CN111672519A - Noble metal-rare earth perovskite type integral three-way catalyst and preparation method thereof - Google Patents
Noble metal-rare earth perovskite type integral three-way catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims description 25
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 34
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 27
- 239000000919 ceramic Substances 0.000 claims abstract description 25
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 239000006255 coating slurry Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 8
- 229910052878 cordierite Inorganic materials 0.000 claims description 7
- 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 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 13
- 238000005245 sintering Methods 0.000 abstract description 7
- 239000007789 gas Substances 0.000 abstract description 6
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 12
- 239000011572 manganese Substances 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 239000002002 slurry Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 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
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910002254 LaCoO3 Inorganic materials 0.000 description 7
- 229910017414 LaAl Inorganic materials 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 5
- 239000011232 storage material Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002273 La1–xSrxCoO3 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- GJFXIYGDVYZDRX-UHFFFAOYSA-N cerium;oxozirconium Chemical compound [Ce].[Zr]=O GJFXIYGDVYZDRX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 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
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J23/70—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
- 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
- B01J23/8986—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 manganese, technetium or rhenium
-
- 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
- B01J37/0215—Coating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a noble metal-rare earth perovskite type integral three-way catalyst, which is characterized in that: the catalyst takes honeycomb ceramics as a carrier, and the rare earth perovskite La is loaded on the honeycomb ceramics1‑XAXCo1‑yByO3And noble metal forming catalyst G-La1‑ xAxCo1‑yByO3Wherein G is one of noble metals, A is one of Ce, Pr, Nd, Y and Sr, B is one of Cu, Mn, Ni and Cr, x and Y are molar values, x is more than or equal to 0.1 and less than or equal to 0.9, and Y is more than or equal to 0.1 and less than or equal to 0.9; the titanium ore and a small amount of Pd are combined for use, the use amount of Pd is reduced, the production cost is further reduced, the prepared catalyst is high in activity, good in stability, high in low-temperature activity and high-temperature sintering resistance, used for purifying automobile exhaust, capable of simultaneously purifying three main harmful gases including CO, HC and NOx in the automobile exhaust, and low in ignition temperature required by the catalyst.
Description
Technical Field
The invention relates to the technical field of automobile exhaust purification, in particular to a noble metal-rare earth perovskite type integral three-way catalyst and a preparation method thereof.
Background
With the increase of the usage amount of automobiles, the emission of a large amount of automobile exhaust poses serious threat to the ecological environment and becomes a main influence factor of urban atmospheric pollution. The three-way catalyst technology has been used for 30 years and still is the most widely used automobile emission control technology in the world at present, and is the core part of the device, and can simultaneously purify three main harmful gases of CO, HC and NOx in automobile exhaust. At present, CeZr oxide is mostly adopted as an oxygen storage material in the three-way catalyst, but the material only has oxygen storage capacity and does not greatly improve the catalytic activity. Rare earth perovskite metal oxide (ABO)3) The catalyst has stable structure, can generate oxygen vacancy due to the substitution of A, B sites, and has better redox performance, so the catalyst not only can be used as an oxygen storage material, but also can be used as an auxiliary agent to improve the activity of the catalyst. Patent CN200710304316 La prepared by sol-gel method0.7Sr0.3Mn0.9Ni0.1O3The oxygen storage performance of the perovskite oxygen storage material is obviously due to the common cerium-zirconium oxygen storage material, but the perovskite oxygen storage material is not actually used for treating automobile exhaust. Patent CN201010136259 for preparing La1-xSrxCoO3The perovskite catalyst has high activity for catalytic conversion of NOx, but the active components are single, so that CO and HC are difficult to treat simultaneously, and the emission requirement is difficult to meet. Patent CN201610971529 preparation of LaMnO by3The perovskite is subjected to organic acid solution washing to improve the catalytic performance of the catalyst, and although the catalyst has certain catalytic activity on methane, CO, VOCs and the like, the required ignition temperature is higher than 400 ℃.
Disclosure of Invention
In view of the above, the present invention aims to provide a precious metal-rare earth perovskite type monolithic three-way catalyst and a preparation method thereof, wherein the precious metal content is low, the activity of the catalyst is high, the stability is good, the catalyst has high low-temperature activity and high-temperature sintering resistance, and the economic cost can be reduced.
The noble metal-rare earth perovskite type integral three-way catalyst takes honeycomb ceramics as a carrier, and the honeycomb ceramics is loaded with rare earth perovskite La1-XAXCo1-yByO3And noble metal forming catalyst G-La1-xAxCo1-yByO3Wherein G is one of noble metals, A is one of Ce, Pr, Nd, Y and Sr, B is one of Cu, Mn, Ni and Cr, x and Y are molar values, x is more than or equal to 0.1 and less than or equal to 0.9, and Y is more than or equal to 0.1 and less than or equal to 0.9;
further, the rare earth perovskite and the noble metal are loaded on the honeycomb ceramic through a carrier oxide;
further, the carrier oxide is low-temperature alumina, and noble metal is impregnated on the mixture of the low-temperature alumina and the rare earth perovskite and then loaded on the honeycomb ceramic in a coating mode;
further, the noble metal is Pd, and the low-temperature alumina is gamma-Al2O3The honeycomb ceramic is cordierite honeycomb;
furthermore, the loading amount of the noble metal is 0.5-1 g/L.
The preparation method of the noble metal-rare earth perovskite type integral three-way catalyst comprises the following steps: coating the coating slurry containing rare earth perovskite and noble metal on honeycomb ceramics, and then drying and roasting;
further, the preparation method of the coating slurry comprises the following steps: mixing low-temperature alumina and rare earth perovskite powder to prepare a solution, then adding lanthanum as an auxiliary agent, fully and uniformly stirring, adding a noble metal salt solution, adjusting the pH value to acidity, and finally performing ball milling to prepare coating slurry;
further, the preparation method of the rare earth perovskite comprises the following steps: mixing a metal nitrate solution with a precipitator, adjusting the pH value to be alkaline, then aging, washing, filtering, drying and grinding into powder;
further, coating and vacuum pumping are adopted, the coated honeycomb ceramic is dried for 2-4 hours at the temperature of 110-130 ℃, and then is roasted for 3-4 hours at the temperature of 500-600 ℃;
further, the precipitant is Na2CO3One of NaOH, ammonium carbonate and ammonia water.
The invention has the beneficial effects that: according to the metal-rare earth perovskite type integral three-way catalyst and the preparation method thereof, the titanium ore and a small amount of Pd are combined for use, the use amount of the Pd is reduced, the production cost is further reduced, the prepared catalyst is high in activity and good in stability, has high low-temperature activity and high-temperature sintering resistance, is used for purifying automobile exhaust, can simultaneously purify three main harmful gases including CO, HC and NOx in the automobile exhaust, and is low in ignition temperature required by the catalyst.
Detailed Description
In the noble metal-rare earth perovskite type monolithic three-way catalyst of the embodiment, the catalyst takes honeycomb ceramics as a carrier, and the honeycomb ceramics is loaded with rare earth perovskite La1-XAXCo1-yByO3And noble metal forming catalyst G-La1-xAxCo1- yByO3Wherein G is one of noble metals, A is one of Ce, Pr, Nd, Y and Sr, B is one of Cu, Mn, Ni and Cr, x and Y are molar values, x is more than or equal to 0.1 and less than or equal to 0.9, and Y is more than or equal to 0.1 and less than or equal to 0.9; G-La1-xAxCo1-yByO3In the formula, La is lanthanum, Co is cobalt, and O is oxygen. The noble metal G is preferably platinum, rhodium or palladium. With rare earth perovskites La1-XAXCo1-yByO3And noble metal is loaded on the honeycomb ceramic at the same time to reduce the dosage of the noble metal, La1-XAXCo1-yByO3The low-temperature activity of the catalyst can be improved only by combining with a small amount of noble metal, and the rare earth perovskite is combined with a small amount of noble metal to form the catalyst with the general formula of G-La1-xAxCo1-yByO3Formed not of a noble metal G substituted rare earth perovskite metal oxide (ABO)3) A, B bit structure in (1).
In this embodiment, the rare earth perovskite and the noble metal are supported on the honeycomb ceramic through a support oxide; the rare earth perovskite and the noble metal are combined through the carrier oxide, and the carrier oxide is used as a second carrier of the catalyst, so that the high-temperature sintering resistance of the catalyst is improved, and the stability of the catalyst is improved.
In this embodiment, the support is oxidized to a low temperature alumina, preferably γ -Al2O3The mixture of the low-temperature alumina carrier and the rare earth perovskite is impregnated with noble metal and then loaded on the honeycomb ceramic in a coating mode; the method is characterized in that low-temperature alumina is used as a carrier of a catalyst, the low-temperature alumina carrier and rare earth perovskite are mixed and then dipped with noble metal (preferably Pd because the volatility Pd, Ir, Pt and Ru are sequentially increased to form coating slurry, and the coating slurry is coated on honeycomb ceramic (preferably cordierite honeycomb), so that the carbon deposition on the surface of the catalyst is prevented, the thermal stability of the alumina is improved, and the sintering resistance is improved.
In the embodiment, the loading amount of the noble metal is 0.5-1 g/L; the perovskite is combined with a small amount of Pd, so that the cost can be reduced, the low-temperature activity and the high-temperature sintering resistance are high, and the utilization rate of the noble metal is greatly improved.
The preparation method of the noble metal-rare earth perovskite type integral three-way catalyst is characterized by comprising the following steps of: the method comprises the following steps: coating the coating slurry containing rare earth perovskite and noble metal on honeycomb ceramics, and then drying and roasting;
in this embodiment, the preparation method of the coating slurry includes the following steps: mixing low-temperature alumina and rare earth perovskite powder to prepare a solution, then adding lanthanum as an auxiliary agent, fully and uniformly stirring, adding a noble metal salt solution, adjusting the pH to acidity (the pH is 3-4), and finally performing ball milling to prepare coating slurry; firstly, low-temperature alumina and rare earth perovskite powder are mixed, and then precious metal is impregnated, so that the thermal stability of the alumina is improved, and the sintering resistance is improved. The doping amount of the auxiliary agent lanthanum is 1-5% by mass in terms of oxide; the addition amount of the rare earth perovskite is 5-30%.
In this embodiment, the preparation method of the rare earth perovskite comprisesThe method comprises the following steps: mixing a metal nitrate solution with a precipitator, adjusting the pH to be alkaline (adjusting the pH to 9-10), aging, washing, filtering, drying and grinding into powder; . Coating by adopting a coating vacuum suction mode, drying the coated honeycomb ceramic at the temperature of 110-130 ℃ for 2-4 h, and roasting at the temperature of 500-600 ℃ for 3-4 h; the precipitant is Na2CO3One of NaOH, ammonium carbonate and ammonia water; the concentration of the precipitant is 0.1-1 mol/L.
Example one
(1)LaCoO3Preparation of perovskite oxide: 25.77g of lanthanum nitrate and 17.32g of cobalt nitrate are dissolved in deionized water to prepare 1mol/L metal salt solution, after the metal salt solution is uniformly stirred by magnetic force, 1mol/L sodium carbonate solution is added, the pH value is adjusted to 9, the mixture is continuously stirred for 3 hours and is aged for 12 hours, the obtained precipitate is filtered by suction, the mixture is washed to be neutral by deionized water and ethanol, the obtained sample is placed in a drying oven to be dried to constant weight at 120 ℃, the sample is taken out and ground, and the powder is placed in a muffle furnace to be roasted for 4 hours at 650 ℃ to prepare LaCoO3 perovskite oxide powder;
(2) preparation of coating slurry: 3.64g of lanthanum nitrate was dissolved in 242g of water, and 13.68g of LaCoO was added3And 121g of gamma-Al2O3Mixing, stirring uniformly, slowly dropwise adding 4.27g of palladium nitrate solution into the slurry, stirring uniformly, adjusting the pH to 3 by using dilute nitric acid, continuously stirring for 8 hours, and performing ball milling for 2 hours to obtain coating slurry;
(3) coating and roasting: coating the slurry prepared in the step (2) on a cordierite honeycomb in a coating vacuum suction mode, drying at 120 ℃, and then roasting in a muffle furnace at 550 ℃ for 3 hours to obtain Pd-LaCoO3a/LaAl monolithic catalyst.
Activity test method:
the performance test of the catalyst is carried out in a stainless steel fixed bed reactor, and the simulated automobile exhaust comprises the following components: CO 0.75%, C3H8300ppm、C3H6600ppm、NO 500ppm、O20.8％、CO210％、N2Is balance gas, and has space velocity of 40000h-1The gas composition was analyzed by a Foster FGA-4100 automobile exhaust gas analyzer.
Example two
(1)La0.1Ce0.9CoO3Preparation of perovskite oxide: dissolving 2.87g of lanthanum nitrate, 25.98g of cerium nitrate and 19.35g of cobalt nitrate in deionized water to prepare 1mol/L metal salt solution, magnetically stirring uniformly, adding 1mol/L sodium carbonate solution, adjusting the pH value to 10, continuously stirring for 3h, aging for 12h, carrying out suction filtration on the obtained precipitate, washing with deionized water and ethanol to neutrality, placing the obtained sample in a drying oven at 120 ℃ to dry to constant weight, taking out and grinding, placing the powder in a muffle furnace at 650 ℃ for roasting for 4h to obtain La0.1Ce0.9CoO3A perovskite oxide powder;
(2) preparation of coating slurry: 3.64g of lanthanum nitrate was dissolved in 237g of water, and 16.42gLa was added0.1Ce0.9CoO3And 119g of gamma-Al2O3Mixing, stirring uniformly, slowly dropwise adding 3.42g of palladium nitrate solution into the slurry, stirring uniformly, adjusting the pH to 4 by using dilute nitric acid, continuously stirring for 8 hours, and performing ball milling for 2 hours to obtain coating slurry;
(3) coating and roasting: Pd-La is prepared as in example one0.1Ce0.9CoO3a/LaAl monolithic catalyst.
Activity test method: in the same manner as in the first embodiment
EXAMPLE III
(1)La0.1Ce0.9Co0.5Mn0.5O3Preparation of perovskite oxide: dissolving 3.63g of lanthanum nitrate, 32.73g of cerium nitrate, 12.19g of cobalt nitrate and 14.99g of manganese nitrate (the concentration of the manganese nitrate solution is 50 wt%) in deionized water to prepare a 1mol/L metal salt solution, uniformly stirring by magnetic force, adding a 1mol/L sodium carbonate solution, adjusting the pH value to 10, continuously stirring for 3 hours, aging for 12 hours, carrying out suction filtration on the obtained precipitate, washing with deionized water and ethanol to be neutral, placing the obtained sample in an oven, drying at 120 ℃ to constant weight, taking out and grinding, placing the powder in a muffle furnace, and roasting at 650 ℃ for 4 hours to obtain La0.1Ce0.9Co0.5Mn0.5O3A perovskite oxide powder;
(2) of coating slurriesPreparation: 10.91g of lanthanum nitrate was dissolved in 224g of water, and 20.52gLa was added0.1Ce0.9Co0.5Mn0.5O3And 112g of gamma-Al2O3Mixing, uniformly stirring, slowly dropwise adding 2.14g of palladium nitrate solution into the slurry, uniformly stirring, adjusting the pH to 3-4 by using dilute nitric acid, continuously stirring for 8 hours, and performing ball milling for 2 hours to obtain coating slurry;
(3) coating and roasting: Pd-La is prepared as in example one0.1Ce0.9Co0.5Mn0.5O3a/LaAl monolithic catalyst.
Activity test method: in the same manner as in the first embodiment
Example four
(1)LaCoO3Preparation of perovskite oxide: 25.77g of lanthanum nitrate and 17.32g of cobalt nitrate are dissolved in deionized water to prepare 1mol/L metal salt solution, after the metal salt solution is uniformly stirred by magnetic force, 1mol/L sodium carbonate solution is added, the pH value is adjusted to 10, the mixture is continuously stirred for 5 hours and is aged for 8 hours, the obtained precipitate is filtered by suction, the mixture is washed to be neutral by deionized water and ethanol, the obtained sample is placed in a drying oven to be dried to constant weight at 130 ℃, the sample is taken out and ground, and the powder is placed in a muffle furnace to be roasted for 6 hours at 850 ℃ to prepare LaCoO3 perovskite oxide powder;
(2) preparation of coating slurry: 3.64g of lanthanum nitrate was dissolved in 242g of water, and 13.68g of LaCoO was added3And 121g of gamma-Al2O3Mixing, stirring uniformly, slowly dropwise adding 4.27g of palladium nitrate solution into the slurry, stirring uniformly, adjusting the pH to 3 by using dilute nitric acid, continuously stirring for 24 hours, and performing ball milling for 1 hour to obtain coating slurry;
(3) coating and roasting: coating the slurry prepared in the step (2) on a cordierite honeycomb in a coating vacuum suction mode, drying at 110 ℃, and then roasting in a muffle furnace at 500 ℃ for 3.5h to obtain Pd-LaCoO3a/LaAl monolithic catalyst.
EXAMPLE five
(1)La0.1Ce0.9CoO3Preparation of perovskite oxide: 2.87g of lanthanum nitrate, 25.98g of cerium nitrate and 19.35g of cobalt nitrate are dissolved in deionized water to prepare 1mol/L metal saltThe solution is magnetically stirred uniformly, then 1mol/L sodium carbonate solution is added, the pH value is adjusted to 9, the solution is continuously stirred for 4 hours and is aged for 12 hours, the obtained precipitate is filtered, washed to be neutral by deionized water and ethanol, the obtained sample is placed in a drying oven at 130 ℃ and dried to constant weight, taken out and ground, the powder is placed in a muffle furnace at 700 ℃ and is roasted for 6 hours, and La is prepared0.1Ce0.9CoO3A perovskite oxide powder;
(2) preparation of coating slurry: 3.64g of lanthanum nitrate was dissolved in 237g of water, and 16.42gLa was added0.1Ce0.9CoO3And 119g of gamma-Al2O3Mixing, stirring uniformly, slowly dropwise adding 3.42g of palladium nitrate solution into the slurry, stirring uniformly, adjusting the pH to 4 by using dilute nitric acid, continuously stirring for 24 hours, and performing ball milling for 1.5 hours to obtain coating slurry;
(3) coating and roasting: coating the slurry prepared in the step (2) on a cordierite honeycomb in a coating vacuum suction mode, drying at 125 ℃, and roasting in a muffle furnace at 600 ℃ for 3.5 hours to obtain Pd-LaCoO3a/LaAl monolithic catalyst.
EXAMPLE six
(1)La0.1Ce0.9Co0.5Mn0.5O3Preparation of perovskite oxide: dissolving 3.63g of lanthanum nitrate, 32.73g of cerium nitrate, 12.19g of cobalt nitrate and 14.99g of manganese nitrate (the concentration of the manganese nitrate solution is 50 wt%) in deionized water to prepare a 1mol/L metal salt solution, uniformly stirring by magnetic force, adding a 1mol/L sodium carbonate solution, adjusting the pH value to 9, continuously stirring for 4 hours, aging for 15 hours, carrying out suction filtration on the obtained precipitate, washing with deionized water and ethanol to be neutral, placing the obtained sample in an oven, drying at 120 ℃ to constant weight, taking out and grinding, placing the powder in a muffle furnace, roasting at 800 ℃ for 5 hours to obtain La0.1Ce0.9Co0.5Mn0.5O3A perovskite oxide powder;
(2) preparation of coating slurry: 10.91g of lanthanum nitrate was dissolved in 224g of water, and 20.52gLa was added0.1Ce0.9Co0.5Mn0.5O3And 112g of gamma-Al2O3Mixing, stirring, and dissolving 2.14g palladium nitrateSlowly dripping the solution into the slurry, uniformly stirring, adjusting the pH to 4 by using dilute nitric acid, continuously stirring for 20 hours, and performing ball milling for 2 hours to obtain coating slurry;
(3) coating and roasting: coating and roasting: coating by vacuum suction, drying at 120 deg.C for 3 hr, and calcining at 520 deg.C in muffle furnace for 3 hr to obtain Pd-La0.1Ce0.9Co0.5Mn0.5O3a/LaAl monolithic catalyst.
In the above examples, the carrier was a cordierite honeycomb carrier having a specification of phi 110mm x 80mm, a cell density of 600cpsi, a cell wall thickness of 4mil, and a volume of 0.76L. The loading on the catalyst was 180 g/L.
The test results are shown in the following table
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. A noble metal-rare earth perovskite type monolithic three-way catalyst is characterized in that: the catalyst takes honeycomb ceramics as a carrier, and the rare earth perovskite La is loaded on the honeycomb ceramics1-XAXCo1-yByO3And noble metal forming catalyst G-La1-xAxCo1- yByO3Wherein G is one of noble metals, A is one of Ce, Pr, Nd, Y and Sr, and B is one of Cu, Mn, Ni and CrX and y are molar values, x is more than or equal to 0.1 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.9.
2. The noble metal-rare earth perovskite-type monolithic three-way catalyst according to claim 1, characterized in that: the rare earth perovskite and the noble metal are loaded on the honeycomb ceramic through a carrier oxide.
3. The noble metal-rare earth perovskite-type monolithic three-way catalyst according to claim 2, characterized in that: the carrier oxide is prepared by impregnating noble metal on low-temperature alumina and a mixture of the low-temperature alumina and rare earth perovskite and then loading the mixture on honeycomb ceramics in a coating mode.
4. The noble metal-rare earth perovskite-type monolithic three-way catalyst according to claim 2, characterized in that: the noble metal is Pd, and the low-temperature alumina is gamma-Al2O3The honeycomb ceramic is a cordierite honeycomb.
5. The noble metal-rare earth perovskite-type monolithic three-way catalyst according to claim 4, characterized in that: the loading amount of the noble metal is 0.5-1 g/L.
6. The method for preparing a noble metal-rare earth perovskite-type monolithic three-way catalyst according to claim 1, characterized in that: the method comprises the following steps: coating the coating slurry containing rare earth perovskite and noble metal on honeycomb ceramics, and then drying and roasting the honeycomb ceramics.
7. The method for preparing a noble metal-rare earth perovskite-type monolithic three-way catalyst according to claim 6, characterized in that: the preparation method of the coating slurry comprises the following steps: mixing low-temperature alumina and rare earth perovskite powder to prepare a solution, then adding lanthanum as an auxiliary agent, fully and uniformly stirring, adding a noble metal salt solution, adjusting the pH value to acidity, and finally performing ball milling to obtain coating slurry.
8. The method for preparing a noble metal-rare earth perovskite-type monolithic three-way catalyst according to claim 7, characterized in that: the preparation method of the rare earth perovskite comprises the following steps: mixing the metal nitrate solution with a precipitator, adjusting the pH value to be alkaline, then aging, washing, filtering, drying and grinding into powder.
9. The method for preparing a noble metal-rare earth perovskite-type monolithic three-way catalyst according to claim 7, characterized in that: the coating adopts a coating vacuum suction mode, the coated honeycomb ceramic is dried for 2-4 hours at the temperature of 110-130 ℃, and then is roasted for 3-4 hours at the temperature of 500-600 ℃.
10. The method for preparing a noble metal-rare earth perovskite-type monolithic three-way catalyst according to claim 8, characterized in that: the precipitant is Na2CO3One of NaOH, ammonium carbonate and ammonia water.
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