JPH0464735B2 - - Google Patents
Info
- Publication number
- JPH0464735B2 JPH0464735B2 JP59036255A JP3625584A JPH0464735B2 JP H0464735 B2 JPH0464735 B2 JP H0464735B2 JP 59036255 A JP59036255 A JP 59036255A JP 3625584 A JP3625584 A JP 3625584A JP H0464735 B2 JPH0464735 B2 JP H0464735B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- supported
- foam
- group
- exhaust gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 claims description 46
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 27
- 239000006260 foam Substances 0.000 claims description 22
- 239000010948 rhodium Substances 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- 229910052703 rhodium Inorganic materials 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 10
- 150000007529 inorganic bases Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- RCMWGBKVFBTLCW-UHFFFAOYSA-N barium(2+);dioxido(dioxo)molybdenum Chemical compound [Ba+2].[O-][Mo]([O-])(=O)=O RCMWGBKVFBTLCW-UHFFFAOYSA-N 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000008188 pellet Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000006262 metallic foam Substances 0.000 claims description 4
- 230000009970 fire resistant effect Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 description 13
- 239000010419 fine particle Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 229910052878 cordierite Inorganic materials 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000013618 particulate matter Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- -1 wire mesh Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910020851 La(NO3)3.6H2O Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000001745 non-dispersive infrared spectroscopy Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 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
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
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The present invention relates to a catalyst for purifying exhaust gas from a diesel engine and a method for producing the same. Specifically, the present invention relates to a catalyst for purifying diesel engine exhaust gas that has excellent performance in burning and removing carbon-based particulates present in diesel engine exhaust gas, and a method for producing the catalyst. In recent years, particulate matter (mainly composed of solid carbon particles, sulfur particles such as sulfates, and liquid or solid high molecular weight hydrocarbon particles) in diesel engine exhaust gas has become a problem in terms of environmental health. This is because most of these fine particles have particle diameters of 1 micron or less and are easily suspended in the atmosphere and easily taken into the human body through breathing. Therefore, studies are underway to tighten regulations on the emission of these particulates from diesel engines. By the way, methods for removing these fine particles can be broadly classified into the following two methods. One is to use a heat-resistant gas filter (ceramic foam, wire mesh, metal foam, sealed ceramic honeycomb, etc.) to pass through the exhaust gas and capture fine particles, and if the pressure drop increases, they will accumulate in a burner, etc. There is a method of regenerating the filter by burning the fine particles, and another method is to carry a catalyst substance on a carrier having this heat-resistant gas filter structure and perform a combustion operation as well as an over-operation to reduce the frequency of the above-mentioned combustion regeneration. This is a method of increasing the combustion activity of the catalyst to such an extent that regeneration is not necessary. In the former case, the higher the particle removal effect, the faster the pressure drop will rise and the more frequently the regeneration will occur, which will be cumbersome and economically disadvantageous. In comparison, the latter method is considered to be a much better method if a catalytic material that can maintain catalytic activity under the exhaust conditions (gas composition and temperature) of diesel engine exhaust gas is employed. However, the exhaust gas temperature of a diesel engine is much lower than that of a gasoline engine, and since light oil is used as fuel, the amount of SO 2 in the exhaust gas is also large. Therefore, it has almost no ability to generate sulfate (SO 2 is further oxidized to SO 3 or sulfuric acid mist), and even the accumulated particulates can be ignited and combusted well within the temperature obtained under normal engine running conditions. Although there is a demand for a catalyst with performance that satisfies this requirement, the current situation is that no catalyst has been proposed that satisfactorily meets this requirement. The object of the present invention is to provide a catalyst that satisfies this requirement. Specifically, we aim to purify diesel engine exhaust gas in a diesel engine exhaust gas temperature range that occurs during normal city driving, in which the fuel behavior of fine particles is good, the pressure drop rises slowly, the specified exhaust gas temperature is reached, and combustion regeneration occurs quickly. The purpose is to provide a catalyst for That is, the present invention is specified as follows. (1) On a porous inorganic substrate supported on a refractory three-dimensional structure having a gas filter function, or on a porous inorganic substrate formed into a pellet, (a) barium molybdate and (b) a compound of at least one metal selected from the group consisting of platinum, rhodium and palladium. Catalyst for engine exhaust gas purification. (2) The catalyst according to the above item 1, wherein the compound selected from groups (a) and (b) has a molar ratio of (a)/(b) = 5 to 90. (3) The fire-resistant three-dimensional structure is ceramic foam,
3. The catalyst according to 1 or 2 above, which is a wire mesh, a metal foam, or a plugged ceramic honeycomb. (4) (a) barium molybdate on a porous inorganic base supported on a refractory three-dimensional structure having a gas filter function, or on a porous inorganic base formed into a pellet shape; and (b) at least one metal compound selected from the group consisting of platinum, rhodium, and palladium, and (b) a compound of at least one metal selected from the group consisting of platinum, rhodium, and palladium. A method for producing a catalyst for purifying diesel engine exhaust gas, which is characterized by heat treatment at a temperature in the range of °C. The present inventors found that the exhaust gas temperature from a diesel engine is extremely low, and the exhaust gas temperature during city driving does not reach 450â even at the manhold exit, so it is 350â.
The combustion behavior of carbon-based fine particles is good even below, and the applanation temperature (the temperature at which the pressure increase due to accumulation of fine particles is equal to the pressure drop due to combustion of fine particles) is 330~
We have found a catalyst system that has characteristics such that the temperature is as low as 350â, the combustion of accumulated particulates starts below 400â, and the pressure drop decreases rapidly, and the formation of sulfate is hardly observed even at 450â. Normally, with catalysts that use only base metals, the combustion behavior of fine particles is such that the pressure drop increases quickly until a predetermined temperature is reached, and if the regeneration temperature is not reached under normal running conditions, external forced regeneration is required frequently. It needs to be done expensively and lacks practicality. On the other hand, catalysts containing precious metals have the ability to oxidize carbon monoxide (CO) and hydrocarbons (HC), but at the same time
Oxidation of SO 2 also occurs, producing sulfate, which is undesirable. However, even in the low temperature range, the combustible components of the fine particles are partially combusted, so the increase in pressure drop is gradual, and the applanation temperature is also lower than when only base metals are used. The present invention provides a catalyst composition that compensates for the above-mentioned drawbacks and does not impair the advantages of each catalyst component. Furthermore, although it is generally believed that molybdenum has high scattering properties and is prone to activity deterioration, the present inventors believe that component (a) can suppress the scattering of molybdenum and have good combustion behavior for fine particulate matter. The present invention has been completed based on the discovery that the sulfate-producing ability of the sulfate-generating ability of the sulfate-producing compound is significantly suppressed. According to the findings of the present inventors, in the above catalyst component dispersedly supported on an inorganic substrate, barium molybdate or lanthanum molybdate of group (a) acts extremely closely on the noble metal of group (b), and It exhibits the effect of effectively suppressing the sulfate generation ability of precious metals. Especially the final firing is 700~
The effect is fully demonstrated in catalysts that are processed at a high temperature of 1000°C. Moreover, the ratio of their coexistence is 5 in the molar ratio of (a)/(b).
90, preferably 8 to 60, and the supported amount of barium molybdate or lanthanum molybdate of group (a) is 8 to 120 g/- carrier,
Preferably it is 10 to 100 g/-carrier, and when the amount of noble metal of group (b) supported is in the range of 0.1-4.0 g/-carrier, preferably 0.3-3.0 g/-carrier, the sulfate-forming ability is most suppressed, Moreover, it was discovered that the combustion behavior of particulate matter is good. In the present invention, the above-mentioned molybdate is specified, but other molybdate metal salts,
For example, it has been recognized that potassium molybdate, lithium molybdate, vanadium molybdate, etc. are undesirable due to the high scattering of molybdenum, and it has also been recognized that strontium molybdate, cobalt molybdate, etc. have poor combustion behavior of particulate matter. Ta. The inorganic bases used in the present invention include alumina, silica, titania, which are usually used as carrier bases,
Zirconia, silica-alumina, alumina-zirconia, alumina-titania, silica-titania, silica-zirconia, titania-zirconia and the like are preferably used, but are not limited thereto. The specific method for preparing the catalyst according to the present invention is as follows. As an example, the above-mentioned inorganic substrate is slurried into a three-dimensional structure having a gas filter structure (for example, ceramic foam, wire mesh, metal foam, sealed type ceramic honeycomb) and coated with wash to form a support layer. A compound containing at least one metal selected from the group consisting of platinum, rhodium, and palladium is supported in the form of a water-soluble or organic solvent (alcohol etc.) solution or dispersion by an impregnation or dipping method. Dry or after drying 300~
Fire at 500â. Next, a water-soluble or organic solvent-soluble salt of molybdenum is impregnated and supported, and after drying,
Bake at 300-500â. The fired product is impregnated with a water-soluble or organic solvent-soluble salt of barium or a water-soluble or organic solvent-soluble salt of lanthanum, dried, and then fired at 700 to 1000°C for 1 to 5 hours. The above compounds include inorganic compounds such as oxides, hydroxides, nitrates, carbonates, phosphates, sulfates, halides, and metal salts, and organic compounds such as carboxylates and complex compounds such as acetates and formates. It is preferable to use one that is easily soluble in water or an alcoholic organic solvent. Furthermore, the order in which the catalyst components are supported may be changed. Furthermore, it is also possible to adopt a method in which the inorganic base material and each catalyst component group are mixed in advance, and then washed, dried, and calcined to obtain a finished catalyst, and a compromise between these methods can also be adopted as appropriate. The form of the catalyst is not limited to the three-dimensional structure described above, but the catalyst component may be supported on a pellet-like structure shown as an inorganic base. The present invention will be described in more detail below with examples and comparative columns. Example 1 Commercially available cordierite foam (bulk density 0.35 g/
cm 3 , porosity 87.5%, volume 1.7), 1 kg of alumina powder is slurried and supported using a wet mill,
After shaking off the excess slurry and drying at 150°C for 3 hours, the product was fired at 500°C for 2 hours to obtain a cordierite foam having an ammina coat layer. Next, a nitric acid solution of dinitrodiammine platinum containing 12.86 g as platinum (Pt) and rhodium (Rh)
The foam was immersed in mixed solution 2 of an aqueous rhodium nitrate solution containing 1.286 g of rhodium, the excess solution was shaken off, and the foam was dried at 150°C for 3 hours and then fired at 500°C for 2 hours to form a foam containing platinum-rhodium. A cordierite foam with an alumina coat layer was obtained. Next, the foam was immersed in aqueous solution 2 containing 350.6 g of ammonium paramolybdate, the excess aqueous solution was shaken off, and the foam was dried at 150°C for 3 hours and then fired at 500°C for 2 hours to produce molybdenum (Mo)-Pt. A cordierite foam with an alumina coat layer containing -Rh was obtained. Next, aqueous solution 2 containing 507.2 g of barium acetate
The foam was immersed, the excess aqueous solution was shaken off, the foam was dried at 150°C for 3 hours, and then fired at 750°C for 2 hours to form barium molybdate (BaMoO 4 ).
A cordierite foam with an alumina coat layer containing BaMoO 4 , Pt, and Rh was obtained. The amount of Pt and Rh supported at this time was 0.90g/0.90g/
- carrier, 0.09 g/- carrier, and the amount of BaMoO 4 supported was 41.3 g/- carrier. The composition of the finished coating layer was 62.3% by weight of alumina, 36.8% by weight of BaMoO 4 , and Pt+Rh (Pt/Rt=10/
1) It was 0.89% by weight. Example 2 353 g of ammonium paramolybdate was dissolved in the ion-exchanged water from step 2, and added while stirring into an aqueous solution in which 41.65 g of barium chloride had been previously dissolved in the ion-exchanged water from step 2, and the precipitate formed was overwashed. Dry at 150â for 5 hours, then dry at 500â for 2 hours.
About 530g of BaMoO 4 powder was obtained by firing for a time. 472g of this powder and 800g of alumina powder were thoroughly mixed in a ball mill, then slurried in a wet mill, supported on cordierite foam 1.7, excess slurry was shaken off, dried at 150â for 3 hours, and then dried at 500â for 3 hours.
After firing for a period of time, a cordierite foam with an alumina coat layer containing BaMoO 4 was obtained. Next, Pt and Rh were supported by a method according to Example 1.
After drying at 150°C for 2 hours, it was fired at 750°C for 2 hours. The composition of the finished coat layer at this time is Example 1
The composition was almost the same. Example 3 A catalyst was prepared in the same manner as in Example 1 except that an aqueous solution of lantum nitrate La(NO 3 ) 3.6H 2 O was used instead of barium acetate .
-Support, lanthanum molybdate [La 2 (MoO 4 ) 3 ]
The supported amounts of Pt and Rh were 35.1 g/-carrier and 0.90 g/-carrier and 0.09 g/-carrier, respectively. The composition of the finished coating layer is Al 2 O 3 66.0% by weight,
La 2 (MoO 4 ) 3 33.1% by weight, Pt + Rh (Pt/Rh=10/
1) It was 0.94% by weight. Example 4 A catalyst was prepared in the same manner as in Example 2 except that Pd was used instead of Pt. The composition of the finished coat layer is 62.3% by weight of Al 2 O 3 ;
BaMoO 4 36.8% by weight, Pd+Rh (Pd/Rh=10/1)
It was 0.89% by weight. Example 5 Exactly the same as in Example 1 except that the cordierite foam was replaced with a sealed type honeycomb structure in which the adjacent holes on both end faces were closed differently to allow gas to pass through only through the partitions. A catalyst was prepared by the method described in . Example 6 Commercially available alumina pellets (3 to 6 mmÏ) 1.7
A catalyst was prepared by supporting Pt, Rt, and BaMoO 4 so as to have the composition of the finished coat layer of Example 1. Comparative Example 1 A catalyst was prepared in the same manner as in Example 1 except that Pt and Rh were not used, and a cordierite foam catalyst was obtained in which 70 g/- of Al 2 O 3 and 41.3 g/- of BaMoO 4 were supported. Comparative Example 2 A catalyst was prepared in the same manner as in Example 1 except that barium acetate was not used, and 70 g of Al 2 O 3 /
-Support, MoO 3 20g/-Support, Pt0.90g/
A cordierite foam was obtained in which each of the -carrier and Rh0.09g/-carrier was supported. Comparative Example 3 A catalyst was prepared in the same manner as in Example 1 except that potassium nitrate was used instead of barium acetate, and Al 2 O 3 70 g/- support and K 2 MoO 4 33.1 g/
-Support, Pt0.90g/-Support, Rh0.09g/-
Cordierite foams each supported on a carrier were obtained. Comparative Example 4 A catalyst was prepared in the same manner as in Example 1 except that potassium molybdate was used instead of ammonium paramolybdate and barium acetate was not used, and a catalyst having the same composition as Comparative Example 3 was obtained. Comparative Example 5 A catalyst was prepared in the same manner as in Example 1 except that the final calcination temperature was changed to 600°C. Example 7 The catalysts obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were evaluated using a 4-cylinder diesel engine with a displacement of 2300 c.c. Particulate capture was carried out for approximately 2 hours under the conditions of engine rotation speed 2500 rpm and torque 4.0 kgã»m, and then the torque was
The pressure drop in the catalyst layer was continuously recorded by increasing the pressure at 0.5 kg/m intervals every 5 minutes, and as the exhaust gas temperature rose on the catalyst, the pressure increase due to the accumulation of fine particles and the pressure drop due to combustion of the fine particles were measured. The temperature (Te) at which these are equal to the temperature (Ti) at which ignition and combustion occur and the pressure drop rapidly decreases was determined. Also 2500rpm, torque
The value of ÎP (mmHg/H) was determined by calculating the change in pressure drop per hour from a chart when capturing fine particles at 4.0 kg·m. In addition, the conversion rate of SO 2 to SO 3 was determined at an exhaust gas temperature of 450â.
I asked for it. The conversion rate of SO 2 is determined by the inlet gas and outlet gas.
The SO 2 concentration was analyzed using a non-dispersive infrared analyzer (NDIR method), and the conversion rate (%) of SO 2 was determined using the following formula. SO 2 conversion rate (%) = Inlet SO 2 concentration (ppm) â Outlet SO 2 concentration (
ppm)/Inlet SO 2 concentration (ppm) x 100 The results are shown in Table 1 below. Next, for each catalyst, 2500 rpm, torque 14 Kgã»m
Similar to the above test, SO 2
The conversion rate, Te, and Ti were determined, and the Mo residual rate of the tested catalyst was determined by fluorescent X-ray analysis. The results are shown in Table-2.
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Claims (1)
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ã®è£œæ³ã[Scope of Claims] 1. On a porous inorganic base supported on a refractory three-dimensional structure having a gas filter function, or on a porous inorganic base formed into a pellet, (a) (b) a compound of at least one metal selected from the group consisting of barium molybdate and lanthanum molybdate; and (b) at least one metal selected from the group consisting of platinum, rhodium, and palladium. A catalyst for purifying diesel engine exhaust gas. 2. The catalyst according to claim 1, wherein the compounds selected from groups (a) and (b) have a molar ratio of (a)/(b)=5 to 90. 3 The fire-resistant three-dimensional structure is ceramic foam,
The catalyst according to claim 1 or 2, which is a wire mesh, a metal foam, or a plugged ceramic honeycomb. 4. (a) Barium molybdate and molybdenum are placed on a porous inorganic base supported on a refractory three-dimensional structure having a gas filter function, or on a porous inorganic base formed into a pellet. A compound of at least one metal selected from the group consisting of lanthanum acid and (b) at least one metal selected from the group consisting of platinum, rhodium, and palladium is dispersed and supported in the air at 700 to 1000°C. A method for producing a catalyst for purifying diesel engine exhaust gas, which is characterized by heat treatment at a temperature within a range.
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JP59036255A JPS60183037A (en) | 1984-02-29 | 1984-02-29 | Exhaust gas purifying catalyst and its preparation |
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JP59036255A JPS60183037A (en) | 1984-02-29 | 1984-02-29 | Exhaust gas purifying catalyst and its preparation |
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JPS60183037A JPS60183037A (en) | 1985-09-18 |
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JP2001347168A (en) * | 2000-06-06 | 2001-12-18 | Toyota Motor Corp | Exhaust gas cleaning catalyst |
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