WO2008038834A1 - Produit chimique portant du rhodium et catalyseur du rhodium préparé à l'aide de celui-ci - Google Patents
Produit chimique portant du rhodium et catalyseur du rhodium préparé à l'aide de celui-ci Download PDFInfo
- Publication number
- WO2008038834A1 WO2008038834A1 PCT/JP2007/069415 JP2007069415W WO2008038834A1 WO 2008038834 A1 WO2008038834 A1 WO 2008038834A1 JP 2007069415 W JP2007069415 W JP 2007069415W WO 2008038834 A1 WO2008038834 A1 WO 2008038834A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rhodium
- chemical solution
- catalyst
- supporting
- organic base
- Prior art date
Links
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 88
- 239000010948 rhodium Substances 0.000 title claims abstract description 86
- 239000000126 substance Substances 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims description 70
- 150000007530 organic bases Chemical class 0.000 claims abstract description 29
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 28
- 230000008093 supporting effect Effects 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 238000011068 loading method Methods 0.000 description 39
- 239000010410 layer Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 238000000746 purification Methods 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000011247 coating layer Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004453 electron probe microanalysis Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 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 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 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 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940126701 oral medication Drugs 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- BJAARRARQJZURR-UHFFFAOYSA-N trimethylazanium;hydroxide Chemical compound O.CN(C)C BJAARRARQJZURR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/024—Multiple impregnation or coating
- B01J37/0242—Coating followed by impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1025—Rhodium
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
Definitions
- the present invention relates to a mouth-medium supporting chemical and a mouth-medium catalyst prepared using the chemical.
- a catalyst in which a noble metal such as platinum, rhodium, and palladium is coated on a support is used.
- a noble metal such as platinum, rhodium, and palladium
- guchijimu is particularly excellent in heat resistance compared to platinum and palladium. Therefore, it is particularly desirable in automobile exhaust gas purification reactions.
- the loading amount of the mouthpiece is 0.1 to 2 g per 1 L of the catalyst.
- rhodium is preferably concentrated in the vicinity of the surface layer of the washcoat layer from the viewpoint of contact efficiency with exhaust gas.
- Japanese Laid-Open Patent Publication No. 0 0-3 0 1 0 0 0 0 0 discloses a technique in which a noble metal such as rhodium is supported on the surface layer portion of a coating layer.
- the loading method used in this is time-consuming and cannot fully enjoy the benefits of high loading. Disclosure of the invention
- the method of impregnating and supporting the catalyst in the chemical as described above is common.
- the support is impregnated and supported in a nitric acid-based mouth solution which has been conventionally used for the preparation of a mouth catalyst
- the catalyst is not only supported on the surface of the catalyst coating layer but also is uniformly supported throughout. For this reason, it is difficult to localize the rhodium particles with respect to the outermost surface of the catalyst coat layer in contact with the exhaust gas.
- the number of oral dust particles in the catalyst that can actually contribute to the exhaust gas purification reaction in the catalyst decreased, and the purification performance of the oral catalyst obtained compared to the amount of rhodium used was not sufficient.
- the amount of the carrier can be adjusted by appropriately adjusting the amount. It was revealed that a chemical solution that can be highly supported on the coating layer can be obtained. Furthermore, it has been clarified that the loading efficiency is further improved by adjusting the pH of the chemical solution to be constant.
- the present invention easily supports a high load near the surface of the catalyst coating layer of the support.
- a rhodium-supporting chemical solution can be provided.
- rhodium-supporting chemical solution of the present invention When the rhodium-supporting chemical solution of the present invention is used, rhodium can be concentrated and supported in the vicinity of the outermost surface of the catalyst coat layer, which is frequently contacted with exhaust gas, specifically, within 20 im from the outermost surface. Rhodium can be used efficiently.
- the rhodium chemical solution of the present invention requires a step such as surface treatment of an inorganic oxide or a precursor thereof, as compared with the production method described in the above Japanese Patent Application Laid-Open No. Therefore, the catalyst coat layer can be easily formed on the support.
- rhodium particles can be concentrated in 85% or more within 20 m from the surface of the catalyst coat layer.
- the rhodium-supporting chemical solution of the present invention contains an appropriate amount of an organic base, so that rhodium particles are converted to acid points on the surface of a substrate such as monolith. It is thought that it can be adsorbed in order.
- the rhodium catalyst produced using the rhodium chemical solution of the present invention is dense with rhodium in the vicinity of the outermost surface of the catalyst coat layer as described above. Therefore, the conventional rhodium with the same rhodium content in the catalyst coat layer is used. Compared to the catalyst, it also excels in exhaust gas purification performance.
- Figure 1 shows the rhodium loading efficiency in the catalysts of Examples 1 to 3 and Comparative Examples 1 and 2 prepared using chemical solutions with rhodium concentrations of 2 g, 2.5 g, and 4.1 g per liter of catalyst volume. It is a graph which shows (%).
- the loading efficiency was calculated by impregnating and supporting the carrier once in the chemical solution, and then comparing the rhodium concentration of the chemical solution before and after loading using atomic absorption spectroscopy (AA).
- AA atomic absorption spectroscopy
- Figure 2 shows the loading efficiency and the tetramethylammonium hydroxide (TMAH) noro in the case of using a chemical solution with a rhodium concentration of 4. lg / L in Figure 1. It is a figure showing the relationship with the molar ratio of Jim.
- TMAH tetramethylammonium hydroxide
- FIG. 3 is a graph comparing the purification performance of the catalysts of Comparative Example 2 and Example 2.
- FIG. 4 is an EPMA data showing the rhodium loading distribution of the catalyst of Comparative Example 2 prepared by dipping and supporting in a rhodium loading chemical solution having a concentration of 0.75 g ZL.
- FIG. 5 is EPMA data showing the rhodium loading distribution of the catalyst of Example 2 prepared by dipping and supporting in a rhodium loading chemical solution having a concentration of 0.75 gZL.
- FIG. 6 is an EPMA data showing the rhodium loading distribution of the catalyst of Example 5 prepared by dipping in a rhodium loading chemical solution having a concentration of 0.75 g / L.
- the present invention provides a medicinal solution for carrying a mouth-medium characterized by containing a rhodium atom and an organic base in a molar ratio of 1 to 0.5 to 35.
- the rhodium contained in the rhodium-supporting chemical solution of the present invention can be obtained, for example, by dissolving oral dimethyl with hydrochloric acid, nitric acid or the like.
- the rhodium-supporting chemical solution of the present invention may contain other noble metal components such as platinum and palladium in addition to the rhodium atom depending on the application.
- the rhodium-supporting chemical solution of the present invention is based on rhodium atoms.
- the organic base is contained in a molar ratio of 0.5 to 35 times.
- the loading efficiency is deteriorated.
- the molar ratio is more than 35 times, the strength of the chemical solution becomes too strong due to a large amount of organic base.
- the carrying properties of the chemical solution to the carrier are lowered, and further, the amount of rhodium contained in the chemical solution is reduced.
- 5 to 35 moles, preferably 20 to 30 moles of organic base per atom of rhodium. can be used.
- the effect of such an organic base is related to the pH of the chemical solution itself in addition to the amount of the organic base used. Specifically, as will be described later, as the pH of the chemical solution becomes more acidic, rhodium is concentrated and supported near the surface of the catalyst layer, and the effect of the organic base increases. Therefore, when the pH of the chemical solution is set near acidic for the purpose of supporting rhodium more concentrated in the vicinity of the catalyst coat layer, the molar ratio of the organic base is 1.5 to 20 mol, depending on the case. Even if it is about 5 to 15 mol, a more excellent surface concentration supporting effect can be exhibited.
- the pH of the rhodium-supporting chemical solution of the present invention can be appropriately changed to acidic or alkaline from the viewpoint of the stability of the chemical solution and the prevention of precipitation.
- the pH of the chemical solution is preferably 4 or less or 9 or more.
- the supported rhodium is preferably as close to the surface of the catalyst coat layer as possible (for example, within 10 m from the outermost surface).
- the chemical solution of the present invention is preferably acidic, specifically about pH 4 or less, preferably about pH 3 or less.
- the lower limit of the pH will be about 1.Q
- rhodium is preferably dispersed and supported to some extent near the surface of the catalyst coating layer.
- the Al strength is set to be not less than pH 10 and more preferably not less than pH 12.
- the upper limit of these ⁇ H should be about 14.
- the carrier means alumina, zirconia, ceria, and composite oxides thereof coated on a substrate such as a honeycomb, and also includes silica, titania, and zeolite. It is possible.
- the carrier may be a material coated on a substrate such as a honeycomb.
- the coating can be performed by a general method in the production of a catalyst, for example, an impregnation support method. Specifically, it can be carried out by impregnating the above carrier in a chemical solution for supporting mouth-drum, adsorbing the mouth-drum particles on the surface of the carrier, and then drying, firing and reducing.
- the loading efficiency of the impregnation loading method is determined by calculating the concentration of rhodium remaining in the mouth-drum carrying chemical solution after loading from the mouth-drum concentration in the mouth-drum carrying chemical solution before loading by atomic absorption spectroscopy (AA). Calculated by subtracting.
- the rhodium-supporting chemical solution of the present invention can support rhodium that is concentrated within 20 xm from the surface of the catalyst coat layer. This is considered to be due to the start of adsorption of the rhodium compound from the acid point on the surface of the coat layer by adding an appropriate amount of organic base.
- the rhodium loading width may vary depending on the chemical
- the rhodium-carrying chemical solution of the present invention can be concentrated on the surface of the catalyst coat layer corresponding to the contact surface with the exhaust gas and can be supported on a catalyst for exhaust gas purification.
- the present invention is not limited to the exhaust gas purifying catalyst, and can be applied to any catalyst that requires rhodium to be supported on the surface of the carrier with high efficiency.
- a rhodium nitrate solution containing 50 g of rhodium per liter was prepared.
- tetramethylammonium hydroxide as an organic base
- rhodium atoms and tetramethylammonium hydroxide are added.
- a rhodium-supporting chemical solution was prepared so that the mixing ratio was 1:10 (rhodium: tetramethylammonium hydroxide).
- the stirring operation was performed for 30 minutes or longer.
- the measured value of PH of the drug solution was in the range of about 13 to 14.
- rhodium was impregnated and supported on the support using the rhodium supporting liquid.
- the carrier is oxidized from alumina, zirconia, lanthanum, etc. wash-coated on a monolith substrate made of cordierite. A mixture of products was used.
- a rhodium-supported catalyst was prepared by passing through drying, calcination, and reduction processes.
- a rhodium-supporting chemical solution was prepared in the same manner as in Example 1 except that the mixing ratio of rhodium and tetramethylammonium hydroxide was 1:20 in molar ratio.
- the measured value of pH of the chemical solution was in the range of about 13 to 14.
- a rhodium-supporting chemical solution was prepared in the same manner as in Example 1 except that the mixing ratio of rhodium and tetramethylammonium hydroxide was 1:30 in molar ratio.
- the measured value of pH of the chemical solution was in the range of about 13 to 14.
- a rhodium-supporting chemical solution was prepared in the same manner as in Example 1 except that the mixing ratio of rhodium and tetramethylammonium hydroxide was 1: 1.5 in molar ratio.
- the chemical solution had a pH of about 2.
- Example 2 Except for the addition of 8.5 moles of nitric acid per mole of rhodium, the mixture ratio of rhodium atoms and tetramethylammonium hydroxide was 1:10 (rhodium: hydroxylated) in the same manner as in Example 1.
- a chemical solution for supporting rhodium of tetramethylammonium was prepared.
- the chemical solution had a pH of about 2.
- a rhodium-supporting chemical solution was prepared in the same manner as in Example 1 except that the mixing ratio of rhodium and tetramethylammonium hydroxide was 1:40 in molar ratio.
- the measured value of PH of the chemical solution is 14 or more. I got it.
- a rhodium nitrate solution prepared according to the procedure described in Example 1 was used as a rhodium-supporting chemical solution as a control containing no organic base.
- the measured pH value of the chemical solution was about 0.5.
- Examples 1 to 5 and Comparative Examples 1 and 2 are diluted with pure water, and the concentrations thereof are 2 g, 2.5 g, and 4 g per liter of the supported carrier volume. Adjusted.
- rhodium was supported by impregnating the carrier with a mixture of oxides made of alumina, zirconia, lanthanum, etc. wash-coated on a monolith substrate made of cordierite. The support after the impregnation supporting step was dried, calcined and reduced to prepare a rhodium supported catalyst.
- the loading efficiency of rhodium in such chemicals is determined by measuring the rhodium concentration in the oral chemical solution before and after impregnating the carrier with atomic absorption spectrometry (AA) analysis based on the following formula. Calculated (Hitachi Z— 5 3 1 0):
- Figure 1 shows the loading efficiency results.
- the catalyst prepared using the chemical solutions of Comparative Examples 1 and 2 Rhodium loading efficiency is 30 ⁇ 4 compared with 2g / L About 0%, especially the 4 I g ZL concentration of Comparative Example 1 decreased by about 60%.
- the catalysts prepared using the chemical solutions of Examples 1 to 5 showed almost no reduction in the loading efficiency even when the mouth zinc concentration was as high as 4.1 g / L.
- the loading efficiency of the chemical solutions of Examples 2, 3 and 5 is high at any concentration, and it can be seen that the increase in the amount of organic base contributes to the improvement of the loading efficiency. From these results, it has been clarified that the rhodium-supporting chemical solutions of Examples 1 to 5 can efficiently support rhodium on a carrier even at a high concentration compared to conventional products.
- Figure 2 shows the relationship between the loading efficiency and the organic base / rhodium molar ratio when the 4.1 lg rhodium / L chemical solution in Fig. 1 is used.
- FIG. 2 shows that there is a certain relationship between the range of the molar ratio of the organic base / rhodium used in the present invention and the loading efficiency of the rhodium. Specifically, when the organic base is contained in an amount of 0.5 to 35 times the molar ratio with respect to the zinc atom (Examples 1 to 5), good loading efficiency can be obtained. On the other hand, when the organic base / rhodium molar ratio is less than 0.5 as in the comparative example, the loading efficiency is greatly reduced.
- the loading efficiency is further remarkably reduced. This is because the rhodium concentration in the chemical solution is relatively lowered due to the increase in the organic base, so that a large amount of organic base is required to prepare a high concentration rhodium-supporting chemical solution of 4.lg rhodium / L. As a result, the presence of a large amount of organic base is considered to have an adverse effect on rhodium loading.
- rhodium-supported catalysts prepared using the chemical solution of the present invention (Examples 2 and 5) were prepared using a chemical solution for supporting a rhodium to which no organic base was added (Comparative Example). Compared to 2), T 50 was lower for all gases, indicating that the purification performance was good.
- the catalysts of Examples 2 and 5 have improved exhaust gas purification performance by concentrating and supporting rhodium at the exhaust gas contact portion in the catalyst as compared with Comparative Example 2. .
- a catalyst having an excellent purification performance can be produced with a small number of impregnation-supporting steps.
Landscapes
- 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)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07829154A EP2075061A4 (en) | 2006-09-29 | 2007-09-27 | CHEMICAL CARRYING RHODIUM AND CATALYST OF RHODIUM PREPARED THEREBY |
US12/443,340 US8691721B2 (en) | 2006-09-29 | 2007-09-27 | Rhodium-loading solution and rhodium catalyst prepared using the same |
JP2008509854A JP5582700B2 (ja) | 2006-09-29 | 2007-09-27 | ロジウム担持用薬液及び当該薬液を用いて調製したロジウム触媒 |
CN200780019865.0A CN101454077B (zh) | 2006-09-29 | 2007-09-27 | 铑担载用溶液及用该溶液制备的铑催化剂 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006-267911 | 2006-09-29 | ||
JP2006267911 | 2006-09-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008038834A1 true WO2008038834A1 (fr) | 2008-04-03 |
Family
ID=39230260
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2007/069415 WO2008038834A1 (fr) | 2006-09-29 | 2007-09-27 | Produit chimique portant du rhodium et catalyseur du rhodium préparé à l'aide de celui-ci |
Country Status (5)
Country | Link |
---|---|
US (1) | US8691721B2 (ja) |
EP (1) | EP2075061A4 (ja) |
JP (1) | JP5582700B2 (ja) |
CN (1) | CN101454077B (ja) |
WO (1) | WO2008038834A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019163446A1 (ja) * | 2018-02-21 | 2019-08-29 | 株式会社キャタラー | 排ガス浄化触媒装置 |
JP2020138162A (ja) * | 2019-02-28 | 2020-09-03 | 国立研究開発法人産業技術総合研究所 | 触媒製造用金属錯体分散液及び触媒の製造方法 |
JPWO2019163403A1 (ja) * | 2018-02-21 | 2021-01-14 | 株式会社キャタラー | 排ガス浄化触媒装置 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2968578B1 (fr) * | 2010-12-14 | 2013-06-28 | IFP Energies Nouvelles | Nouveau procede de preparation de catalyseurs a base de palladium et utilisation de ces catalyseurs en hydrogenation selective |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05293376A (ja) * | 1992-04-15 | 1993-11-09 | Nissan Motor Co Ltd | 排ガス浄化用触媒及び排ガス浄化方法 |
JP2000279818A (ja) * | 1999-03-29 | 2000-10-10 | Tanaka Kikinzoku Kogyo Kk | 触媒金属コロイド |
JP2000301000A (ja) | 1999-04-23 | 2000-10-31 | Toyota Central Res & Dev Lab Inc | 排ガス浄化用触媒及びその製造方法 |
JP2002001119A (ja) * | 2000-06-16 | 2002-01-08 | Tanaka Kikinzoku Kogyo Kk | 排ガス浄化触媒の製造方法及びその方法により製造される排ガス浄化触媒 |
JP2002282692A (ja) | 2001-03-26 | 2002-10-02 | Toyota Motor Corp | 排ガス浄化用触媒 |
JP2004267961A (ja) * | 2003-03-11 | 2004-09-30 | Tanaka Kikinzoku Kogyo Kk | 多元系金属コロイドを用いて製造される触媒 |
JP2005314739A (ja) | 2004-04-28 | 2005-11-10 | Cataler Corp | 貴金属溶液及び貴金属触媒の製造方法 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
HU177860B (en) * | 1979-05-22 | 1982-01-28 | Mta Koezponti Hivatala | Method for producing carrier metal catalyzers |
US4737483A (en) * | 1986-09-22 | 1988-04-12 | Uop Inc. | Trimetallic reforming catalyst |
US4791087A (en) * | 1986-09-22 | 1988-12-13 | Uop Inc. | Trimetallic reforming catalyst |
US4923595A (en) * | 1986-09-22 | 1990-05-08 | Uop | Trimetallic reforming catalyst |
US4865719A (en) * | 1986-09-22 | 1989-09-12 | Uop | Trimetallic reforming catalyst |
US4714539A (en) * | 1986-09-22 | 1987-12-22 | Uop Inc. | Reforming of hydrocarbons utilizing a trimetallic catalyst |
US4714538A (en) * | 1986-09-22 | 1987-12-22 | Uop Inc. | Trimetallic reforming catalyst |
US4714540A (en) * | 1986-09-22 | 1987-12-22 | Uop Inc. | Reforming of hydrocarbons utilizing a trimetallic catalyst |
US4677094A (en) * | 1986-09-22 | 1987-06-30 | Uop Inc. | Trimetallic reforming catalyst |
US5376610A (en) * | 1992-04-15 | 1994-12-27 | Nissan Motor Co., Ltd. | Catalyst for exhaust gas purification and method for exhaust gas purification |
DE19827844A1 (de) * | 1998-06-23 | 1999-12-30 | Aventis Res & Tech Gmbh & Co | Verfahren zur Herstellung von Schalenkatalysatoren durch CVD-Beschichtung |
JP3646076B2 (ja) * | 2001-06-19 | 2005-05-11 | 直本工業株式会社 | オールスチームアイロン |
ITMI20012267A1 (it) * | 2001-10-29 | 2003-04-29 | Chemi Spa | Preparazione ed uso di un catalizzatore eterogeneo per l'idrogenerazione di un doppio legame di un composto carbonilico b-insaturo |
JP3776086B2 (ja) * | 2003-01-29 | 2006-05-17 | タキゲン製造株式会社 | 可変式シリンダー錠 |
JP2005097642A (ja) * | 2003-09-22 | 2005-04-14 | Tanaka Kikinzoku Kogyo Kk | 貴金属−金属酸化物複合クラスター |
US20050113614A1 (en) * | 2003-11-24 | 2005-05-26 | Lowe David M. | Catalyst and process for selective hydrogenation |
GB0413771D0 (en) * | 2004-06-21 | 2004-07-21 | Johnson Matthey Plc | Metal oxide sols |
JP2006043654A (ja) * | 2004-08-09 | 2006-02-16 | Toyota Motor Corp | 排ガス浄化触媒及びその製造方法 |
WO2006057067A1 (ja) * | 2004-11-25 | 2006-06-01 | Cataler Corporation | 排ガス浄化用触媒 |
US20080063594A1 (en) * | 2006-09-13 | 2008-03-13 | Formfactor, Inc. | Rhodium sulfate production for rhodium plating |
-
2007
- 2007-09-27 JP JP2008509854A patent/JP5582700B2/ja not_active Expired - Fee Related
- 2007-09-27 WO PCT/JP2007/069415 patent/WO2008038834A1/ja active Application Filing
- 2007-09-27 CN CN200780019865.0A patent/CN101454077B/zh not_active Expired - Fee Related
- 2007-09-27 EP EP07829154A patent/EP2075061A4/en not_active Withdrawn
- 2007-09-27 US US12/443,340 patent/US8691721B2/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05293376A (ja) * | 1992-04-15 | 1993-11-09 | Nissan Motor Co Ltd | 排ガス浄化用触媒及び排ガス浄化方法 |
JP2000279818A (ja) * | 1999-03-29 | 2000-10-10 | Tanaka Kikinzoku Kogyo Kk | 触媒金属コロイド |
JP2000301000A (ja) | 1999-04-23 | 2000-10-31 | Toyota Central Res & Dev Lab Inc | 排ガス浄化用触媒及びその製造方法 |
JP2002001119A (ja) * | 2000-06-16 | 2002-01-08 | Tanaka Kikinzoku Kogyo Kk | 排ガス浄化触媒の製造方法及びその方法により製造される排ガス浄化触媒 |
JP2002282692A (ja) | 2001-03-26 | 2002-10-02 | Toyota Motor Corp | 排ガス浄化用触媒 |
JP2004267961A (ja) * | 2003-03-11 | 2004-09-30 | Tanaka Kikinzoku Kogyo Kk | 多元系金属コロイドを用いて製造される触媒 |
JP2005314739A (ja) | 2004-04-28 | 2005-11-10 | Cataler Corp | 貴金属溶液及び貴金属触媒の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2075061A4 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019163446A1 (ja) * | 2018-02-21 | 2019-08-29 | 株式会社キャタラー | 排ガス浄化触媒装置 |
JPWO2019163446A1 (ja) * | 2018-02-21 | 2021-01-07 | 株式会社キャタラー | 排ガス浄化触媒装置 |
JPWO2019163403A1 (ja) * | 2018-02-21 | 2021-01-14 | 株式会社キャタラー | 排ガス浄化触媒装置 |
JP7017621B2 (ja) | 2018-02-21 | 2022-02-08 | 株式会社キャタラー | 排ガス浄化触媒装置 |
US11524285B2 (en) | 2018-02-21 | 2022-12-13 | Cataler Corporation | Exhaust gas purification catalyst device |
US11633724B2 (en) | 2018-02-21 | 2023-04-25 | Cataler Corporation | Methods for exhaust gas purification |
JP2020138162A (ja) * | 2019-02-28 | 2020-09-03 | 国立研究開発法人産業技術総合研究所 | 触媒製造用金属錯体分散液及び触媒の製造方法 |
JP7228157B2 (ja) | 2019-02-28 | 2023-02-24 | 国立研究開発法人産業技術総合研究所 | 触媒製造用金属錯体分散液及び触媒の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2008038834A1 (ja) | 2010-01-28 |
EP2075061A1 (en) | 2009-07-01 |
US20100075841A1 (en) | 2010-03-25 |
JP5582700B2 (ja) | 2014-09-03 |
EP2075061A4 (en) | 2011-10-12 |
CN101454077A (zh) | 2009-06-10 |
CN101454077B (zh) | 2014-02-26 |
US8691721B2 (en) | 2014-04-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6871178B2 (ja) | Scrシステム内で先頭になるように設計されたアンモニアスリップ触媒 | |
JP5373255B2 (ja) | NOx還元触媒、NOx還元触媒システム、及びNOx還元方法 | |
KR101974704B1 (ko) | 선택적 암모니아 산화를 위한 이원기능 촉매 | |
CN107262090B (zh) | 一体化SCR和AMOx催化剂*** | |
EP2656913A1 (en) | A method for manufacturing a catalyst comprising copper CHA zeolite catalysts | |
JP2018528847A (ja) | 排気システム用の亜酸化窒素除去触媒 | |
JPH0838897A (ja) | 排気ガス浄化用触媒の製造方法 | |
JP2004512162A (ja) | Co、vocおよびハロゲン化有機物の放出物を消失させる触媒 | |
EP2611536A1 (en) | Catalyst for gasoline lean burn engines with improved nh3-formation activity | |
US20160144344A1 (en) | Exhaust gas purifying catalyst | |
US20020132730A1 (en) | Catalytic metal plate | |
WO2008038834A1 (fr) | Produit chimique portant du rhodium et catalyseur du rhodium préparé à l'aide de celui-ci | |
JPH05237390A (ja) | 排気ガス浄化用触媒 | |
JPH11276907A (ja) | 排気ガス浄化用触媒及びその製造方法 | |
JPH07108172A (ja) | 排気ガス浄化用触媒及びその製造方法 | |
JP3488487B2 (ja) | 排気ガス浄化方法 | |
JP6126858B2 (ja) | 内燃機関の排ガス浄化装置 | |
JP2000197819A (ja) | 排ガス浄化材及びその製造方法 | |
JP4106762B2 (ja) | 排気ガス浄化用触媒装置及び浄化方法 | |
JP2000042369A (ja) | 内燃機関の排ガス浄化装置,排ガス浄化方法及び排ガス浄化触媒 | |
JPH1176819A (ja) | 排ガス浄化用触媒 | |
US20230001387A1 (en) | Catalyst for simultaneously inhibiting emission of ammonia and nitrous oxide | |
JP2001058131A (ja) | 排ガス浄化用触媒 | |
JP3695654B2 (ja) | 排気ガス浄化用触媒の製造方法 | |
JP2000024515A (ja) | 排ガス浄化用触媒及びその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200780019865.0 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 2008509854 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07829154 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007829154 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12443340 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |