CN117380212A - Catalyst for removing carbon monoxide by low-temperature oxidation and preparation method thereof - Google Patents
Catalyst for removing carbon monoxide by low-temperature oxidation and preparation method thereof Download PDFInfo
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- CN117380212A CN117380212A CN202311504455.2A CN202311504455A CN117380212A CN 117380212 A CN117380212 A CN 117380212A CN 202311504455 A CN202311504455 A CN 202311504455A CN 117380212 A CN117380212 A CN 117380212A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 57
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 44
- 230000003647 oxidation Effects 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 178
- 238000003756 stirring Methods 0.000 claims abstract description 95
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 89
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000005406 washing Methods 0.000 claims abstract description 30
- 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 abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 25
- 229910001868 water Inorganic materials 0.000 claims abstract description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011258 core-shell material Substances 0.000 claims abstract description 22
- 239000000725 suspension Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 17
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229960000583 acetic acid Drugs 0.000 claims abstract description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 10
- 238000007873 sieving Methods 0.000 claims abstract description 10
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004729 solvothermal method Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 229910000510 noble metal Inorganic materials 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003546 flue gas Substances 0.000 description 8
- -1 steel Chemical compound 0.000 description 8
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 239000002082 metal nanoparticle Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000010187 selection method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002912 waste gas Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
Abstract
The invention discloses a preparation method of a catalyst for removing carbon monoxide by low-temperature oxidation, which comprises the steps of dispersing gaseous titanium dioxide P25 into absolute ethyl alcohol, and adding glacial acetic acid and tetrabutyl titanate under a stirring state to obtain pretreated titanium dioxide; adding graphene oxide and copper nitrate into ethanol water solution, stirring uniformly, dropwise adding into pretreated titanium dioxide, stirring at 60-80 ℃ for 10-30min, centrifuging, filtering, and washing to obtain core-shell titanium dioxide; adding core-shell titanium dioxide into a sodium hydroxide solution, uniformly mixing, performing solvothermal reaction for 48-56 hours at 150-160 ℃, performing solid-liquid separation, washing solid matters, and adding the solid matters into water to obtain a titanium dioxide doped suspension; adding manganese nitrate and cerium nitrate into water, stirring uniformly, dropwise adding the titanium dioxide-doped suspension under stirring, stirring until precipitation is obtained, standing, separating solid from liquid, washing, drying, roasting at 500-600 ℃ for 5-10h, granulating, and sieving.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for removing carbon monoxide by low-temperature oxidation and a preparation method thereof.
Background
Carbon monoxide is the product of incomplete oxidation of carbon. Incomplete combustion of traditional fossil fuels such as coal, petroleum, natural gas and the like and biomass fuels is a main source of carbon monoxide.
The development of a catalyst capable of removing carbon monoxide at low temperature and high efficiency is the simplest and most convenient method at present. Although the production of carbon monoxide can be reduced by adopting the technical means of sintering flue gas circulation, adding a burner at the primary flue gas discharge port of the converter, improving the combustion efficiency of the coke oven combustion chamber gas, controlling the air quantity of the dry quenching furnace and the like, a certain amount of residual carbon monoxide is unavoidable in the flue gas, and further purification treatment is still required to realize the environmental protection aim of low carbon monoxide discharge.
The method adopts a proper catalyst to make carbon monoxide in the flue gas undergo the oxidation reaction and convert the carbon monoxide into carbon dioxide, and is one of the accepted effective treatment methods, and the core of the method is the selection and preparation method of the catalyst. Currently, carbon monoxide oxidation catalysts are largely classified into two major categories, noble metals and non-noble metals, depending on the catalytically active components thereof. Most of the noble metal catalysts are Pd, pt, au, ag and supported catalysts in which multicomponent noble metals are supported on carriers such as cordierite and activated alumina, but noble metal catalysts are expensive and limited in use. The non-noble metal catalyst means that the active component of the catalyst can be pure metal or alloy, and the non-noble metal catalyst can be used independently or loaded on a carrier, so that the catalyst has more application ways. The non-noble metal catalyst becomes the catalyst with the most application value due to the convenient preparation process, excellent catalytic performance and recoverability.
However, the non-noble metal nano particles are easy to agglomerate in the preparation process, so that the particle size of the generated non-noble metal particles is often larger, the subsequent application of the material is greatly influenced, the catalytic performance of the non-noble metal is reduced, and meanwhile, the complete conversion temperature is high, and the general conversion temperature is higher than 200 ℃, so that the energy consumption of the device is high, so that the problem to be solved is needed.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a catalyst for removing carbon monoxide by low-temperature oxidation and a preparation method thereof.
A preparation method of a catalyst for removing carbon monoxide by low-temperature oxidation comprises the following steps:
s1, dispersing gas-phase titanium dioxide P25 powder into absolute ethyl alcohol, and sequentially adding glacial acetic acid and tetrabutyl titanate in a stirring state to obtain pretreated titanium dioxide;
s2, adding graphene oxide and copper nitrate into an ethanol water solution, uniformly stirring, dropwise adding the mixture into pretreated titanium dioxide in a stirring state, stirring for 10-30min at 60-80 ℃, regulating the pH value of the system to 11-12, continuously stirring, centrifuging, filtering, and washing to obtain core-shell titanium dioxide;
s3, adding the core-shell titanium dioxide into a sodium hydroxide solution, uniformly mixing, performing solvothermal reaction for 48-56 hours at 150-160 ℃, performing solid-liquid separation, washing solids, and adding the solids into water to obtain a doped titanium dioxide suspension;
s4, adding manganese nitrate and cerium nitrate into water, uniformly stirring, dropwise adding the doped titanium dioxide suspension under the stirring condition, stirring until precipitation is complete, standing for 1-5h, carrying out solid-liquid separation, washing the solid to be neutral, drying, roasting at 500-600 ℃ for 5-10h, granulating, and sieving to obtain the carbon monoxide low-temperature oxidation removal catalyst.
Preferably, in S1, the mass ratio of the gas-phase titanium dioxide P25 to the absolute ethyl alcohol to the glacial acetic acid to the tetrabutyl titanate is 1-5:40-100:2-3:5-10.
Preferably, in S2, the mass fraction of the ethanol aqueous solution is 40-60%, and the mass ratio of graphene oxide, copper nitrate, the ethanol aqueous solution and pretreated titanium dioxide is 1-3:0.1-1:20-50:50-110.
Preferably, in S2, the pH value of the system is adjusted to 11-12 by adopting sodium hydroxide solution with the concentration of 0.5-1.2 mol/L.
Preferably, in S2, the filter is followed by 1-3 washes with absolute ethanol.
Preferably, in S3, the concentration of the sodium hydroxide solution is 9-12mol/L, and the mass ratio of the core-shell titanium dioxide to the sodium hydroxide solution to the water is 9-22:20-30:20-30.
Preferably, in S3, the solid is washed with deionized water to a pH of 10.5-11.2.
Preferably, in S4, the mass ratio of the manganese nitrate to the cerium nitrate to the water to the doped titanium dioxide suspension is 1-2:0.1-1:40-100:30-50.
Preferably, in S4, the drying temperature is 100-120 ℃.
The catalyst for low-temperature oxidation removal of carbon monoxide is prepared by adopting the preparation method of the catalyst for low-temperature oxidation removal of carbon monoxide.
The beneficial effects are that:
the invention adopts gas-phase titanium dioxide P25 as a core, nano titanium dioxide is deposited and combined on the surface of the gas-phase titanium dioxide P25, and graphene oxide and copper nitrate are doped in a deposition layer to form a spherical structure body taking the gas-phase titanium dioxide P25 as a core and the nano titanium dioxide doped with the graphene oxide and the copper nitrate as a shell; through solvothermal reaction, the bonding strength is high, the structural stability is high, graphene oxide on the shell structure can be effectively removed through roasting, a large number of active void structures are formed, the specific surface area of the doped titanium dioxide is positively large, and the catalytic activity is high.
According to the invention, copper, manganese and cerium of the non-noble metal nano-particles are respectively carried out isolation and load, so that the agglomeration growth of the non-noble metal nano-particles is effectively inhibited, and the particle size of the nano-particles is effectively reduced; and the applicant found that: copper nitrate is doped in a shell structure doped with titanium dioxide, and manganese nitrate and cerium nitrate are loaded outside the shell structure, so that the ignition temperature can be greatly reduced on the basis of greatly improving the catalytic oxidation performance of the catalyst on carbon monoxide, and the catalytic effect is excellent.
The invention adopts the doped titanium dioxide as the carbon monoxide oxidation catalyst carrier, has high structural stability, positive specific surface, high pore volume, high mesoporous order degree, high catalytic activity and excellent sulfur resistance, and has good catalytic performance for the catalytic oxidation removal of carbon monoxide from the flue gas containing sulfur dioxide.
The invention takes the doped titanium dioxide as a carrier, loads copper, manganese and cerium metal components, is used for realizing the high-efficiency catalytic oxidation removal of carbon monoxide in waste gas, has low ignition temperature and low complete conversion temperature, and has the airspeed of not more than 4000h -1 Under the condition of the ignition temperature of the catalyst is lower than 112 ℃ and 145 ℃, the complete conversion of carbon monoxide can be realized, and the catalyst is suitable for purifying fixed source flue gas such as steel, coking, cement and the like and has wide industrial application range.
Drawings
FIG. 1 is N of the catalysts obtained in example 5 and comparative examples 1-2 2 Adsorption-desorption isotherms.
FIG. 2 is a graph showing pore size distribution of the catalysts obtained in example 5 and comparative examples 1 to 2.
FIG. 3 is a graph comparing light-off temperature, full conversion temperature and carbon monoxide conversion for the catalysts obtained in example 5 and comparative examples 1-2.
FIG. 4 is a graph comparing carbon monoxide conversion and sulfur dioxide conversion for the catalyst obtained in example 5.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
A preparation method of a catalyst for removing carbon monoxide by low-temperature oxidation comprises the following steps:
s1, dispersing 1g of gas-phase titanium dioxide P25 powder into 40g of absolute ethyl alcohol, sequentially adding 2g of glacial acetic acid and 5g of tetrabutyl titanate in a stirring state, and stirring at a speed of 500r/min for 1h to obtain pretreated titanium dioxide;
s2, adding 1g of graphene oxide and 0.1g of copper nitrate into 20g of ethanol aqueous solution with the mass fraction of 40%, uniformly stirring, dropwise adding into 50g of pretreated titanium dioxide in a stirring state, stirring at the stirring speed of 50r/min, stirring at the temperature of 60 ℃ for 10min, regulating the pH value of a system to 11-12 by adopting sodium hydroxide solution with the concentration of 0.5mol/L, stirring at the speed of 100r/min for 5min, centrifuging, filtering, and washing by adopting absolute ethanol for 1 time to obtain core-shell titanium dioxide;
s3, adding 9g of core-shell titanium dioxide into 20g of sodium hydroxide solution with the concentration of 9mol/L, uniformly mixing, sending into a hydrothermal reaction kettle lined with polytetrafluoroethylene, standing at the temperature of 150 ℃ for 48 hours, carrying out solid-liquid separation, washing the solid with deionized water until the pH value is 10.5-11.2, and adding into 20g of water to prepare a doped titanium dioxide suspension;
s4, adding 1g of manganese nitrate and 0.1g of cerium nitrate into 40g of water, uniformly stirring, dropwise adding 30g of doped titanium dioxide suspension under the stirring condition, stirring until precipitation is complete, standing for 1h, performing solid-liquid separation, washing solid matters to be neutral by adopting deionized water, drying at 100 ℃, roasting at 500 ℃ for 5h in a muffle furnace, granulating, and sieving with a 40-mesh sieve to obtain the carbon monoxide low-temperature oxidation removal catalyst.
Example 2
A preparation method of a catalyst for removing carbon monoxide by low-temperature oxidation comprises the following steps:
s1, dispersing 5g of gas-phase titanium dioxide P25 powder into 100g of absolute ethyl alcohol, sequentially adding 3g of glacial acetic acid and 10g of tetrabutyl titanate in a stirring state, and stirring at a speed of 1500r/min for 2 hours to obtain pretreated titanium dioxide;
s2, adding 3g of graphene oxide and 1g of copper nitrate into 50g of 60% ethanol water solution with mass fraction, uniformly stirring, dropwise adding into 110g of pretreated titanium dioxide in a stirring state, stirring at the stirring speed of 100r/min for 30min at the temperature of 80 ℃, regulating the pH value of a system to 11-12 by adopting 1.2mol/L sodium hydroxide solution, stirring at the speed of 500r/min for 20min, centrifuging, filtering, and washing for 3 times by adopting absolute ethanol to obtain core-shell titanium dioxide;
s3, adding 22g of core-shell titanium dioxide into 30g of 12mol/L sodium hydroxide solution, uniformly mixing, sending into a hydrothermal reaction kettle lined with polytetrafluoroethylene, standing at 160 ℃ for 56 hours, carrying out solid-liquid separation, washing the solid with deionized water until the pH value is 10.5-11.2, and adding into 30g of water to prepare a doped titanium dioxide suspension;
s4, adding 2g of manganese nitrate and 1g of cerium nitrate into 100g of water, uniformly stirring, dropwise adding 50g of doped titanium dioxide suspension under the stirring condition, stirring until precipitation is complete, standing for 5h, performing solid-liquid separation, washing solid matters to be neutral by adopting deionized water, drying at 120 ℃, roasting at 600 ℃ for 10h in a muffle furnace, granulating, and sieving with a 60-mesh sieve to obtain the carbon monoxide low-temperature oxidation removal catalyst.
Example 3
A preparation method of a catalyst for removing carbon monoxide by low-temperature oxidation comprises the following steps:
s1, dispersing 2g of gas-phase titanium dioxide P25 powder into 80g of absolute ethyl alcohol, sequentially adding 2.2g of glacial acetic acid and 9g of tetrabutyl titanate in a stirring state, and stirring at a speed of 800r/min for 100min to obtain pretreated titanium dioxide;
s2, adding 1.5g of graphene oxide and 0.7g of copper nitrate into 30g of ethanol water solution with the mass fraction of 55%, uniformly stirring, dropwise adding into 70g of pretreated titanium dioxide in a stirring state, stirring at the stirring speed of 90r/min, stirring at the temperature of 65 ℃ for 25min, regulating the pH value of a system to 11-12 by adopting sodium hydroxide solution with the concentration of 0.8mol/L, stirring at the speed of 400r/min for 10min, centrifuging, filtering, and washing by adopting absolute ethanol for 2 times to obtain core-shell titanium dioxide;
s3, adding 18g of core-shell titanium dioxide into 22g of 11mol/L sodium hydroxide solution, uniformly mixing, sending into a hydrothermal reaction kettle lined with polytetrafluoroethylene, standing at the temperature of 152 ℃ for 54h, carrying out solid-liquid separation, washing the solid with deionized water until the pH value is 10.5-11.2, and adding into 22g of water to prepare a doped titanium dioxide suspension;
s4, adding 1.7g of manganese nitrate and 0.3g of cerium nitrate into 80g of water, uniformly stirring, dropwise adding 35g of doped titanium dioxide suspension under the stirring condition, stirring until precipitation is complete, standing for 4 hours, performing solid-liquid separation, washing a solid with deionized water to be neutral, drying at 105 ℃, roasting at 580 ℃ for 7 hours in a muffle furnace, granulating, and sieving with a 55-mesh sieve to obtain the carbon monoxide low-temperature oxidation removal catalyst.
Example 4
A preparation method of a catalyst for removing carbon monoxide by low-temperature oxidation comprises the following steps:
s1, dispersing 4g of gas-phase titanium dioxide P25 powder into 60g of absolute ethyl alcohol, sequentially adding 2.8g of glacial acetic acid and 7g of tetrabutyl titanate in a stirring state, and stirring at a speed of 1200r/min for 80min to obtain pretreated titanium dioxide;
s2, adding 2.5g of graphene oxide and 0.3g of copper nitrate into 40g of 45% ethanol water solution with mass fraction, uniformly stirring, dropwise adding into 90g of pretreated titanium dioxide in a stirring state, stirring at 70r/min for 15min at the temperature of 75 ℃, regulating the pH value of a system to 11-12 by adopting 1mol/L sodium hydroxide solution, stirring at 200r/min for 16min, centrifuging, filtering, and washing for 2 times by adopting absolute ethanol to obtain core-shell titanium dioxide;
s3, adding 14g of core-shell titanium dioxide into 28g of 10mol/L sodium hydroxide solution, uniformly mixing, sending into a hydrothermal reaction kettle lined with polytetrafluoroethylene, standing at 158 ℃ for 50 hours, carrying out solid-liquid separation, washing the solid with deionized water until the pH value is 10.5-11.2, and adding into 28g of water to prepare a doped titanium dioxide suspension;
s4, adding 1.3g of manganese nitrate and 0.7g of cerium nitrate into 60g of water, uniformly stirring, dropwise adding 45g of doped titanium dioxide suspension under the stirring condition, stirring until precipitation is complete, standing for 2h, performing solid-liquid separation, washing solid matters to be neutral by adopting deionized water, drying at 115 ℃, roasting at 520 ℃ for 9h in a muffle furnace, granulating, and sieving with a 45-mesh sieve to obtain the carbon monoxide low-temperature oxidation removal catalyst.
Example 5
A preparation method of a catalyst for removing carbon monoxide by low-temperature oxidation comprises the following steps:
s1, dispersing 3g of gas-phase titanium dioxide P25 powder into 70g of absolute ethyl alcohol, sequentially adding 2.5g of glacial acetic acid and 8g of tetrabutyl titanate in a stirring state, and stirring at a speed of 1000r/min for 90min to obtain pretreated titanium dioxide;
s2, adding 2g of graphene oxide and 0.5g of copper nitrate into 35g of ethanol aqueous solution with the mass fraction of 50%, uniformly stirring, dropwise adding into 80g of pretreated titanium dioxide in a stirring state, stirring at the stirring speed of 80r/min for 20min at the temperature of 70 ℃, regulating the pH value of a system to 11-12 by adopting sodium hydroxide solution with the concentration of 0.9mol/L, stirring at the speed of 300r/min for 13min, centrifuging, filtering, and washing for 2 times by adopting absolute ethanol to obtain core-shell titanium dioxide;
s3, adding 16g of core-shell titanium dioxide into 25g of 10.5mol/L sodium hydroxide solution, uniformly mixing, sending into a hydrothermal reaction kettle lined with polytetrafluoroethylene, standing at 155 ℃ for 52 hours, carrying out solid-liquid separation, washing the solid with deionized water until the pH value is 10.5-11.2, and adding into 25g of water to prepare a doped titanium dioxide suspension;
s4, adding 1.5g of manganese nitrate and 0.5g of cerium nitrate into 70g of water, uniformly stirring, dropwise adding 40g of doped titanium dioxide suspension under the stirring condition, stirring until precipitation is complete, standing for 3h, performing solid-liquid separation, washing solid matters to be neutral by adopting deionized water, drying at 110 ℃, roasting at 550 ℃ for 8h in a muffle furnace, granulating, and sieving with a 50-mesh sieve to obtain the carbon monoxide low-temperature oxidation removal catalyst.
Comparative example 1
A preparation method of a catalyst for removing carbon monoxide by low-temperature oxidation comprises the following steps:
s1, dispersing 3g of gas-phase titanium dioxide P25 powder into 70g of absolute ethyl alcohol, sequentially adding 2.5g of glacial acetic acid and 8g of tetrabutyl titanate in a stirring state, and stirring at a speed of 1000r/min for 90min to obtain pretreated titanium dioxide;
s2, adding 0.5g of copper nitrate into 35g of ethanol aqueous solution with the mass fraction of 50%, uniformly stirring, dropwise adding into 80g of pretreated titanium dioxide in a stirring state, stirring at the stirring speed of 80r/min, stirring at the temperature of 70 ℃ for 20min, regulating the pH value of a system to 11-12 by adopting sodium hydroxide solution with the concentration of 0.9mol/L, stirring at the speed of 300r/min for 13min, centrifuging, filtering, washing by adopting absolute ethanol for 2 times, and obtaining core-shell titanium dioxide;
s3, adding 16g of core-shell titanium dioxide into 25g of 10.5mol/L sodium hydroxide solution, uniformly mixing, sending into a hydrothermal reaction kettle lined with polytetrafluoroethylene, standing at 155 ℃ for 52 hours, carrying out solid-liquid separation, washing the solid with deionized water until the pH value is 10.5-11.2, and adding into 25g of water to prepare a doped titanium dioxide suspension;
s4, adding 1.5g of manganese nitrate and 0.5g of cerium nitrate into 70g of water, uniformly stirring, dropwise adding 40g of doped titanium dioxide suspension under the stirring condition, stirring until precipitation is complete, standing for 3h, performing solid-liquid separation, washing solid matters to be neutral by adopting deionized water, drying at 110 ℃, roasting at 550 ℃ for 8h in a muffle furnace, granulating, and sieving with a 50-mesh sieve to obtain the carbon monoxide low-temperature oxidation removal catalyst.
Comparative example 2
A preparation method of a catalyst for removing carbon monoxide by low-temperature oxidation comprises the following steps:
s1, dispersing 3g of gas-phase titanium dioxide P25 powder into 70g of absolute ethyl alcohol, sequentially adding 2.5g of glacial acetic acid and 8g of tetrabutyl titanate in a stirring state, and stirring at a speed of 1000r/min for 90min to obtain pretreated titanium dioxide;
s2, adding 2g of graphene oxide into 35g of ethanol aqueous solution with the mass fraction of 50%, uniformly stirring, dropwise adding into 80g of pretreated titanium dioxide in a stirring state, stirring at the stirring speed of 80r/min, stirring at the temperature of 70 ℃ for 20min, regulating the pH value of a system to 11-12 by adopting sodium hydroxide solution with the concentration of 0.9mol/L, stirring at the speed of 300r/min for 13min, centrifuging, filtering, washing by adopting absolute ethyl alcohol for 2 times, and obtaining core-shell titanium dioxide;
s3, adding 16g of core-shell titanium dioxide into 25g of 10.5mol/L sodium hydroxide solution, uniformly mixing, sending into a hydrothermal reaction kettle lined with polytetrafluoroethylene, standing at 155 ℃ for 52 hours, carrying out solid-liquid separation, washing the solid with deionized water until the pH value is 10.5-11.2, and adding into 25g of water to prepare a doped titanium dioxide suspension;
s4, adding 1.5g of manganese nitrate, 0.5g of cerium nitrate and 0.5g of copper nitrate into 70g of water, uniformly stirring, dropwise adding 40g of doped titanium dioxide suspension under the stirring condition, stirring until precipitation is complete, standing for 3 hours, carrying out solid-liquid separation, washing the solid with deionized water to be neutral, drying at 110 ℃, roasting at 550 ℃ for 8 hours in a muffle furnace, granulating, and sieving with a 50-mesh sieve to obtain the carbon monoxide low-temperature oxidation removal catalyst.
N was conducted on the catalysts obtained in example 5 and comparative examples 1 to 2 2 Adsorption desorption isotherm analysis (BET): the sample was degassed at 200 ℃ for 4 hours before testing, the specific surface area was calculated using the BET method, and the pore size and pore volume were calculated using the BJH method.
As shown in fig. 1 and 2, the catalysts obtained in example 5 and comparative examples 1-2 all show IV adsorption isothermal curves, which indicate that the three catalysts are mesoporous structures, but the catalyst obtained in example 5 has larger specific surface area and pore diameter and is easier to absorb carbon monoxide for oxidation treatment.
The applicant believes that: the invention adopts gas-phase titanium dioxide P25 as a core, nano titanium dioxide is deposited and combined on the surface of the gas-phase titanium dioxide P25, and graphene oxide and copper nitrate are doped in a deposition layer to form a spherical structure body taking the gas-phase titanium dioxide P25 as a core and the nano titanium dioxide doped with the graphene oxide and the copper nitrate as a shell; through solvothermal reaction, the bonding strength is high, the structural stability is high, graphene oxide on the shell structure can be effectively removed through roasting, a large number of active void structures are formed, the specific surface area of the doped titanium dioxide is positively large, and the catalytic activity is high.
The catalysts obtained in example 5 and comparative examples 1 to 2 were subjected to activity test of the catalyst: taking 0.1g of each group of samples, respectively placing the samples into a fixed bed quartz tube reactor (quartz tube inner diameter=6mm), and simulating flue gas to be formed by CO and O 2 And N 2 Composition, wherein the carbon monoxide concentration is 10000ppm, O 2 Volume fraction of 10%, N 2 Volume fraction of 89%, airspeed 30000h -1 The reaction temperature is 100-200 ℃.
As a result, as shown in FIG. 3, the catalyst obtained in example 5 had the lowest light-off temperature and the highest conversion of carbon monoxide. The applicant believes that: the invention is characterized in that the copper, manganese and cerium of the non-noble metal nano particles are respectively carried out isolation, thus not only effectively inhibiting the agglomeration growth of the non-noble metal nano particles and effectively reducing the particle diameter of the nano particles, but also firstly doping copper nitrate into the shell structure doped with titanium dioxide, then loading manganese nitrate and cerium nitrate outside the shell structure, and greatly reducing the ignition temperature and having excellent catalytic effect on the basis of greatly improving the catalytic oxidation performance of the catalyst on carbon monoxide.
The catalyst obtained in example 5 was tested for its water and sulfur resistance: taking 0.1g of each group of samples, respectively placing the samples into a fixed bed quartz tube reactor (quartz tube inner diameter=6mm), and simulating flue gas from CO and SO 2 Steam, O 2 And N 2 Composition, wherein the carbon monoxide concentration is 10000ppm, SO 2 Concentration of 300ppm, water vapor volume fraction of 10%, O 2 Volume fraction 10%, the remainder N 2 Space velocity 30000h -1 The temperature was maintained at 150℃and the other test conditions were unchanged.
As shown in FIG. 4, the catalyst obtained in example 5 was proved to have a strong water-and sulfur-resistance.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The preparation method of the catalyst for removing carbon monoxide by low-temperature oxidation is characterized by comprising the following steps:
s1, dispersing gas-phase titanium dioxide P25 powder into absolute ethyl alcohol, and sequentially adding glacial acetic acid and tetrabutyl titanate in a stirring state to obtain pretreated titanium dioxide;
s2, adding graphene oxide and copper nitrate into an ethanol water solution, uniformly stirring, dropwise adding the mixture into pretreated titanium dioxide in a stirring state, stirring for 10-30min at 60-80 ℃, regulating the pH value of the system to 11-12, continuously stirring, centrifuging, filtering, and washing to obtain core-shell titanium dioxide;
s3, adding the core-shell titanium dioxide into a sodium hydroxide solution, uniformly mixing, performing solvothermal reaction for 48-56 hours at 150-160 ℃, performing solid-liquid separation, washing solids, and adding the solids into water to obtain a doped titanium dioxide suspension;
s4, adding manganese nitrate and cerium nitrate into water, uniformly stirring, dropwise adding the doped titanium dioxide suspension under the stirring condition, stirring until precipitation is complete, standing for 1-5h, carrying out solid-liquid separation, washing the solid to be neutral, drying, roasting at 500-600 ℃ for 5-10h, granulating, and sieving to obtain the carbon monoxide low-temperature oxidation removal catalyst.
2. The method for preparing the catalyst for low-temperature oxidation removal of carbon monoxide according to claim 1, wherein in S1, the mass ratio of the gas-phase titanium dioxide P25 to the absolute ethyl alcohol to the glacial acetic acid to the tetrabutyl titanate is 1-5:40-100:2-3:5-10.
3. The method for preparing the catalyst for low-temperature oxidation removal of carbon monoxide according to claim 1, wherein in S2, the mass fraction of the ethanol aqueous solution is 40-60%, and the mass ratio of graphene oxide, copper nitrate, the ethanol aqueous solution and pretreated titanium dioxide is 1-3:0.1-1:20-50:50-110.
4. The method for preparing the catalyst for low-temperature oxidation removal of carbon monoxide according to claim 1, wherein in S2, a sodium hydroxide solution with the concentration of 0.5-1.2mol/L is adopted to adjust the pH value of the system to 11-12.
5. The method for preparing a catalyst for low-temperature oxidation removal of carbon monoxide according to claim 1, wherein in S2, the catalyst is washed 1-3 times with absolute ethanol after filtration.
6. The method for preparing the catalyst for low-temperature oxidation removal of carbon monoxide according to claim 1, wherein in S3, the concentration of sodium hydroxide solution is 9-12mol/L, and the mass ratio of core-shell titanium dioxide, sodium hydroxide solution and water is 9-22:20-30:20-30.
7. The method for preparing a catalyst for low-temperature oxidation removal of carbon monoxide according to claim 1, wherein in S3, the solid is washed with deionized water to a pH of 10.5 to 11.2.
8. The method for preparing the catalyst for low-temperature oxidation removal of carbon monoxide according to claim 1, wherein in the S4, the mass ratio of manganese nitrate, cerium nitrate, water and doped titanium dioxide suspension is 1-2:0.1-1:40-100:30-50.
9. The method for preparing a catalyst for low-temperature oxidation removal of carbon monoxide according to claim 1, wherein the drying temperature in S4 is 100-120 ℃.
10. A catalyst for the low-temperature oxidation removal of carbon monoxide, which is prepared by the method for preparing the catalyst for the low-temperature oxidation removal of carbon monoxide according to any one of claims 1 to 9.
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