CN117085696A - Catalytic combustion catalyst and preparation method and application thereof - Google Patents
Catalytic combustion catalyst and preparation method and application thereof Download PDFInfo
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- CN117085696A CN117085696A CN202311211075.XA CN202311211075A CN117085696A CN 117085696 A CN117085696 A CN 117085696A CN 202311211075 A CN202311211075 A CN 202311211075A CN 117085696 A CN117085696 A CN 117085696A
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- catalyst
- supported catalyst
- coating agent
- catalytic combustion
- roasting
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- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 62
- 239000002243 precursor Substances 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000003546 flue gas Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 19
- 239000012752 auxiliary agent Substances 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000011068 loading method Methods 0.000 claims description 15
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 14
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 230000002209 hydrophobic effect Effects 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000012051 hydrophobic carrier Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- 150000003754 zirconium Chemical class 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052717 sulfur Inorganic materials 0.000 abstract description 30
- 239000011593 sulfur Substances 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 13
- 239000010410 layer Substances 0.000 abstract description 3
- 239000002103 nanocoating Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000576 coating method Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical group [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- -1 starting from 50 °C Chemical compound 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalytic combustion catalyst, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing a carrier, an active metal precursor and a solvent, performing solid-liquid separation, drying and roasting to obtain a supported catalyst; mixing a carbon source, a coating agent precursor and the supported catalyst, performing solid-liquid separation, drying and roasting to obtain the catalytic combustion catalyst. According to the preparation method, the carbon source is introduced, and the nano coating layer is introduced on the surface of the catalyst, so that the catalyst not only has strong activity on CO, but also improves the water-resistant and sulfur-resistant stability of the catalyst, and the catalytic combustion catalyst has strong CO catalytic combustion stability under the condition of industrial flue gas containing water and sulfur.
Description
Technical Field
The invention belongs to the technical field of polluted gas treatment, and relates to a catalytic combustion catalyst, a preparation method and application thereof.
Background
Carbon monoxide, a common pollutant in the atmosphere, is mainly derived from fossil combustionDischarge after incomplete combustion of the material and some chemical production processes. Since CO is a toxic and harmful gas, the emission into the atmosphere not only causes environmental pollution, but also brings harm to human health. Therefore, a technology capable of greatly reducing CO emission is developed, and the technology has important significance for protecting the environment and human health. The toxic and harmful CO in the tail gas is converted into non-toxic and harmless CO by a catalytic combustion method 2 Is a viable method.
The technology for converting carbon monoxide into carbon dioxide has the advantages of high CO elimination efficiency, low energy consumption, no secondary pollution, wide applicable concentration and the like. However, in some special fumes discharged from industries such as steel, coal chemical industry, pharmacy and metallurgy, even if meeting ultra-low emission standards, the fumes may still contain up to 35mg/m 3 SO of (2) 2 A certain amount of H 2 O and dust, etc. Noble metal catalysts and metal oxide catalysts are conventional CO removal catalysts. These catalysts, although exhibiting extremely high activity for CO catalytic combustion, are susceptible to rapid decrease in catalyst activity and inability to regenerate due to binding of sulfides and active components or formation of sulfates on the support surface in the presence of sulfides. Therefore, the development of efficient, water-tolerant and sulfur poisoning-resistant CO catalytic combustion catalysts is a key to solving the above-mentioned emissions sources.
As CN 116251586a discloses a sulfur-resistant CO oxidation catalyst, a preparation method and an application thereof, in the preparation method of the sulfur-resistant CO oxidation catalyst, the area of honeycomb ceramic coated with a firm composite oxide coating is obtained through preparation of coating slurry, coating of the coating on a honeycomb ceramic carrier, and drying and calcining; that is, it adds TiO mainly by wave-assisted method 2 -SiO 2 The specific surface area and pore volume of the coating optimize the pore canal structure of the catalyst and improve impurity SO 2 The sulfate generated by the side reaction blocks the micropore channel of the catalyst to cause the deactivation of the catalyst.
As CN 114210335a discloses a low-temperature water-resistant sulfur-resistant non-noble metal catalyst for removing carbon monoxide, which is a perovskite-type transition metal oxide, takes cobalt as a main active ingredient, is doped with a certain amount of perovskite-type transition metal oxide of lanthanum and strontium, can overcome the problems of high cost and poor stability of the traditional noble metal catalyst, and has strong water-resistant sulfur-resistant stability; however, the catalysts disclosed in the above prior art have a certain sulfur resistance, but the water resistance and sulfur resistance are still further improved.
Based on the above studies, it is required to provide a method for producing a catalytic combustion catalyst, which can give a catalyst exhibiting a strong activity against CO and having excellent water-and sulfur-resistant properties.
Disclosure of Invention
The invention aims to provide a catalytic combustion catalyst and a preparation method and application thereof, and particularly relates to a water-resistant and sulfur-resistant CO catalytic combustion catalyst and a preparation method and application thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method of preparing a catalytic combustion catalyst, the method comprising the steps of:
(1) Mixing a carrier, an active metal precursor and a solvent, performing solid-liquid separation, drying and roasting to obtain a supported catalyst;
(2) Mixing a carbon source, a coating agent precursor and the supported catalyst in the step (1), performing solid-liquid separation, drying and roasting to obtain the catalytic combustion catalyst.
According to the invention, the carrier, the catalytic active metal precursor and the solvent are mixed, subjected to solid-liquid separation, drying, roasting and the like to prepare the supported catalyst, and then the coating step of the step (2) is carried out, wherein the carbon source is easily supported on the surface of the carrier in the step (1), and the carbon source in the step (2) is taken as an auxiliary coating agent and is combined with the coating agent precursor, so that the carbon source can bring the coating agent precursor to the surface of the carrier, and finally, after the carbon source is removed by roasting, the coating of the coating agent is realized, and the catalytic activity and the water-resistant sulfur-resistant stability of the catalyst are greatly improved due to the existence of the coating layer.
Preferably, the coating agent precursor of step (2) comprises a metal salt and/or a silicon source, preferably a metal salt.
The coating agent of the present invention is preferably a metal salt, and since the metal salt can react with an active center such as Pt to form a Pt-O-M metal bond such as Pt-O-Ti, wherein-O-has a strong oxidizing property, carbon monoxide can be oxidized to carbon dioxide, and SO 2 Will not adsorb at-O-, SO that SO 2 Pt poisoning is not caused, so that the sulfur resistance stability of the catalyst is improved.
Preferably, the metal salt comprises a titanium salt and/or a zirconium salt, illustratively comprising zirconium nitrate and/or titanium nitrate.
Preferably, the silicon source comprises ethyl orthosilicate.
Preferably, the mass ratio of the coating agent precursor in step (2) to the supported catalyst in step (1) is (0.05-0.3): 1, which may be, for example, 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1 or 0.3:1, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The use amount of the coating agent precursor can influence the thickness of a coating layer, if the use amount of the coating agent precursor is too large, a thicker coating layer is formed, a reactant (CO) cannot contact with an active center, the activity of a catalyst can be reduced, and if the use amount of the coating agent precursor is too small, the coating agent precursor cannot completely form a coating active center (such as Pt), so that the effect of protecting the active center cannot be achieved.
Preferably, the mass ratio of the carbon source to the coating agent precursor in the step (2) is (8-50): 1, for example, 10:1, 20:1, 30:1, 40:1 or 50:1, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the carbon source of step (2) comprises dopamine hydrochloride.
The carbon source is preferably dopamine hydrochloride, and the dopamine hydrochloride can be complexed with the coating agent precursor, and meanwhile, the dopamine hydrochloride can be firmly attached to the surface of the catalyst after polymerization, so that the coating agent precursor can be brought to the surface of the catalyst to form a coating form.
Preferably, the mixing in step (2) comprises dispersing the carbon source in water having a pH of 7.5 to 10.5, for example 7.5, 8.5 or 10.5, then adding the coating agent precursor, stirring, adding the supported catalyst, and continuing stirring.
Preferably, the stirring time is 1-4 hours, for example, 1 hour, 2 hours, 3 hours or 4 hours, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, after the mixing in the step (2), solid-liquid separation, washing and drying are performed first, and then roasting is performed.
Preferably, the roasting atmosphere in the step (2) comprises a nitrogen atmosphere and an air atmosphere.
Preferably, the firing in step (2) comprises first firing at 700-900 ℃, such as 700 ℃, 800 ℃ or 900 ℃, for 3-5 hours, such as 3 hours, 4 hours or 5 hours, in a nitrogen atmosphere, and then firing at 400-600 ℃, such as 400 ℃, 500 ℃ or 600 ℃, for 3-5 hours, such as 3 hours, 4 hours or 5 hours, in an air atmosphere, such as 400 ℃, 500 ℃ or 600 ℃, but not limited to the recited values, other non-recited values in the range of values being equally applicable.
Preferably, the support of step (1) comprises a hydrophobic support.
Preferably, the hydrophobic support comprises hydrophobic alumina and/or hydrophobic silica.
Preferably, the solvent used in step (1) comprises an organic solvent.
In order to match the hydrophobic carrier, the invention preferably adopts an organic solvent for dispersion, thereby improving the dispersity of the active metal.
Preferably, the organic solvent includes any one or a combination of at least two of methanol, ethanol, acetic acid, ethyl acetate, and methyl ethyl ketone.
Preferably, the metal element in the active metal precursor in step (1) includes any one or a combination of at least two of Pd, pt, cu, mn or Co.
Preferably, in the supported catalyst in step (1), the loading of Pd and/or Pt is 0-1wt%, and may be, for example, 0wt%, 0.2wt%, 0.4wt%, 0.6wt%, 0.8wt%, or 1wt%, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, in the supported catalyst in step (1), the loading of any one or at least two of Cu, mn or Co is 5-10wt%, for example, 5wt%, 7wt%, 9wt% or 10wt%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, an auxiliary agent is further added during the mixing in the step (1), and the metal element in the auxiliary agent comprises any one or a combination of at least two of Co, ce, la, zr, cu or Mn.
Preferably, in the supported catalyst in step (1), the loading of the metal element in the auxiliary agent is 0-10wt%, but not 0wt%, for example, may be 1wt%, 3wt%, 5wt%, 7wt%, 9wt% or 10wt%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the mixing of step (1) comprises mixing the support with the solvent, and then adding the reactive metal precursor and the promoter and continuing to stir.
Preferably, the temperature of the calcination in step (1) is 450-550 ℃, for example, 450 ℃, 500 ℃ or 550 ℃, and the time is 3-5 hours, for example, 3 hours, 4 hours or 5 hours, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the temperature of the drying in step (1) is 80-100deg.C, such as 80 ℃, 90 ℃ or 100deg.C, and the time is 4-8 hours, such as 4 hours, 5 hours, 6 hours, 7 hours or 8 hours, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferable technical scheme of the preparation method, the preparation method comprises the following steps:
(1) Mixing a hydrophobic carrier, an active metal precursor, an auxiliary agent and an organic solvent, performing solid-liquid separation, drying at 80-100 ℃ for 4-8 hours and roasting at 450-550 ℃ for 3-5 hours to obtain a supported catalyst;
the metal element in the active metal precursor comprises any one or a combination of at least two of Pd, pt, cu, mn and Co; in the supported catalyst in the step (1), the loading amount of Pd and/or Pt is 0-1wt%, and the loading amount of any one or a combination of at least two of Cu, mn and Co is 5-10wt%;
the metal element in the auxiliary agent comprises any one or a combination of at least two of Co, ce, la, zr, cu and Mn, and in the supported catalyst in the step (1), the load of the metal element in the auxiliary agent is 0-10wt% but not 0wt%;
(2) Dispersing dopamine hydrochloride in water with the pH value of 7.5-10.5, adding a coating agent precursor, stirring, adding a supported catalyst, continuously stirring, performing solid-liquid separation, washing and drying, roasting at the temperature of 700-900 ℃ for 3-5h in an air-nitrogen atmosphere, and roasting at the temperature of 400-600 ℃ for 3-5h in an air atmosphere to obtain the catalytic combustion catalyst;
the mass ratio of the coating agent precursor to the supported catalyst in the step (1) is (0.05-0.3): 1, and the mass ratio of the carbon source to the coating agent precursor is (8-50): 1; the coating agent precursor comprises any one or a combination of at least two of titanium salt, zirconium salt or silicon source.
In a second aspect, the present invention provides a catalytic combustion catalyst prepared by the method of preparation according to the first aspect.
In a third aspect, the present invention provides the use of a catalytic combustion catalyst as described in the second aspect, said use comprising the conversion of carbon monoxide for use in industrial flue gas conditions.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a carbon source is introduced in the calcination process, and the nano coating layer is introduced on the surface of the catalyst, so that the catalyst not only has stronger activity on CO, but also improves the water-resistant and sulfur-resistant stability of the catalyst, and the catalytic combustion catalyst has stronger CO catalytic combustion performance and stability under the condition of industrial flue gas containing water and sulfur.
Drawings
FIG. 1 is a graph showing the reactivity of the catalytic combustion catalyst of example 1 according to the present invention under aqueous sulfur-containing conditions over the reaction time.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of a catalytic combustion catalyst, which comprises the following steps:
(1) 5g of hydrophobic alumina (purity: 99.5%, specific surface area BET:280 m) 2 Per g, particle size 15-30 nm) is put into a mixed solution of 300mL of ethyl acetate and 100mL of ethanol, stirred for 1h, then 0.15g of active metal precursor and 0.079g of auxiliary agent are added, stirring is continued for 4h, filtering, washing with deionized water, drying at 80 ℃ for 4h and roasting at 500 ℃ for 4h, thus obtaining the supported catalyst;
the active metal precursor is a platinum nitrate solution with the concentration of 10%, and in the supported catalyst in the step (1), the load of Pt is 0.3wt%; the auxiliary agent is cerous nitrate hexahydrate, and in the supported catalyst in the step (1), the loading amount of metal elements in the auxiliary agent is 0.5wt%;
(2) Dispersing 2.5g of dopamine hydrochloride in 500mL of water with the pH of 8.5, then adding 0.09g of coating agent precursor, stirring for 1h, adding 1g of the supported catalyst in the step (1), continuously stirring for 4h, filtering, washing with deionized water, drying at 80 ℃ for 8h, roasting at 800 ℃ for 4h in nitrogen atmosphere, and roasting at 500 ℃ for 4h in air atmosphere to obtain the catalytic combustion catalyst;
the coating agent precursor is titanium nitrate, the mass ratio of the coating agent precursor to the supported catalyst in the step (1) is 0.09:1, and the mass ratio of the dopamine hydrochloride to the coating agent precursor is 28:1;
the catalytic combustion catalyst obtained in this example weighed 0.5g, and in a fixed bed reactor, 250ml/min of a mixed gas was introduced into the reactor, and the composition of the mixed gas was: 8000ppm CO, 50ppm SO 2 10% of water vapor, 10% of O 2 And nitrogen, continuously reacting for 200h at 200 ℃, recording the change of the activity of the catalyst along with the change of time, and obtaining a graph of the change of the reactivity along with the change of the reaction time, wherein the graph is shown in figure 1.
Example 2
The embodiment provides a preparation method of a catalytic combustion catalyst, which comprises the following steps:
(1) 5g of hydrophobic silica (CAS number: 60676-86-0, macklin, purity: 99.8%, specific surface area BET:230 m) 2 Per g, particle size 7-40 nm) is put into 400mL of ethyl acetate, stirred for 1h, then 0.95g of copper nitrate trihydrate and 1.61g of manganese nitrate hexahydrate are added for continuous stirring for 4h, filtration and deionized water washing, and after drying at 100 ℃ for 4h and roasting at 550 ℃ for 3h, the supported catalyst is obtained;
in the supported catalyst in the step (1), the loading of Cu is 5wt% and the loading of Mn is 6wt%;
(2) Dispersing 2.5g of dopamine hydrochloride in 500mL of water with the pH of 8.5, then adding 0.05g of coating agent precursor, stirring for 1h, adding 1g of the supported catalyst in the step (1), continuously stirring for 4h, filtering, washing with deionized water, drying at 100 ℃ for 4h, roasting at 700 ℃ for 5h in nitrogen atmosphere, and roasting at 600 ℃ for 5h in air atmosphere to obtain the catalytic combustion catalyst;
the coating agent precursor is titanium nitrate, the mass ratio of the coating agent precursor to the supported catalyst in the step (1) is 0.05:1, and the mass ratio of the dopamine hydrochloride to the coating agent precursor is 50:1.
Example 3
The embodiment provides a preparation method of a catalytic combustion catalyst, which comprises the following steps:
(1) 5g of hydrophobic silica (CAS number: 60676-86-0, macklin, purity: 99.8%, specific surface area BET:230 m) 2 Per g, particle size 7-40 nm) is put into 400mL of ethyl acetate, stirred for 1h, then copper nitrate trihydrate and manganese nitrate hexahydrate are continuously stirred for 4h, filtered, washed by deionized water, dried for 4h at 80 ℃ and baked for 5h at 450 ℃ to obtain a supported catalyst;
in the supported catalyst in the step (1), the Cu loading is 7wt% and the Mn loading is 10wt%;
(2) Dispersing 2.5g of dopamine hydrochloride in 500mL of water with pH of 8, adding 0.3g of coating agent precursor, stirring for 1h, adding 1g of the supported catalyst in the step (1), continuously stirring for 4h, filtering, washing with deionized water, drying at 80 ℃ for 4h, roasting at 900 ℃ for 3h in nitrogen atmosphere, and roasting at 400 ℃ for 3h in air atmosphere to obtain the catalytic combustion catalyst;
the coating agent precursor is zirconium nitrate, the mass ratio of the coating agent precursor to the supported catalyst in the step (1) is 0.3:1, and the mass ratio of the dopamine hydrochloride to the coating agent precursor is 8.3:1.
Example 4
This example provides a method for preparing a catalytic combustion catalyst except that the hydrophobic alumina of step (1) is replaced by gamma-Al 2 O 3 The procedure was the same as in example 1 except that the other components were the same.
Example 5
This example provides a method for preparing a catalytic combustion catalyst, which is the same as example 1 except that no auxiliary agent is added in step (1).
Example 6
This example provides a method of preparing a catalytic combustion catalyst, which is the same as example 1, except that the coating agent precursor in step (2) is ethyl orthosilicate.
Example 7
The present example provides a method for preparing a catalytic combustion catalyst, which is the same as example 1, except that the mass ratio of the coating agent precursor in step (2) to the supported catalyst in step (1) is 0.02:1.
Example 8
The present example provides a method for preparing a catalytic combustion catalyst, which is the same as example 1, except that the mass ratio of the coating agent precursor in step (2) to the supported catalyst in step (1) is 0.4:1.
Comparative example 1
The present comparative example provides a method for preparing a catalytic combustion catalyst, comprising the steps of:
weighing 0.95g of copper nitrate trihydrate and 1.61g of manganese nitrate hexahydrate, and dissolving the copper nitrate trihydrate and the manganese nitrate hexahydrate in 2.5g of deionized water to form an impregnating solution; slowly dripping the solution into 5g of gamma-Al 2 O 3 Stirring while dripping, standing for 4 hours after dripping, drying at 80 ℃ for 8 hours, and roasting at 500 ℃ for 4 hours to obtain the catalytic combustion catalyst.
Comparative example 2
This comparative example provides a method for preparing a catalytic combustion catalyst, which is the same as example 1 except that dopamine hydrochloride is not added in step (2).
Comparative example 3
This comparative example provides a method for preparing a catalytic combustion catalyst, which is the same as example 1 except that the step (2) is not performed with calcination.
Comparative example 4
This comparative example provides a method of preparing a catalytic combustion catalyst, which is the same as example 1 except that the step (2) directly mixes the coating agent precursor with the supported catalyst and then calcines it;
step (2) of this comparative example includes: mixing 0.09g of the coating agent precursor with 1g of the supported catalyst in the step (1) for 4 hours, then roasting at 700-900 ℃ for 3-5 hours in a nitrogen atmosphere, and then roasting at 400-600 ℃ for 3-5 hours in an air atmosphere.
The catalysts obtained in the above examples and comparative examples were subjected to activity, sulfur resistance stability and water and sulfur resistance stability tests, the activity test method comprising: 0.5g of powder catalyst is weighed in a fixed bed reactor, 250ml/min of mixed gas is introduced into the reactor, and the mixed gas comprises the following components: 8000ppm CO, 10% O 2 And nitrogen, namely, starting from 50 ℃, measuring the concentration of carbon monoxide in the tail gas of the reactor under different reaction temperature conditions by temperature programming, calculating the conversion rate of the carbon monoxide according to the change of the concentration of the carbon monoxide, recording the temperature at which the conversion rate of the carbon monoxide is 99%, and testing to obtain the T99 of the fresh catalyst.
0.5g of powder catalyst is weighed in a fixed bed reactor, 250ml/min of mixed gas is introduced into the reactor, and the mixed gas comprises the following components: 8000ppm CO, 50ppm SO 2 、10％O 2 And nitrogen, namely, measuring the concentration of carbon monoxide in the tail gas of the reactor under the conditions of different reaction temperatures by temperature programming from 50 ℃, calculating the conversion rate of the carbon monoxide according to the change of the concentration of the carbon monoxide, and recording the temperature at which the conversion rate of the carbon monoxide is 99% to obtain the T99 of the catalyst under the condition of containing sulfur.
0.5g of powder catalyst is weighed in a fixed bed reactor, 250ml/min of mixed gas is introduced into the reactor, and the mixed gas comprises the following components: 8000ppm CO, 50ppm SO 2 10% of water vapor, 10% of O 2 And nitrogen, namely, measuring the concentration of carbon monoxide in the tail gas of the reactor under the conditions of different reaction temperatures by temperature programming from 50 ℃, calculating the conversion rate of the carbon monoxide according to the change of the concentration of the carbon monoxide, and recording the temperature at which the conversion rate of the carbon monoxide is 99% to obtain the T99 of the catalyst under the conditions of water and sulfur.
The test results are shown in table 1:
TABLE 1
As can be seen from table 1:
the catalyst obtained by the invention has higher activity on carbon monoxide, higher sulfur resistance stability and higher water resistance and sulfur resistance stability, T99 under the condition of no water and no sulfur can reach below 115 ℃, T99 under the condition of sulfur can reach below 120 ℃, and T99 under the condition of water and sulfur can reach below 125 ℃; from example 1 and comparative example, the catalyst prepared by the conventional impregnation method has poor stability against sulfur and water; as is clear from examples 1 and comparative examples 2 to 3, the carbon source of the present invention as an auxiliary coating agent can bring the coating agent to the surface of the carrier and can be removed after calcination, and thus the catalyst obtained in example 1 has excellent catalytic activity and water-and sulfur-resistant stability as compared with comparative examples 2 to 3; as is clear from examples 1 and 4, only by simply mixing and calcining the coating agent precursor with the supported catalyst, the coating is uneven, and the coating metal covers the active center, so that the catalytic activity and the water-and sulfur-resistant stability of the obtained catalyst are reduced; from examples 1 and 4-8, it is clear that the carrier selection, addition of the auxiliary agent, selection of the coating agent precursor and addition of the coating agent precursor of the present invention all affect the catalyst activity and the water and sulfur resistance stability.
In summary, the invention provides a catalytic combustion catalyst, and a preparation method and application thereof, wherein a carbon source is introduced in the calcination process, and a nano coating layer is introduced on the surface of the catalyst, so that the catalyst not only has stronger activity on CO, but also has improved water-resistance and sulfur-resistance stability, and the catalytic combustion catalyst has stronger CO catalytic combustion stability under the condition of industrial flue gas containing water and sulfur.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (10)
1. A method of preparing a catalytic combustion catalyst, the method comprising the steps of:
(1) Mixing a carrier, an active metal precursor and a solvent, performing solid-liquid separation, drying and roasting to obtain a supported catalyst;
(2) Mixing a carbon source, a coating agent precursor and the supported catalyst in the step (1), performing solid-liquid separation, drying and roasting to obtain the catalytic combustion catalyst.
2. The method of claim 1, wherein the coating agent precursor of step (2) comprises a metal salt and/or a silicon source, preferably a metal salt;
preferably, the metal salt comprises a titanium salt and/or a zirconium salt;
preferably, the silicon source comprises ethyl orthosilicate;
preferably, the mass ratio of the coating agent precursor in the step (2) to the supported catalyst in the step (1) is (0.05-0.3): 1;
preferably, the mass ratio of the carbon source to the coating agent precursor in the step (2) is (8-50): 1.
3. The method of claim 1 or 2, wherein the carbon source of step (2) comprises dopamine hydrochloride;
preferably, the mixing in the step (2) comprises dispersing a carbon source in water with the pH of 7.5-10.5, adding a coating agent precursor, stirring, adding a supported catalyst, and continuing stirring;
preferably, the stirring time is 1-4 hours;
preferably, after the mixing in the step (2), solid-liquid separation, washing and drying are performed first, and then roasting is performed.
4. A method according to any one of claims 1 to 3, wherein the atmosphere for calcination in step (2) comprises a nitrogen atmosphere and an air atmosphere;
preferably, the firing in step (2) comprises firing at a temperature of 700-900 ℃ for 3-5 hours in a nitrogen atmosphere and then at a temperature of 400-600 ℃ for 3-5 hours in an air atmosphere.
5. The method of any one of claims 1-4, wherein the carrier of step (1) comprises a hydrophobic carrier;
preferably, the hydrophobic support comprises hydrophobic alumina and/or hydrophobic silica;
preferably, the solvent used in step (1) comprises an organic solvent;
preferably, the organic solvent includes any one or a combination of at least two of methanol, ethanol, acetic acid, ethyl acetate, and methyl ethyl ketone.
6. The method of any one of claims 1 to 5, wherein the metal element in the active metal precursor of step (1) comprises any one or a combination of at least two of Pd, pt, cu, mn or Co;
preferably, in the supported catalyst in the step (1), the Pd and/or Pt loading is 0-1wt%;
preferably, in the supported catalyst in the step (1), the loading amount of any one or at least two of Cu, mn or Co is 5 to 10wt%.
7. The method according to any one of claims 1 to 6, wherein an auxiliary agent is further added during the mixing in the step (1), and the metal element in the auxiliary agent comprises any one or a combination of at least two of Co, ce, la, zr, cu and Mn;
preferably, in the supported catalyst in the step (1), the loading amount of the metal element in the auxiliary agent is 0-10wt% but not 0wt%;
preferably, the roasting temperature in the step (1) is 450-550 ℃ and the time is 3-5h;
preferably, the temperature of the drying in the step (1) is 80-100 ℃ and the time is 4-8h.
8. The preparation method according to any one of claims 1 to 7, characterized in that the preparation method comprises the steps of:
(1) Mixing a hydrophobic carrier, an active metal precursor, an auxiliary agent and an organic solvent, performing solid-liquid separation, drying at 80-100 ℃ for 4-8 hours and roasting at 450-550 ℃ for 3-5 hours to obtain a supported catalyst;
the metal element in the active metal precursor comprises any one or a combination of at least two of Pd, pt, cu, mn and Co; in the supported catalyst in the step (1), the loading amount of Pd and/or Pt is 0-1wt%, and the loading amount of any one or a combination of at least two of Cu, mn and Co is 5-10wt%;
the metal element in the auxiliary agent comprises any one or a combination of at least two of Co, ce, la, zr, cu and Mn, and in the supported catalyst in the step (1), the load of the metal element in the auxiliary agent is 0-10wt% but not 0wt%;
(2) Dispersing dopamine hydrochloride in water with the pH value of 7.5-10.5, adding a coating agent precursor, stirring, adding a supported catalyst, continuously stirring, performing solid-liquid separation, washing and drying, roasting at the temperature of 700-900 ℃ for 3-5h in a nitrogen atmosphere, and roasting at the temperature of 400-600 ℃ for 3-5h in an air atmosphere to obtain the catalytic combustion catalyst;
the mass ratio of the coating agent precursor to the supported catalyst in the step (1) is (0.05-0.3): 1, and the mass ratio of the carbon source to the coating agent precursor is (8-50): 1; the coating agent precursor comprises any one or a combination of at least two of titanium salt, zirconium salt or silicon source.
9. A catalytic combustion catalyst prepared by the method of any one of claims 1-8.
10. Use of the catalytic combustion catalyst of claim 9, wherein the use comprises the conversion of carbon monoxide under industrial flue gas conditions.
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