaction is not facilitated, so that the catalytic activity is low; the catalyst prepared in the comparative example 2 has too high content of active ingredients, so that the active ingredients are accumulated on the surface of the carrier and cannot be well dispersed, the waste of the active ingredients which are not exposed on the surface is caused, and the active ingredients fall off, so that the catalytic activity is not high; the catalysts prepared in comparative example 3 and comparative example 4 did not support copper and manganese, respectively, affecting CuOxAnd MnOxThe catalytic synergistic effect between the two is not beneficial to the improvement of the catalytic activity.
It can be seen from the above examples that, on one hand, the catalyst of the present invention improves the mechanical strength of the catalyst by using the spherical carrier; on the other hand, the transition metal oxide is adopted as the main active component of the catalyst, SO that the preparation cost is reduced, secondary pollution is avoided, CO in the sintering flue gas can be efficiently removed, and SO is not contained in the sintering flue gas2The average removal rate of CO in the sintering flue gas can reach 98.81 percent, and the sintering flue gas contains SO2The average removal rate of CO in the sintering flue gas reaches above 85.11%; and further loading cerium and further controlling the mass ratio between active ingredients to make the active ingredients contain SO2The average removal rate of CO in the sintering flue gas can reach above 92.19%; the preparation method has the advantages of simple process flow, easily obtained raw materials and low cost, and the prepared catalyst is not influenced by NO in the flue gas, has the capability of partially and synergistically removing NO, and has good industrial application prospect.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It will be apparent to those skilled in the art that any modifications to the present invention, equivalents to the operation of the invention, additions of additional operations, selection of specific ways, etc., are within the scope and disclosure of the invention.
Claims (10)
1. The catalyst for removing CO in sintering flue gas is characterized by comprising 88-92 wt% of spherical carrier and 8-12 wt% of active ingredient;
the active ingredient comprises an active component; the active component consists of CuOxAnd MnOxComposition is carried out;
the CuOxAnd MnOxThe mass ratio of (1-2.5) to (1).
2. The catalyst of claim 1, wherein the spherical support comprises alumina pellets;
preferably, the diameter of the spherical carrier is 1-2 mm;
preferably, the active ingredient further comprises a co-agent;
preferably, the coagent is a rare earth metal oxide, preferably CeOx；
Preferably, the mass ratio of the active component to the active auxiliary agent is (1.5-2): 1.
3. A method for preparing a catalyst according to claim 1 or 2, characterized in that it comprises the following steps:
(1) mixing the pretreated spherical carrier with a solution containing an active metal precursor, and performing rotary evaporation and calcination to obtain a catalyst sample;
(2) and (3) carrying out in-situ activation on the catalyst sample obtained in the step (2) to obtain a catalyst finished product.
4. The production method according to claim 3, wherein the spherical support of step (1) comprises alumina pellets;
preferably, the active metal in step (1) is a metal element included in the active component;
preferably, the pretreatment of the step (1) comprises washing and drying in sequence;
preferably, the cleaning mode is ultrasonic cleaning;
preferably, the cleaning time is 1-2 h;
preferably, the drying temperature is 120-130 ℃;
preferably, the drying time is not less than 12 hours.
5. The production method according to claim 3 or 4, wherein the solution containing the active metal precursor of step (1) comprises a nitrate solution containing an active metal;
preferably, the nitrate solution comprises a manganese nitrate solution and a copper nitrate solution;
preferably, the nitrate solution further comprises a cerium nitrate solution.
6. The method according to any one of claims 3 to 5, wherein the mixing in step (1) is followed by heating in a water bath;
preferably, the temperature of the water bath heating is 80-90 ℃;
preferably, the water bath heating time is 3-4 h;
preferably, the water bath heating is carried out in an electromagnetic stirrer;
preferably, the rotary evaporation of step (1) is carried out in a rotary evaporator;
preferably, the temperature of the rotary evaporation in the step (1) is 80-90 ℃;
preferably, the rotary evaporation time in the step (1) is 3-4 h;
preferably, drying is carried out after the rotary evaporation in the step (1);
preferably, the drying mode is air blast drying;
preferably, the drying temperature is 120-130 ℃;
preferably, the drying time is 12-15 h.
7. The method according to any one of claims 3 to 6, wherein the calcination of step (1) is carried out in a high-temperature tube furnace;
preferably, the calcining temperature in the step (1) is 400-500 ℃;
preferably, the calcining time in the step (1) is 6-8 h.
8. The production method according to any one of claims 3 to 7, wherein the component in the catalyst sample in the step (1) comprises CuOx、MnOxAnd CeOx；
Preferably, the CuOxAnd MnOxThe mass ratio of (1-2.5) to (1);
preferably, the CuOxAnd MnOxTotal mass of (D) and CeOxThe mass ratio of (1.5-2) to (1).
9. The method for preparing a porous material according to any one of claims 3 to 8, wherein the temperature of the in-situ activation in the step (2) is 400 to 420 ℃;
preferably, said in situ activation of step (2) is carried out under a non-oxidizing atmosphere;
preferably, the non-oxidizing atmosphere comprises carbon monoxide and a protective gas;
preferably, the protective gas comprises nitrogen and/or an inert gas;
preferably, the content of carbon monoxide in the non-oxidizing atmosphere is 8-12 vol.%;
preferably, the in-situ activation time in the step (2) is 90-110 min.
10. The method of any one of claims 3 to 9, comprising the steps of:
(1) ultrasonically cleaning an aluminum oxide pellet with the diameter of 1-2 mm for 1-2 h, and drying at 120-130 ℃ for at least 12h after cleaning; mixing the dried small aluminum oxide balls with a solution containing manganese nitrate, copper nitrate and cerium nitrate, then placing the mixture in an electromagnetic stirrer to be heated in a water bath at the temperature of 80-90 ℃ for 3-4 h, placing the mixture in a rotary evaporator to be subjected to rotary evaporation at the temperature of 80-90 ℃ for 3-4 h after being heated in the water bath, blowing and drying the mixture for 12-15 h at the temperature of 120-130 ℃, and placing the dried mixture in a high-temperature tubular furnace to be calcined at the temperature of 400-500 ℃ for 6-8 h to obtain a catalyst sample; CuO in the catalyst samplexAnd MnOxThe mass ratio of (1-2.5) to (1) CuOxAnd MnOxTotal mass of (D) and CeOxThe mass ratio of (1.5-2) to (1);
(2) and (3) activating the catalyst sample obtained in the step (2) in situ for 90-110 min at 400-420 ℃ in an atmosphere containing carbon monoxide and protective gas to obtain a catalyst finished product, wherein the content of the carbon monoxide is 8-12 vol.%.
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