CN1077806C - Air purifying catalyst carrying noble metal particle and its preparing method - Google Patents
Air purifying catalyst carrying noble metal particle and its preparing method Download PDFInfo
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- CN1077806C CN1077806C CN96119452A CN96119452A CN1077806C CN 1077806 C CN1077806 C CN 1077806C CN 96119452 A CN96119452 A CN 96119452A CN 96119452 A CN96119452 A CN 96119452A CN 1077806 C CN1077806 C CN 1077806C
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Abstract
The present invention relates to an atmospheric cleaning catalyst containing platinum palladium oxide particles, which is composed of substrate and Al2O3 coating, wherein porous honeycomb ceramics is used as the substrate, and the Al2O3 coating carries noble metal oxide. The catalyst has the compositions that the weight of the Al2O3 coating composition containing the noble metal and metal oxide is 60 to 180 grams per litre, the weight of the noble metal Pt and the Pd is 0.8 to 1.4 gram, and the metal oxide is metal oxide particles of which the average particle diameters are 0.3 to 25 mu m. The catalyst is especially suitable for being used as a three-way catalyst for purifying tail gas emitted from vehicles. The present invention has high activity at low temperature and outstanding high-temperature endurance and stability. The present invention is characterized in that active composition without a Rh element still keeps the performance of an exhaust gas purified 'three-way' catalyst.
Description
The present invention is a kind of Catalysts and its preparation method that is used for the cleaning atmospheric pollution thing, particularly can eliminate the hydrocarbons (HC) in the I. C. engine exhaust simultaneously, carbon monoxide (CO), what is called " triple effect " catalyst and the preparation method of nitrogen oxide (NOx).
Purification catalyst for automobile exhaust has the research and development history of three more than ten years, and the catalyst that is used for vehicle discharging purifier the earliest is for being soaked with Pt, the Al of Pd
2O
3Bead, the eighties develop into and scribble Al on the ceramic honey comb
2O
3Coating is a carrier, supporting Pt, and Pd is an active constituent, and its activity mainly shows CO, and the elimination performance of two kinds of pernicious gases of HC is referred to as meaning " two imitate " catalyst or combustion catalyst usually.Along with severization to the automobile emission restriction, begin to occur and can eliminate CO simultaneously from the eighties, HC, new " triple effect " catalyst (TWC) of three kinds of pollutants of NOx, and become the main flow that current purification catalyst for automobile exhaust develops.Its active constituent of existing " triple effect " catalyst is Pt, Rh or Pt, Pd, Rh, practical " triple effect " catalyst in for example typical Europe is Pt, Rh, its bullion content is 1.24～1.41 gram/liters, (draws from " Ctalysis and Automotive pollution Control " 81-95.Proceedings of the First International Sympolium Brussels.September 8-11 1986) with Pt, Pd, Rh noble metal are that the patent of " triple effect " catalyst activity component is a lot.Representational work has: USP4,868,149,4,407,738, DEP4204421.9,4003939.0, EP0393612,0251708,0427493A2, JP18219/87 (CN88100589A), JP230026/87 (CN87106740A), JP90310/88 (CN1038222A), JP90311/88 and spy open clear 63-54940,61-11147, CN1087031A.Though above-mentioned catalyst is had nothing in common with each other in preparation method and noble metal dosage, its common ground is all to use the effective ingredient of Rh element as reducing NOx.Since noble metal resource Pt, Pd, the shortage of Rh, the particularly feedback of Rh resource are weary, and early existing many researchers begin to pay attention to developing the new catalyst of non-precious metal catalyst or minimizing noble metal dosage.E.I.Du Pont Company is at USP3, the ABO in 897,367
3Type perovskite type catalyst and similar afterwards work thereof all do not get practicability owing to the weakness of sulfur tolerance.After this noble metal---base metal composite catalyst that has many work to concentrate on the position in the alternative B position of small amount of precious metals and constitute.This class work has: USP4, and 134,852,4,748,143, and a large amount of Chinese patent CN1074629A, 1072107A, 1060793A, 1087034A; It is the ABO of active constituent that these catalyst common ground are to use rare earths and transition group base metal
3The perovskite structure catalyst, this class catalyst sulfur resistance and anti-high heat aging performance are relatively poor, may show below 800 ℃ CO, HC, the triple effect performance that NOx purifies, but lost reducing power to NOx at 1100 ℃ of aging back base tables, only finally shown as CO, HC has " two imitate " catalyst or the title oxidation catalyst of detergent power.
The work close with the present invention has DEP3736810.9, number is CN1032749A in Chinese patents, and its principal character is at Pt, on the Pd oxidation catalyst basis with Al
2O
3CeO in the carrier
2Content reach 25～52% (Wt), use common immersion process for preparing, soak Pd after soaking Pt earlier, catalyst is lived through the oxygen reduction processing, this method complex process, the cost height, high high-temp stability is poor.With another close work of the present invention be JP1827/87,90310/88,90311/88, DEP4003939.0, use particle method technology of preparing in the described catalyst preparation process, but catalyst activity component is not broken away from the active constituent for NOx reduction in " triple effect " catalyst with Rh yet.
The object of the present invention is to provide a kind of novel atmospheric cleaning with catalyst and preparation method.This catalyst can be eliminated CO simultaneously, HC, and three kinds of pollutants of NOx, and do not use Rh in the active constituent, and only with two kinds of component Pt, Pd just can reach the function of " triple effect " catalyst usually, and this catalyst is particularly suitable for the cleaning catalyst as motor vehicle emission tail gas.
For achieving the above object, the intrinsic carrier of catalyst of the present invention adopts the oxide fine particle of the stabilisation on high surface, and the active component in the catalyst is precious metals pt and the Pd that is supported on the particulate, constitutes the particulate supported catalyst, and this catalyst is sneaked into Al
2O
3Directly prepare practical atmospheric cleaning catalyst with the kiss-coating method in the coating.Omit the integral honeycomb pottery in its preparation and hung Al
2O
3Soak the process of catalyst activity component after the coating again, thereby simplified production technology.And the Al in the coating
2O
3Existing be the carrier of catalyst again but provide the support coating of gas passage, make catalyst have good activity and reach purpose of the present invention to particle catalyst.
Specifically the intrinsic carrier of catalyst of the present invention is to exist with the oxide microparticle state, and the particulate average diameter is at 0.3～25 μ m.Comprise CeO in the oxide fine particle
2, La
2O
3, ZrO
2, Al
2O
3Or SiO
2In one or both, wherein the preferably is CeO
2Particulate or close CeO
2Mixed oxide.Oxide is with containing Ce, La, and Zr, the nitrate of Al or Si, acylate, carbonate or hydroxide direct heat are decomposed or are made sediment after roasting makes with the ammonium ion coprecipitation method, and its specific area is at 50～120m
2/ g.Also available zeolite, for example the ZSM-5 zeolite microparticles replaces oxide fine particle.
Oxide fine particle of the present invention must use behind the modification agent upgrading, modification agent comprises Zr, Mg, Ce, La, the aqueous solution of the soluble-salt of Y or Ca, roasting again behind dipping or spraying evaporate to dryness, make on the oxide fine particle surface and form composite oxides, in the carrier particles behind the upgrading, the ratio of the metallic atom of oxide is 1: 1.5～8 in modification agent metallic atom and the particulate.
Catalyst activity component of the present invention is Pt and Pd, and with the aqueous solution of soluble-salt dipping or be sprayed on the upgrading particulate, drying obtains microgranular catalyst after the roasting, and wherein Pt and Pd mole ratio are 1: 1～16.The weight of two kinds of noble metals in particle catalyst accounts for 1～25%, 3～5% being the best, two kinds of noble metals can be the mixed solution mode or respectively impregnation method be supported on one or both upgrading chloride particulates.
Air cleaning Preparation of catalysts for practicality of the present invention is above-mentioned particle to be blended into by multiple refractory oxides grind the Al that forms
2O
3Be to constitute mixed serum in the glue of leading under vacuum, to be coated in the duct of ceramic honey comb, behind the unnecessary glue in stripping duct, integral catalyzer is made in dry and roasting, the material of described honeycomb ceramic body as catalyst substrates can be a cordierite, mullite, Alpha-alumina, zirconia, silica etc., wherein with 200～600 holes/time
2Honeycomb ceramic body is best.The Al that contains particle catalyst
2O
3The weight of coating in practical catalyst is 60～180 gram/liters, and 80～120 gram/liters are best.The particle catalyst particle is at butt Al
2O
3Account for 10～30% in the coating.
Above-mentioned Al
2O
3The coating glue is by Al
2O
3: BaO: MgO=30～55: 2～4: 2～4 ratios are mixed, and add water and nitric acid in ball mill, and adjust pH is 3～4, and wearing into average grain diameter is 3～6 μ m, and viscosity is the glue of 1～4 pascal second.
Method for preparing catalyst of the present invention carries out according to the following steps:
1. the preparation of metal oxide microparticle (intrinsic carrier)
Get Ce, Zr, La, one or both solubility salts in Al or the Si element prepare metal oxide or composite oxide particle by direct decomposition or with the ammonium salt coprecipitation method through roasting.Thermal decomposition and roasting were carried out under 400～700 ℃ 1～10 hour, and particulate technology control mean particle diameter routinely is in 0.3～25 mu m range.
2. the modification of metal oxide microparticle
The modification agent of choosing with metal oxide different metal element contains Zr, Ce, La, Mg, one or more solubility salts of Y or Ca element, be supported on the metal oxide microparticle of above-mentioned 1 preparation with dipping or spraying process, behind the drying evaporate to dryness, under 400～700 ℃, carry out roasting 1～10 hour, but this process repeated multiple times, until promoter metal liquid is all loaded in the metal oxide microparticle, grind to form the particulate of particle diameter 1～5 μ m.
3. supporting Pt, the catalyst particles preparation of Pd
Preparation contains the aqueous solution of platinum and palladium respectively, get upgrading oxide fine particle one or both soak or flood altogether or spray arbitrary above-mentioned precious metal solution with dividing, through air-dry, 80～120 ℃ of dryings 1～10 hour, 400～700 ℃ of roastings grind to form 0.5～25 μ m particle after 1～10 hour, make the metal oxide microparticle of platiniferous palladium.Another method for making of the present invention is that Pt is loaded on separately on a kind of particulate, and Pd loads on separately on another particulate, and two kinds of particulates mix the back by a certain percentage to be used.
4. the preparation of aluminum oxide coating layer glue
Get Al
2O
3, Ba and Mg oxide or salt mix in proportion, add H
2O and HNO
3It is that＜5 μ m viscosity are 1～4 pascal second that conciliation pH3～4 ball millings become average grain diameter.
5. atmospheric cleaning Preparation of catalysts
The above-mentioned catalyst particles that takes by weighing a certain amount of platiniferous palladium joins in the aluminum oxide coating layer glue and mixes, with honeycomb ceramic body under vacuum with above-mentioned mixed glue solution kiss-coating, soaked 1～30 minute, blow down unnecessary glue in the duct, 80～120 ℃ of dryings, 600～1000 ℃ of roastings 1～10 hour, repetitive operation one or repeatedly, 500～600 ℃ of calcination activations 1～5 hour, make the integral honeycomb ceramic catalyst at last.It is 60～180 gram/liters in the catalyst block that this coating is calculated with butt.Catalyst particles accounts for 10～30% (butts) of coating, and it is 0.8～1.4 gram that every liter catalyst contains noble metal platinum palladium total amount.Above-mentioned vacuum gluing can carry out according to a conventional method.
Below by embodiment the present invention is further specified.
Example 1
Take by weighing Ce (NO
3)
39H
2O500 gram, 200 ℃ of roastings 1 hour, 450 ℃ 1 hour, make average grain diameter 2～4 μ m, have surface area 93m
2The CeO of/g
2Particulate.124.7 gram Zr (NO
3)
45H
2The O water join the solution of 41.4% concentration, earlier with part solution impregnation 100 gram CeO
2Particulate, 60 ℃ of evaporates to dryness or dry in the shade, 120 ℃ of dryings 2 hours, roasting is 5 hours in 300～500 ℃ of air, and the solution of repeated impregnations remainder loads on 100 gram CeO up to 124.7 gram zirconium nitrates
2On, this (Zr/CeO
2) Zr and Ce atomic ratio are 1: 2 in the particle.Take by weighing again; 62 gram H
2PtCl
66H
2O and 4.55 gram PdCl
2Soluble in water altogether, with 100 gram (Zr/CrO
2) particle immerses this solution, through 120 ℃ of dryings 2 hours, in 200 ℃ of air 1 hour, 400 ℃ 1 hour, 600 ℃ of roastings in 3 hours, grinding to form average grain diameter is 0.5～20 μ m, makes the catalyst particles that the platiniferous palladium is 3.93% (wt).
Take by weighing 180 gram Al
2O
3H
2O, 230 gram Al (OH)
3, 300 gram γ-Al
2O
3(γ-the Al after 1000 ℃ of roastings
2O
3), aluminum nitrate, barium nitrate, each 40 gram of magnesium carbonate, 2500mlH
2O, 50mlHNO
3(67% concentration) ball milling 15～20 hours as the aluminium oxide glue, takes by weighing 2600ml when average grain diameter is＜5 μ m, with the above-mentioned (Pt+PdO/Zr/CeO of 180 grams
2Catalyst particles is sneaked into back ball milling 5 hours, and it is 2 pascal seconds that thin up is regulated viscosity, get 300～400 holes/cun
2Put into above-mentioned glue after ceramic honey comb block 1.2 liters were found time 10 minutes and apply in impregnation goes out, behind the glue, dried 2 hours for 120 ℃ in the blowing duct, 500 ℃ 1 hour, 800 ℃ 3 hours, repeat above-mentioned kiss-coating once, became catalyst (A) in 3 hours at 600 ℃ of calcination activations.
Example 2
According to the method for example 1, replace zirconium nitrate to CeO with the magnesium nitrate solution of 40% concentration
2Particles modified, prepare magnesium-modified (Mg/CeO
2) particulate replacement (Zr/CeO
2), all the other are constant, prepare catalyst (B).(Mg: Ce atomic ratio 1: 2).
Example 3
According to the preparation method of example 1, with the cerium oxide particulate (Zr/CeO of 100 gram modified zirconias
2) be divided into each 50 gram, be 2.9% solution and the solution dip-coating that contains palladium 5.8% with platiniferous respectively, prepare two kinds of catalyst particles, to mix the back and replace its modified zirconia cerium oxide catalyst particle that soaks of platinum palladium, all the other steps are constant, prepare catalyst (C).
Example 4
Get the particulate (Zr/CeO that uses in the example 1
2) 50 grams, get (the Mg/CeO that uses in the example 2
2) 50 grams; Use platinum solution and the dip-coating of palladium solution in the example 3 respectively, prepare two kinds of catalyst particles: the platinum catalyst particulate of modified zirconia cerium oxide and magnesium-modified cerium oxide palladium-containing catalyst particulate; After two kinds of particulates are mixed, make catalyst (D) according to the preparation method of example 1.
Example 5
According to the preparation method of example 1, replace zirconium nitrate that cerium oxide is carried out upgrading with lanthanum nitrate, make (La/CeO
2) particulate (La: the Ce atomic ratio is 1: 2), replace (the Mg/CeO in the example 4
2) particulate make the palladium-containing catalyst grain of the modified oxidized cerium of lanthanum and 50 grams again with example 4 in platinum catalyst particulate 50 gram mix use, all the other steps are identical, prepare catalyst (E).
Example 6
The palladium solution of getting in the example 3 adds magnesium nitrate, and the solution dip-coating 50 that was mixed with palladium and magnesium mole ratio and is 1: 10 restrains (Zr/CeO
2) make the catalyst particles that contains palladium magnesium, again with example 4 in (the Zr/CeO of dip-coating platinum
2) catalyst particles mixing use, all the other steps such as example 3 are prepared catalyst (F).
Example 7
According to the method for example 6, with containing Pd, (the La/CeO that uses in the solution dip-coating 50 gram examples 5 of Mg
2), prepare and contain Pd, the catalyst particles of Mg, all the other methods are identical with example 6, prepare catalyst (G).
Example 8
The palladium solution of getting in the example 3 that contains adds lanthanum nitrate, and making palladium lanthanum mole ratio in the solution is 1: 10 mixed solution, (the Zr/CeO that uses in the dip-coating 50 gram examples 1
2) particulate, prepare the catalyst particles that contains the palladium lanthanum, again with example 4 in 50 grams contain the (Zr/CeO of Pt
2) particulate mixing use. all the other steps are identical with example 3, prepare catalyst (H).
Example 9
Get the palladium lanthanum solution in the example 8, (the Mg/CeO in the dipping example 2
2) particulate 50 gram prepares and contain Pd, the catalyst particles of La, all the other steps and the example 8 identical catalyst (I) of preparing.
Example 10
Get the CeO in the 178gZSM-5 zeolite molecular sieve particulate replacement example 1
2Particulate, other preparation process and the example 1 identical catalyst (J) of preparing.
Comparative example 1
According to the method for example 1, use Zr (NO
3)
45H
2It is 80m that the method that O rolls liquid and ammoniacal liquor co-precipitation is prepared specific area
2The ZrO of/g
2Particulate replaces the cerium oxide particulate (Zr/CeO of modified zirconia
2), directly use as carrier, dip-coating platinum palladium, method is identical with example 1, prepares catalyst (K).
Comparative example 2
Getting 100 gram specific areas is 120m
2The Al of/g
2O
3Replace the ZrO in the comparative example 1
2Particulate, all the other steps are identical with comparative example 1, prepare catalyst (L).
Comparative example 3
According to example 1, with 100 gram modified zirconia cerium oxide (Zr/CaO
2) particulate directly sneaks in the coating glue, all the other steps are with example 1.Prepare earlier and contain (Zr/CeO
2) monolithic catalyst support after again with platinum palladium mixed liquor dipping preparation catalyst, make the content of platinum palladium in integer catalyzer identical with example 1, promptly every liter catalyst platiniferous palladium total amount is 1 to restrain, Pe: Pd=1: 2 (gram molecules), this catalyst are (M).
Example 10
Get commercially available practical three-way catalyst (N), its Pt, Pd, Rh total content are 1.4 grams/1.2 liters, Pt/Rh=1: 5, with above-mentioned A, B, C, D, E, F, G, H, I, J, K, L, M, N catalyst in air through 950 ℃ of high temperature ageings 105 hours, after carry out the evaluation of three-effect catalysis performance, from wherein selecting A, C, F, H, L again, M, N catalyst in air 1100 ℃ strengthen roastings and revalue its three-effect catalysis performance after 5 hours, the gained result lists table 1 respectively in, in 2.
Estimating the condition of using is: 400 ℃, and 80,000 o'clock
-1O under the condition
2Content is by changing in 0.2～1.0% scope.It is CO1% that unstripped gas is formed, C
3H
6850ppm, NOx600ppm, CO
214%, H
2O10%, all the other are N
2Gas.Change the oxygen content in the unstripped gas, be determined at the CO under the different O/R values, HC, NOx conversion ratio, the elimination factor of (being equivalent to chemically correct fuel 14.7/1) three kinds of pollutants is represented catalyst triple effect activity when α=1, and the method for counting of O/R value is:
Table 1 catalyst is in 950 ℃ of air agings performance after 105 hours
| Catalyst | 400 ℃ of reaction temperatures, 80,00h -1The conversion (%) of air speed α=1 o'clock | ||
| A B C D E F G H I J K L M N | CO | HC | NOx |
| 96.1 94.8 97.5 92.8 92.0 92.3 94.0 98.8 93.0 92.9 74.5 80.4 85.8 95.0 | 97.5 93.7 98.8 95.4 92.8 95.5 95.2 96.1 95.6 95.5 81.6 85.3 91.4 96.2 | 86.1 85.5 85.0 86.2 84.9 89.0 84.5 87.6 88.0 89.1 61.0 46.5 64.0 80.2 | |
Aging catalytic activity after 5 hours in 1100 ℃ of air of table 2
| Catalyst | 400 ℃ of reaction temperatures, 80,000h -1The conversion (%) of air speed α=1 o'clock | ||
| A C F H K M N | CO | HC | NO 4 |
| 95.0 96.4 93.0 97.3 75.0 81.0 88.9 | 97.5 98.2 95.0 96.8 78.8 84.5 97.5 | 83.2 85.0 84.2 86.0 57.2 50.1 67.7 | |
By the result of above-mentioned example and comparative example, catalyst low-temperature activity height of the present invention at high temperature shows outstanding durability and stability, and its maximum is characterised in that the performance of not using the Rh element still to keep exhaust gas purification " triple effect " catalyst in the active constituent.
Claims (9)
1. one kind is that matrix is loaded with the Al that contains Pt and Pd noble metal and metal oxide with the porous honeycomb ceramic
2O
3The atmospheric cleaning catalyst of coating is characterized in that:
1) catalyst consists of the Al that contains noble metal and metal oxide in every liter catalyst
2O
3Coating ingredients weight is 60～180 grams, and the weight of precious metals pt and Pd is 0.8～1.4 gram;
2) contain the Al of noble metal and metal oxide
2O
3The content of noble metal and metal oxide is 10～30% in the coating ingredients;
3) weight ratio that contains precious metals pt and Pd is 1: 1～16.
4) so-called metal oxide is that mean particle diameter is the metal oxide microparticle of 0.3～25 μ m.
2. according to the described atmospheric cleaning agent of claim 1, it is characterized in that the Al of noble metal and metal oxide in every liter catalyst
2O
3Coating ingredients weight is 80～120 grams.
3. according to the described atmospheric cleaning catalyst of claim 1, it is characterized in that metal oxide microparticle is CeO
2, ZrO
2, La
2O
3, Al
2O
3Or SiO
2In one or both or zeolite; And adding the metal oxide modification agent in the metal oxide, is 1: 1.5～8 as the metallic atom ratio of the metallic atom content of modification agent and metal oxide; So-called metal oxide modification agent is Zr, Ce, and La, Mg, one or more mixtures in the oxide of Y or Ca, but the oxide of selecting for use of making modification agent is different with the virgin metal oxide.
4. according to the described atmospheric cleaning catalyst of claim 1, it is characterized in that Al
2O
3Contain Ba and Mg oxide in the coating, and Al
2O
3: the weight ratio of BaO: MgO is: 30～55: 2～4: 2～4.
5. according to the described atmospheric cleaning catalyst of claim 4, it is characterized in that Al
2O
3Al in the coating
2O
3Employing is by Al
2O
3H
2O, Al (OH)
3, γ-Al
2O
3And Al (NO
3)
39H
2O is by 18～28: 23～33: 30～40: the Al that the mixture of 4～8 weight proportion preparation is made
2O
3Coating.
6. according to the described atmospheric cleaning catalyst of claim 1, it is characterized in that porous honeycomb ceramic matrix is the honeycomb support that cordierite, mullite, Alpha-alumina, zirconia or silica are made.
7. one kind according to the described atmospheric cleaning Preparation of catalysts of claim 1 method, it is characterized in that the platiniferous palladium oxide particulate of preparing joins in the aluminum oxide coating layer glue mixes, vacuum gluing technology makes honeycomb ceramic body carry out kiss-coating routinely, soaked 1～30 minute, blow down unnecessary glue in the duct, drying and 600～1000 ℃ of following roastings were made in 1～10 hour.
8. according to the described preparation method of claim 7, it is characterized in that the aluminum oxide coating layer glue is Al
2O
3, Ba and Mg oxide or salt add water and nitric acid after mixing, and reconcile pH3～4, and ball milling becomes average grain diameter＜5 μ m, and viscosity is the glue of 1～4 pascal second.
9. according to the described preparation method of claim 7, it is characterized in that grinding to form after the metal oxide microparticle preparation of platiniferous palladium the particulate of 0.5～25 μ m.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96119452A CN1077806C (en) | 1996-10-04 | 1996-10-04 | Air purifying catalyst carrying noble metal particle and its preparing method |
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|---|---|---|---|
| CN96119452A CN1077806C (en) | 1996-10-04 | 1996-10-04 | Air purifying catalyst carrying noble metal particle and its preparing method |
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| CN1077806C true CN1077806C (en) | 2002-01-16 |
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| EP0722767A1 (en) * | 1995-01-17 | 1996-07-24 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Catalyst for purifying exhaust gases |
| JPH08206501A (en) * | 1995-02-06 | 1996-08-13 | Hino Motors Ltd | Catalyst for purifying exhaust gas and its production and exhaust gas purifying device using the same |
-
1996
- 1996-10-04 CN CN96119452A patent/CN1077806C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032749A (en) * | 1987-10-30 | 1989-05-10 | 底古萨有限公司 | Rhodium-free three-member catalyst |
| DE4229014A1 (en) * | 1992-09-02 | 1994-03-03 | Butzbacher Weichenbau Gmbh | Device for fastening a rail |
| CN1119127A (en) * | 1994-09-24 | 1996-03-27 | 华夏海南开发建设经营公司 | Purifying catalyst for gas exhausted from internal combustion engine |
| EP0722767A1 (en) * | 1995-01-17 | 1996-07-24 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Catalyst for purifying exhaust gases |
| JPH08206501A (en) * | 1995-02-06 | 1996-08-13 | Hino Motors Ltd | Catalyst for purifying exhaust gas and its production and exhaust gas purifying device using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1178717A (en) | 1998-04-15 |
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