CN116493023A - Tail gas catalyst for gasoline generating set and preparation method thereof - Google Patents
Tail gas catalyst for gasoline generating set and preparation method thereof Download PDFInfo
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- CN116493023A CN116493023A CN202310466141.1A CN202310466141A CN116493023A CN 116493023 A CN116493023 A CN 116493023A CN 202310466141 A CN202310466141 A CN 202310466141A CN 116493023 A CN116493023 A CN 116493023A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000011268 mixed slurry Substances 0.000 claims abstract description 31
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005303 weighing Methods 0.000 claims abstract description 20
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 15
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 15
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910003446 platinum oxide Inorganic materials 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 11
- KQJQGYQIHVYKTF-UHFFFAOYSA-N cerium(3+);trinitrate;hydrate Chemical compound O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KQJQGYQIHVYKTF-UHFFFAOYSA-N 0.000 claims abstract description 10
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 44
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- -1 alcohol compound Chemical class 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 17
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2825—Ceramics
- F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Toxicology (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a gasoline generator set tail gas catalyst and a preparation method thereof. The preparation method comprises the following steps: weighing cerium nitrate hydrate capable of theoretically generating 50-70 g of cerium oxide, adding the cerium nitrate hydrate into deionized water, and regulating pH by using carboxylic acid to obtain a mixed solution; weighing ferric nitrate hydrate capable of theoretically generating 5-20 g of ferric oxide, adding the ferric nitrate hydrate into deionized water, and dripping a platinum nitrate solution capable of theoretically generating 0.1-2 g of platinum oxide to obtain a mixed solution; mixing the two mixed solutions, regulating the pH with ammonia water, and adding alcohol compounds; drying and roasting the mixed slurry, and then crushing and ball-milling to obtain finished slurry; and (3) coating the slurry on a carrier, and drying and roasting to obtain the catalyst. The catalyst disclosed by the invention has the advantages of simple preparation process, high CO conversion rate, good high-temperature resistance and long service life, and is prepared by only adopting noble metal Pt as a catalytic active component, so that the preparation cost is low.
Description
Technical Field
The invention belongs to the technical field of catalytic materials for air purification, and particularly relates to a tail gas catalyst of a gasoline generating set and a preparation method thereof.
Background
The gasoline generator set is a device for converting the heat energy of fuel (gasoline) into mechanical energy and driving a generator to convert the mechanical energy into electric energy. When the engine works, air and fuel are mixed into mixed gas by the air inlet mechanism and then enter the combustion chamber to do combustion work and then are discharged. The tail gas discharged by the generator set using gasoline as fuel is basically composed of CO, HC and NO x The composition is mostly a partial concentrated atmosphere (lambda<1). The U.S. safety regulations for gasoline generating sets in the export united states, beginning at month 4 of 2023, have increased the emission requirement of CO (UL 2201), which must be less than 150g/h and require 500 hours of endurance testing. According to the current condition of the gasoline generating set, the carburetor is basically adopted, the emission amount of CO is 1500-3000 g/h, and if the safety regulation of the gasoline generating set in the United states is required to be achieved, the conversion rate of CO is at least more than 95%.
The Chinese patent No. 2007101602554 provides a method for treating tail gas of a gasoline generating set, but only provides noble metal content, contains three noble metals of Pt, pd and Rh, and does not provide a specific preparation method of a catalyst. The Chinese patent No. 2020102961920 provides a method and a device for treating the tail gas of a gasoline generating set, which have the advantages of higher cleaning degree, convenient disassembly, cleaning, monitoring and observation, and capability of judging whether the tail gas reaches the standard after being treated. But also does not relate to specific catalyst preparation techniques.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a gasoline generator set tail gas catalyst with high CO conversion rate, good high temperature resistance and long service life and a preparation method thereof.
According to the technical scheme provided by the invention, the tail gas catalyst of the gasoline generating set comprises a metal honeycomb carrier and a catalyst positioned on the metal honeycomb carrier, wherein in the catalyst, the content of cerium oxide is 50-70 g/L, the content of ferric oxide is 5-20 g/L, and the content of platinum oxide is 0.5-2 g/L.
The preparation method of the tail gas catalyst of the gasoline generating set comprises the following steps:
(1) Weighing cerium nitrate hydrate capable of theoretically generating 50-70 g of cerium oxide, adding the cerium nitrate hydrate into deionized water, stirring for 0.5-2 h, regulating pH value to be 2-4 by using carboxylic acid, and stirring for 2-10 h to obtain a mixed solution for later use;
(2) Weighing ferric nitrate hydrate capable of theoretically generating 5-20 g of ferric oxide, adding the ferric nitrate hydrate into deionized water, stirring for 0.5-2 h, slowly dripping a platinum nitrate solution capable of theoretically generating 0.1-2 g of platinum oxide, and continuously stirring for 0.5-2 h to obtain a mixed solution;
(3) Slowly dripping the mixed solution obtained in the step (2) into the mixed solution obtained in the step (1), stirring for 0.5-2 h, adjusting the pH value to be 7-7.5 by ammonia water, stirring for 2-10 h, then adding an alcohol compound, and continuously stirring for 2-10 h to obtain mixed slurry;
(4) Drying the mixed slurry in the step (3) at 60-80 ℃ for 4-10 h, drying at 120-150 ℃ for 4-10 h, roasting at 400-600 ℃ for 2-10 h to obtain Pt-containing catalyst powder, crushing, adding deionized water, and ball milling to obtain Pt-containing finished slurry;
(5) And (3) coating the finished slurry obtained in the step (4) on a metal honeycomb carrier, drying the metal honeycomb carrier for 0.5 to 20 hours at the temperature of 80 to 200 ℃, and roasting the dried carrier for 0.5 to 20 hours at the temperature of 400 to 600 ℃ to obtain the tail gas catalyst of the gasoline generating set.
Preferably, in the step (1), the carboxylic acid is one or more of formic acid, acetic acid, oxalic acid, propionic acid and malonic acid.
Preferably, in the step (3), the alcohol compound is one or more of methanol, ethanol, ethylene glycol, propanol, propylene glycol and glycerol.
The catalyst disclosed by the invention has the advantages of simple preparation process, high CO conversion rate, good high-temperature resistance and long service life, and is prepared by only adopting noble metal Pt as a catalytic active component, so that the preparation cost is low. The cerium oxide is used as a carrier for loading noble metal Pt and base metal Fe, so that the oxygen concentration in the oxidation reaction can be increased, the catalytic oxidation capacity of Pt can be improved, and the high-temperature aging resistance of Pt can be increased; the addition of Fe can further improve the conversion efficiency of CO.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
(1) Weighing cerium nitrate hydrate capable of theoretically generating 70g of cerium oxide, adding 0.2L of deionized water, stirring for 1h, dropwise adding acetic acid into a cerium nitrate aqueous solution, adjusting the pH value of the solution to be 3, and stirring for 2h to obtain a mixed solution for later use;
(2) Weighing ferric nitrate hydrate capable of theoretically generating 5g of ferric oxide, adding 0.1L of deionized water, stirring for 1h, slowly dripping a platinum nitrate solution capable of theoretically generating 0.5g of platinum oxide, and stirring for 1h to obtain a mixed solution;
(3) Slowly adding the mixed solution prepared in the step (2) into the mixed solution prepared in the step (1), and stirring for 1h; dropwise adding ammonia water, adjusting the pH to be 7.2, and stirring for 2h; weighing 10g of ethylene glycol, slowly adding into the mixed slurry, and continuously stirring for 2 hours to obtain the mixed slurry;
(4) Drying the mixed slurry obtained in the step (3) at 70 ℃ for 10 hours, drying the mixed slurry at 150 ℃ for 10 hours, roasting the mixed slurry at 500 ℃ for 2 hours, crushing the mixed slurry after roasting, and adding 100g of deionized water for ball milling to obtain finished slurry;
(5) And (3) coating the finished slurry obtained after ball milling in the step (4) on a metal carrier with the specification of phi 80 x 60 x 50/300cpsi according to the coating amount of 75.5g/L, drying at 150 ℃ for 4 hours, and roasting at 450 ℃ for 2 hours to obtain the tail gas catalyst of the generator set.
The catalyst obtained in example 1 had a cerium oxide content of 70g/L, an iron oxide content of 5g/L and a platinum oxide content of 0.5g/L.
Example 2
(1) Weighing cerium nitrate hydrate capable of theoretically generating 60g of cerium oxide, adding 0.2L of deionized water, stirring for 0.5h, dropwise adding oxalic acid into a cerium nitrate aqueous solution, adjusting the pH value of the solution to be=3, and stirring for 2h to obtain a mixed solution for later use;
(2) Weighing ferric nitrate hydrate capable of theoretically generating 10g of ferric oxide, adding 0.1L of deionized water, stirring for 1h, slowly dripping a platinum nitrate solution capable of theoretically generating 0.5g of platinum oxide, and stirring for 1h to obtain a mixed solution;
(3) Slowly adding the mixed solution prepared in the step (2) into the mixed solution prepared in the step (1), and stirring for 1h; dropwise adding ammonia water, adjusting the pH to be 7.5, and stirring for 5 hours; weighing 10g of propylene glycol, slowly adding the propylene glycol into the mixed slurry, and continuously stirring for 5 hours to obtain the mixed slurry;
(4) Drying the mixed slurry obtained in the step (3) at 60 ℃ for 10 hours, drying the mixed slurry at 120 ℃ for 10 hours, roasting the mixed slurry at 400 ℃ for 10 hours, crushing the mixed slurry after roasting, and adding 100g of deionized water for ball milling to obtain finished slurry;
(5) And (3) coating the finished slurry obtained after ball milling in the step (4) on a metal carrier with the specification of phi 80 x 60 x 50/300cpsi according to the coating amount of 70.5g/L, drying at 150 ℃ for 4 hours, and roasting at 450 ℃ for 2 hours to obtain the tail gas catalyst of the generator set.
The catalyst obtained in example 2 had a cerium oxide content of 60g/L, an iron oxide content of 10g/L and a platinum oxide content of 0.5g/L.
Example 3
(1) Weighing cerium nitrate hydrate capable of theoretically generating 50g of cerium oxide, adding 0.2L of deionized water, stirring for 2 hours, dropwise adding formic acid into a cerium nitrate aqueous solution, adjusting the pH value of the solution to be 2, and stirring for 6 hours to obtain a mixed solution for later use;
(2) Weighing ferric nitrate hydrate capable of theoretically generating 20g of ferric oxide, adding 0.1L of deionized water, stirring for 2 hours, slowly dripping a platinum nitrate solution capable of theoretically generating 0.5g of platinum oxide, and stirring for 2 hours to obtain a mixed solution;
(3) Slowly adding the mixed solution prepared in the step (2) into the mixed solution prepared in the step (1), and stirring for 0.5h; dropwise adding ammonia water, adjusting the pH to be 7, and stirring for 8 hours; weighing 10g of methanol, slowly adding the methanol into the mixed slurry, and continuously stirring for 8 hours to obtain the mixed slurry;
(4) Drying the mixed slurry obtained in the step (3) at 80 ℃ for 4 hours, drying the mixed slurry at 150 ℃ for 4 hours, roasting the mixed slurry at 600 ℃ for 2 hours, crushing the mixed slurry after roasting, and adding 100g of deionized water for ball milling to obtain finished slurry;
(5) And (3) coating the finished slurry obtained after ball milling in the step (4) on a metal carrier with the specification of phi 80 x 60 x 50/300cpsi according to the coating amount of 70.5g/L, drying at 80 ℃ for 20h, and roasting at 400 ℃ for 20h to obtain the tail gas catalyst of the generator set.
The catalyst obtained in example 3 had a cerium oxide content of 50g/L, an iron oxide content of 20g/L and a platinum oxide content of 0.5g/L.
Example 4
(1) Weighing cerium nitrate hydrate capable of theoretically generating 70g of cerium oxide, adding 0.2L of deionized water, stirring for 1h, dropwise adding propionic acid into cerium nitrate aqueous solution, adjusting the pH value of the solution to be 4, and stirring for 10h to obtain a mixed solution for later use;
(2) Weighing ferric nitrate hydrate capable of theoretically generating 5g of ferric oxide, adding 0.1L of deionized water, stirring for 0.5h, slowly dripping a platinum nitrate solution capable of theoretically generating 1.0g of platinum oxide, and stirring for 0.5h to obtain a mixed solution;
(3) Slowly adding the mixed solution prepared in the step (2) into the mixed solution prepared in the step (1), and stirring for 2 hours; dropwise adding ammonia water, adjusting the pH to be 7, and stirring for 10 hours; weighing 10g of propanol, slowly adding the propanol into the mixed slurry, and continuously stirring for 10 hours to obtain the mixed slurry;
(4) Drying the mixed slurry obtained in the step (3) at 70 ℃ for 10 hours, drying the mixed slurry at 150 ℃ for 10 hours, roasting the mixed slurry at 500 ℃ for 2 hours, crushing the mixed slurry after roasting, and adding 100g of deionized water for ball milling to obtain finished slurry;
(5) And (3) coating the finished slurry obtained after ball milling in the step (4) on a metal carrier with the specification of phi 80 x 60 x 50/300cpsi according to the coating amount of 76.0g/L, drying at 200 ℃ for 0.5h, and roasting at 600 ℃ for 0.5h to obtain the generator set tail gas catalyst.
The catalyst obtained in example 4 had a cerium oxide content of 70g/L, an iron oxide content of 5g/L and a platinum oxide content of 1.0g/L.
Comparative example 1
(1) Weighing 70g of cerium oxide powder, adding 150g of deionized water, stirring for 2 hours, and performing ball milling;
(2) And (3) coating the slurry subjected to ball milling in the step (1) on a metal carrier with the specification of phi 80 x 60 x 50/300cpsi according to the coating amount of 71g/L, drying at 150 ℃ for 4h, and roasting at 450 ℃ for 2h to obtain the generator set tail gas catalyst.
Comparative example 2
(1) Weighing 70g of gamma-alumina powder, adding 150g of deionized water, stirring for 2 hours, and performing ball milling;
(2) And (3) coating the slurry subjected to ball milling in the step (1) on a metal carrier with the specification of phi 80 x 60 x 50/300cpsi according to the coating amount of 71g/L, drying at 150 ℃ for 4h, and roasting at 450 ℃ for 2h to obtain the generator set tail gas catalyst.
The generator set exhaust catalysts obtained in example 1, example 2, example 3, example 4 and comparative example 1 and comparative example 2 were subjected to a 0h exhaust emission test on a gasoline generator set with a discharge capacity of 420cc and a power of 8.8kw, the test cycle was performed by a six-condition method, and the exhaust tests after 500h of endurance were respectively performed, and the test results are shown in table 1.
TABLE 1
| Emission value of 0h-CO (g/h) | Durable 500h-CO emission value (g/h) | |
| Example 1 | 80.8 | 125.7 |
| Example 2 | 75.3 | 120.4 |
| Example 3 | 66.4 | 121.5 |
| Example 4 | 50.4 | 71.3 |
| Comparative example 1 | 90.7 | 175.4 |
| Comparative example 2 | 99.6 | 153.3 |
From the test data in Table 1, it can be seen that the noble metal Pt content is the same in examples 1-3, the increase in the amount of ferric oxide improves CO emissions for 0h, and the emission value after 500h durability is substantially similar, but still meets the emission standard of UL 2201; the catalyst of example 4 exhibited good catalytic oxidation performance due to the increased noble metal Pt content, both 0h and 500h durability. The noble metal Pt content in comparative example 1 and comparative example 2 was the same as in example 4, but CO emissions of 0h have exhibited relative disadvantages, and the CO emission value after 500h durability has exceeded the limit of UL2201 regulations.
Claims (4)
1. A kind of petrol generator set tail gas catalyst, characterized by: the catalyst comprises a metal honeycomb carrier and a catalyst positioned on the metal honeycomb carrier, wherein in the catalyst, the content of cerium oxide is 50-70 g/L, the content of ferric oxide is 5-20 g/L, and the content of platinum oxide is 0.5-2 g/L.
2. The method for preparing the tail gas catalyst of the gasoline generating set, which is characterized by comprising the following steps:
(1) Weighing cerium nitrate hydrate capable of theoretically generating 50-70 g of cerium oxide, adding the cerium nitrate hydrate into deionized water, stirring for 0.5-2 hours, adjusting pH=2-4 by using carboxylic acid, and stirring for 2-10 hours to obtain a mixed solution for later use;
(2) Weighing ferric nitrate hydrate capable of theoretically generating 5-20 g of ferric oxide, adding the ferric nitrate hydrate into deionized water, stirring for 0.5-2 h, slowly dripping a platinum nitrate solution capable of theoretically generating 0.1-2 g of platinum oxide, and continuously stirring for 0.5-2 h to obtain a mixed solution;
(3) Slowly dripping the mixed solution obtained in the step (2) into the mixed solution obtained in the step (1), stirring for 0.5-2 h, adjusting the pH value to be 7-7.5 by ammonia water, stirring for 2-10 h, then adding an alcohol compound, and continuously stirring for 2-10 h to obtain mixed slurry;
(4) Drying the mixed slurry obtained in the step (3) at 60-80 ℃ for 4-10 hours, drying the mixed slurry at 120-150 ℃ for 4-10 hours, roasting the mixed slurry at 400-600 ℃ for 2-10 hours to obtain catalyst powder containing Pt, crushing the catalyst powder, adding deionized water, and ball milling the crushed catalyst powder to obtain finished slurry containing Pt;
(5) And (3) coating the finished slurry obtained in the step (4) on a metal honeycomb carrier, drying the metal honeycomb carrier at 80-200 ℃ for 0.5-20 h, and roasting the dried carrier at 400-600 ℃ for 0.5-20 h to obtain the tail gas catalyst of the gasoline generator set.
3. The method for preparing the tail gas catalyst of the gasoline generating set, according to claim 2, is characterized in that: in the step (1), the carboxylic acid is one or more of formic acid, acetic acid, oxalic acid, propionic acid and malonic acid.
4. The method for preparing the tail gas catalyst of the gasoline generating set, according to claim 2, is characterized in that: in the step (3), the alcohol compound is one or more of methanol, ethanol, glycol, propanol, propylene glycol and glycerol.
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