US20030202926A1 - Use of a catalyst for reducing the quantity and/or size of particulates in diesel exhaust - Google Patents

Use of a catalyst for reducing the quantity and/or size of particulates in diesel exhaust Download PDF

Info

Publication number
US20030202926A1
US20030202926A1 US10/440,936 US44093603A US2003202926A1 US 20030202926 A1 US20030202926 A1 US 20030202926A1 US 44093603 A US44093603 A US 44093603A US 2003202926 A1 US2003202926 A1 US 2003202926A1
Authority
US
United States
Prior art keywords
zeolite
catalyst
elements
particulates
sio
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.)
Abandoned
Application number
US10/440,936
Inventor
Lothar Puppe
Axel Konig
Ulrich-Dieter Standt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US09/967,452 external-priority patent/US20020114751A1/en
Application filed by Individual filed Critical Individual
Priority to US10/440,936 priority Critical patent/US20030202926A1/en
Publication of US20030202926A1 publication Critical patent/US20030202926A1/en
Abandoned legal-status Critical Current

Links

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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
    • 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
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • 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
    • B01J37/0246—Coatings comprising a zeolite
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
    • F01N2370/04—Zeolitic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • This invention relates to the use of a catalyst for reducing the quantity and/or size of particulates in the exhaust gas of a diesel engine by means of a bifunctional catalyst containing a transition metal oxide and an acidic zeolite.
  • a well-known measure widely used to prevent particulate emissions is to use filters.
  • the disadvantage of filters lies in the danger of blockage by the particulates after a relatively short operating time. Accordingly, measures have to be taken to regenerate the particulate filters, for example by brief heating of the filters by suitable devices to the ignition temperature of the deposited particulates. Devices such as these are complicated and expensive and are not a practical solution, for example, for diesel-powered automobiles.
  • the problem addressed by the present invention was further to reduce the quantity and/or size of the particulates.
  • zeolite-containing catalysts which have acidic or cracking properties and which additionally contain oxides of the transition metals distinctly reduce the quantity and/or size of particulates in relation to the prior art without at the same time oxidizing the SO 2 in the exhaust gas to sulfates.
  • the zeolite catalysts containing the added metal oxides have no oxidizing effect on the SO 2 in the exhaust gas, even at relatively high exhaust gas temperatures.
  • the metal oxide addition also has a favorable effect on particulate reduction at relatively low temperatures so that particulate reduction is up to 50% greater than in the case of an acidic zeolite catalyst with no metal oxide addition.
  • the present invention relates to the use of a catalyst for reducing the quantity and/or size of particulates in the exhaust gas of a diesel engine by means of a catalyst which is a combination of a zeolite having acidic properties and one or more transition metal oxides and/or oxides of the rare earths.
  • Suitable metal oxide additions are, preferably, TiO 2 , V 2 O 5 , Cr 2 O 3 , MnO 2 , Fe 2 O 3 , CoO, NiO, CuO, Y 2 O 3 , ZrO 2 , Nb 2 O 5 , Ta 2 O 5 , WO 3 , MoO 3 , La 2 O 3 , Ce 2 O 3 , WO 3 , etc. or mixtures of these oxides.
  • the oxides are preferably added in quantities of 0.1 to 20% by weight and, more preferably, in quantities of 0.5 to 10% by weight.
  • Particularly suitable metal oxide additions are TiO 2 , V 2 O 5 , WO 3 , MoO 3 , La 2 O 3 and Ce 2 O 3 .
  • the metal oxides are normally added to the zeolite.
  • a binder is added so that the mixture may be adhesively applied to a support (for example of cordierite or of metal) or press-molded to form self-supporting shaped structures.
  • the mixture is homogenized by intensive grinding, for example in stirred ball mills.
  • the mixtures are then dried to a moisture content suitable for granulation and are press-molded to form shaped structures in suitable units, for example roller-type granulators, extruders.
  • supports for example in the form of shaped structures or monolithic honeycombs, may also be coated with a suspension of the active components.
  • the zeolite-containing catalysts may also be coated with salts of the transition metals or rare earths which may then be thermally decomposed.
  • Zeolites particularly suitable for use in accordance with the invention include the following structure types: faujasites, pentasils, mordenites, ZSM 12, zeolite ⁇ , zeolite L, zeolite ⁇ , PSH-3, ZSM 22, ZSM 23, ZSM 48M EU-1, NU-86, offretith, ferrierite, etc.
  • the pentasil type zeolite preferably has an SiO 2 to Al 2 O 3 ratio of 25 to 2000:1 and, more preferably 40 to 600:1.
  • M 1 is an equivalent of an exchangeable cation
  • n standing for the valency and the number corresponds to the charge equalization of M 2 ,
  • M 2 is a trivalent element which, together with the Si, forms the oxidic skeleton of the zeolite,
  • y/x is the SiO2/M 2 2 O 3 ratio
  • q is the quantity of water adsorbed.
  • zeolites are crystalline alumosilicates which are made up of a network of SiO 4 and M 2 O 4 tetrahedrons.
  • the individual tetrahedrons are linked to one another by oxygen bridges over the corners of the tetrahedrons and form a three-dimensional network which is uniformly permeated by passages and voids.
  • the individual zeolite structures differ in the arrangement and size of the passages and voids and in their composition.
  • Exchangeable cations are incorporated to equalize the negative charge of the lattice arising out of the M2 component.
  • the adsorbed water phase qH 2 O can be reversibly removed without the skeleton losing its structure.
  • M 2 is often aluminium, but may be completely or partly replaced by certain other trivalent elements.
  • zeolites A detailed account of zeolites can be found, for example, in D. W. Breck's book entitled “Zeolite Molecular Sieves, Structure, Chemistry and Use”, J. Wiley & Sons, New York, 1974. Another account, particularly of the zeolites relatively rich in SiO 2 which are of interest in catalytic applications, can be found in the book by P.A. Jacobs and J. A. Martens entitled “Synthesis of High-Silica Aluminosilicate Zeolites”, Studies in Surface Science and Catalysis, Vol. 33, Ed. B. Delmon and J. I. Yates, Elsevier, Amsterdam/Oxford/New York/Tokyo, 1987.
  • M 2 stands for one or more elements from the group consisting of Al, B, Ga, In, Fe, Cr, V, As and Sb and, preferably, for one or more elements from the group consisting of Al, B, Ga and Fe.
  • the zeolites mentioned may contain rare earths and/or protons as exchangeable cations M 1 .
  • exchangeable cations are, for example, those of Mg, Ca, Sr, Ba, Zn, Cd and also transition metal cations such as, for example, Cr, Mn, Fe, Co, Ni, Cu, V, Nb, Mo, Ru, Rh, Pd, Ag, Ta, W, Re or Pt.
  • preferred catalysts are those which contain zeolites of the structure types mentioned above, in which at least part, preferably 50 to 100% and, more preferably, 80 to 100% of all the metal cations originally present have been replaced by hydrogen ions, and which also contain the metal oxide additions.
  • the acidic H forms of the zeolites are preferably produced by exchanging metal ions for ammonium ions and subsequently calcining the zeolite thus exchanged.
  • zeolites of the faujasite type repetition of the exchange process and subsequent calcination under defined conditions lead to so-called ultrastable zeolites relatively poor in aluminium which are made thermally and hydrothermally more stable by this dealuminization process.
  • Another method of obtaining zeolites of the faujasite type rich in SiO 2 is to subject the anhydrous zeolite to a controlled treatment with SiCl 4 at relatively high temperatures ( ⁇ 150° C.). As a result of this treatment, aluminium is removed and at the same time silicon is incorporated in the lattice. Under certain conditions, treatment with ammonium hexafluorosilicate also leads to a faujasite rich in SiO 2 .
  • Another method of replacing/exchanging protons is to carry out the process with mineral acids in the case of zeolites which have a sufficiently high SiO 2 to Al 2 O 3 ratio (>5). Dealuminized zeolites can also be obtained in this way.
  • SE zeolite Y rare-earth-exchanged acidic zeolite Y with an SiO 2 to Al 2 O 3 ratio of 4.9 and a degree of exchange of approx. 90% and containing 2% WO 3 , (based on the zeolite component.
  • H zeolite Y dealuminized acidic zeolite Y with a molar SiO 2 to Al 2 O 3 ratio of 50 and an addition of 2% WO 3 , based on the zeolite.
  • Engine Temp. at HC con- Particulate speed Pme manifold version conversion [r.p.m.] [bar] [0C] [%] [%] 2000 1 159 34.3 26.3 2000 6 425 29.5 36.1
  • H zeolite Y dealuminized acidic zeolite Y with a molar SiO 2 to Al 2 O 3 ratio of 50 and an addition of 2% MoO 3 , based on the zeolite.
  • Engine Temp. at HC con- Particulate speed Pme manifold version conversion [r.p.m.] [bar] [C] [%] [%] 2000 1 159 30.9 21.5 2000 6 425 26.7 34.8

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Combustion & Propulsion (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

In the reduction of at least one of the quantity and size of particulates in the exhaust of a diesel engine, wherein said exhaust is contacted with a catalyst, the improvement wherein the catalyst comprises a combination of a zeolite having acidic properties and at least one oxide of a transition metal or rare earth. SO2 in the exhaust gas is not oxidized to sulfates.

Description

  • This invention relates to the use of a catalyst for reducing the quantity and/or size of particulates in the exhaust gas of a diesel engine by means of a bifunctional catalyst containing a transition metal oxide and an acidic zeolite. [0001]
  • One of the problems of using diesel engines, more particularly to drive motor vehicles, is that they emit particulates which are difficult to prevent from entering the atmosphere. [0002]
  • A well-known measure widely used to prevent particulate emissions is to use filters. The disadvantage of filters lies in the danger of blockage by the particulates after a relatively short operating time. Accordingly, measures have to be taken to regenerate the particulate filters, for example by brief heating of the filters by suitable devices to the ignition temperature of the deposited particulates. Devices such as these are complicated and expensive and are not a practical solution, for example, for diesel-powered automobiles. [0003]
  • It is also known that the quantity of particulates can be catalytically reduced. Oxidation catalysts containing platinum as active component on aluminium oxide are used for this purpose. The disadvantage of monofunctional noble metal catalysts of this type is that, although they reduce the quantity of particulates in the exhaust gas, they also have a strong oxidizing effect on the SO[0004] 2 component of the exhaust gases. The resulting formation of sulfate makes the particulates hygroscopic and, under certain conditions, even leads to an increase in the quantity of particulates. In addition, sulfate particles are deposited on the catalyst, reducing its effectiveness.
  • It is known from a hitherto patent application (P 41 05 534) that the quantity of particulates can be reduced without additional sulfate formation. It was found that zeolite-containing catalysts with acidic or cracking properties reduce the quantity and/or size of particulates and the quantity of hydrocarbons without at the same time oxidizing the SO[0005] 2 in the exhaust gas to sulfates. The disadvantage is that small quantities of particulates are still formed, above all at temperatures ≦200° C.
  • Accordingly, the problem addressed by the present invention was further to reduce the quantity and/or size of the particulates. [0006]
  • It has now been found that zeolite-containing catalysts which have acidic or cracking properties and which additionally contain oxides of the transition metals distinctly reduce the quantity and/or size of particulates in relation to the prior art without at the same time oxidizing the SO[0007] 2 in the exhaust gas to sulfates. Surprisingly, the zeolite catalysts containing the added metal oxides have no oxidizing effect on the SO2 in the exhaust gas, even at relatively high exhaust gas temperatures.
  • The metal oxide addition also has a favorable effect on particulate reduction at relatively low temperatures so that particulate reduction is up to 50% greater than in the case of an acidic zeolite catalyst with no metal oxide addition. [0008]
  • Now, the present invention relates to the use of a catalyst for reducing the quantity and/or size of particulates in the exhaust gas of a diesel engine by means of a catalyst which is a combination of a zeolite having acidic properties and one or more transition metal oxides and/or oxides of the rare earths. [0009]
  • Suitable metal oxide additions are, preferably, TiO[0010] 2, V2O5, Cr2O3, MnO2, Fe2O3, CoO, NiO, CuO, Y2O3, ZrO2, Nb2O5, Ta2O5, WO3, MoO3, La2O3, Ce2O3, WO3, etc. or mixtures of these oxides.
  • The oxides are preferably added in quantities of 0.1 to 20% by weight and, more preferably, in quantities of 0.5 to 10% by weight. [0011]
  • Particularly suitable metal oxide additions are TiO[0012] 2, V2O5, WO3, MoO3, La2O3 and Ce2O3.
  • The metal oxides are normally added to the zeolite. In addition, a binder is added so that the mixture may be adhesively applied to a support (for example of cordierite or of metal) or press-molded to form self-supporting shaped structures. The mixture is homogenized by intensive grinding, for example in stirred ball mills. The mixtures are then dried to a moisture content suitable for granulation and are press-molded to form shaped structures in suitable units, for example roller-type granulators, extruders. As already mentioned, supports, for example in the form of shaped structures or monolithic honeycombs, may also be coated with a suspension of the active components. [0013]
  • The zeolite-containing catalysts may also be coated with salts of the transition metals or rare earths which may then be thermally decomposed. [0014]
  • Zeolites particularly suitable for use in accordance with the invention include the following structure types: faujasites, pentasils, mordenites, ZSM 12, zeolite β, zeolite L, zeolite Ω, PSH-3, ZSM 22, ZSM 23, ZSM 48M EU-1, NU-86, offretith, ferrierite, etc. [0015]
  • The pentasil type zeolite preferably has an SiO[0016] 2 to Al2O3 ratio of 25 to 2000:1 and, more preferably 40 to 600:1.
  • Zeolites are characterized by the following general formula (I): [0017]
  • M1 2/nO.xM2 2O3 ySiO2 .qH2O  (I)
  • in which [0018]
  • M[0019] 1 is an equivalent of an exchangeable cation, n standing for the valency and the number corresponds to the charge equalization of M2,
  • M[0020] 2 is a trivalent element which, together with the Si, forms the oxidic skeleton of the zeolite,
  • y/x is the SiO2/M[0021] 2 2O3 ratio,
  • q is the quantity of water adsorbed. [0022]
  • In terms of their basic structure, zeolites are crystalline alumosilicates which are made up of a network of SiO[0023] 4 and M2O4 tetrahedrons. The individual tetrahedrons are linked to one another by oxygen bridges over the corners of the tetrahedrons and form a three-dimensional network which is uniformly permeated by passages and voids. The individual zeolite structures differ in the arrangement and size of the passages and voids and in their composition. Exchangeable cations are incorporated to equalize the negative charge of the lattice arising out of the M2 component. The adsorbed water phase qH2O can be reversibly removed without the skeleton losing its structure.
  • M[0024] 2 is often aluminium, but may be completely or partly replaced by certain other trivalent elements.
  • A detailed account of zeolites can be found, for example, in D. W. Breck's book entitled “Zeolite Molecular Sieves, Structure, Chemistry and Use”, J. Wiley & Sons, New York, 1974. Another account, particularly of the zeolites relatively rich in SiO[0025] 2 which are of interest in catalytic applications, can be found in the book by P.A. Jacobs and J. A. Martens entitled “Synthesis of High-Silica Aluminosilicate Zeolites”, Studies in Surface Science and Catalysis, Vol. 33, Ed. B. Delmon and J. I. Yates, Elsevier, Amsterdam/Oxford/New York/Tokyo, 1987.
  • In the zeolites used in accordance with the invention, M[0026] 2 stands for one or more elements from the group consisting of Al, B, Ga, In, Fe, Cr, V, As and Sb and, preferably, for one or more elements from the group consisting of Al, B, Ga and Fe.
  • The zeolites mentioned may contain rare earths and/or protons as exchangeable cations M[0027] 1. Other suitable exchangeable cations are, for example, those of Mg, Ca, Sr, Ba, Zn, Cd and also transition metal cations such as, for example, Cr, Mn, Fe, Co, Ni, Cu, V, Nb, Mo, Ru, Rh, Pd, Ag, Ta, W, Re or Pt.
  • According to the invention, preferred catalysts are those which contain zeolites of the structure types mentioned above, in which at least part, preferably 50 to 100% and, more preferably, 80 to 100% of all the metal cations originally present have been replaced by hydrogen ions, and which also contain the metal oxide additions. [0028]
  • The acidic H forms of the zeolites are preferably produced by exchanging metal ions for ammonium ions and subsequently calcining the zeolite thus exchanged. In the case of zeolites of the faujasite type, repetition of the exchange process and subsequent calcination under defined conditions lead to so-called ultrastable zeolites relatively poor in aluminium which are made thermally and hydrothermally more stable by this dealuminization process. Another method of obtaining zeolites of the faujasite type rich in SiO[0029] 2 is to subject the anhydrous zeolite to a controlled treatment with SiCl4 at relatively high temperatures (≧150° C.). As a result of this treatment, aluminium is removed and at the same time silicon is incorporated in the lattice. Under certain conditions, treatment with ammonium hexafluorosilicate also leads to a faujasite rich in SiO2.
  • Another method of replacing/exchanging protons is to carry out the process with mineral acids in the case of zeolites which have a sufficiently high SiO[0030] 2 to Al2O3 ratio (>5). Dealuminized zeolites can also be obtained in this way.
  • It is also known that ion exchange with trivalent rare earth metal ions (individually and/or in the form of mixtures) which may preferably be rich in lanthanum or cerium, leads to acidic centers, above all in the case of faujasite. It is also known that acidic centers are formed when polyvalent metal cations are introduced into zeolites. [0031]
  • The following Examples illustrate the effectiveness of the acidic zeolitic or zeolite-containing catalysts additionally containing added metal oxides in particulate conversion and hydrocarbon conversion in exhaust gases of diesel engines. The Examples are not intended to limit the invention in any way. [0032]
  • The results were obtained from a diesel engine under the conditions shown in the Tables. The catalysts were coated monoliths 102 mm in diameter and 152 mm in length.[0033]
    • EXAMPLE 1
  • SE zeolite Y, rare-earth-exchanged acidic zeolite Y with an SiO[0034] 2 to Al2O3 ratio of 4.9 and a degree of exchange of approx. 90% and containing 2% WO3, (based on the zeolite component.
    Engine Temp. at HC con- Particulate
    speed Pme manifold version conversion
    [r.p.m.] [bar] [° C.] [%] [%]
    2000 1 159 26.8 20.4
    2000 6 425 33.4 34.9
    • EXAMPLE 2
  • SE zeolite Y, rare-earth-exchanged acidic zeolite Y with an SiO[0035] 2 to Al2O3 ratio of 4.9 and a degree of exchange of approx. 90% and containing 2% MoO3, based on the zeolite component.
    Engine Temp. at HC con- Particulate
    speed Pme manifold version conversion
    [r.p.m.] [bar] [0C] [%] [%]
    2000 1 159 22.3 19.5
    2000 6 425 30.6 36.1
    • EXAMPLE 3
  • H zeolite Y, dealuminized acidic zeolite Y with a molar SiO[0036] 2 to Al2O3 ratio of 50 and an addition of 2% WO3, based on the zeolite.
    Engine Temp. at HC con- Particulate
    speed Pme manifold version conversion
    [r.p.m.] [bar] [0C] [%] [%]
    2000 1 159 34.3 26.3
    2000 6 425 29.5 36.1
    • EXAMPLE 4
  • H zeolite Y, dealuminized acidic zeolite Y with a molar SiO[0037] 2 to Al2O3 ratio of 50 and an addition of 2% MoO3, based on the zeolite.
    Engine Temp. at HC con- Particulate
    speed Pme manifold version conversion
    [r.p.m.] [bar] [C] [%] [%]
    2000 1 159 30.9 21.5
    2000 6 425 26.7 34.8
    • COMPARISON EXAMPLE 5
  • SE zeolite Y, rare-earth-exchanged acidic zeolite Y with an SiO[0038] 2 to Al2O3 ratio of 4.9 and a degree of exchange of approx. 90% (no metal oxide addition).
    Engine Temp. at HC con- Particulate
    speed Pme manifold version conversion
    [r.p.m.] [bar] [0C] [%] [%]
    2000 1 159 20.6 15.1
    2000 6 425 27.8 34.0

Claims (14)

1. The use of a catalyst for reducing the quantity and/or size of particulates in the exhaust of the diesel engine, characterized in that the catalyst is a combination of a zeolite having acidic properties and one or more transition metal oxides and/or oxides of the rare earths.
2. The use of a catalyst as claimed in claim 1, characterized in that the zeolite having acidic properties corresponds to the following general formula:
M1 2/nO*xM2 2O3 .ySiO2 .qH2O  (I)
in which
M1 is an equivalent of an exchangeable cation of which the number corresponds to the percentage content of M2, n standing for the valency of the cation,
M2 is a trivalent element which, together with the Si, forms the oxidic skeleton of the zeolite,
y/x is the SiO2/M2 2O3 ratio,
q is the quantity of water adsorbed.
3. The use claimed in claim or 2, characterized in that the zeolite is of the faujasite type.
4. The use claimed in claim 3, characterized in that the zeolite is a dealuminized faujasite.
5. The use claimed in claim 1 or 2, characterized in that the zeolite is of the pentasil type.
6. The use claimed in claim 5, characterized in that the pentasil type zeolite has an SiO2 to Al2O3 ratio of 25 to 2000:1 and preferably 40 to 600:1.
7. The use claimed in claim 1 or 2, characterized in that the zeolite is a zeolite of the mordenite type.
8. The use claimed in claim 7, characterized in that the zeolite is a dealuminized mordenite.
9. The use claimed in one or more of claims 1 to 8, characterized in that the zeolite contains one or more elements from the group of elements of the second main group of the periodic system of elements and/or the rare earth elements as exchanged cations.
10. The use claimed in one or more of claims 1 to 8, characterized in that the zeolite contains one or more transition elements as exchanged cations.
11. The use claimed in claim 10, characterized in that the transition elements are Cu, Ni, Co, Fe, Cr, Mn and/or V.
12. The use claimed in claim 10, characterized in that the zeolite contains Cu as transition element.
13. The use claimed in claim 1, characterized in that TiO2, V2O5, Cr2O3, MnO2, Fe2O3, CoO, NiO, CuO, Y2O3, ZrO2, Nb2O5, Ta2O5, WO3, MoO3, La2O3, Ce2O3, WO3 or mixtures thereof are used as the transition metal oxides and/or as oxides of the rare earths.
14. The use claimed in claim 1, characterized in that the oxides are used in quantities of 0.1 to 20% by weight, based on zeolite.
US10/440,936 1992-08-07 2003-05-19 Use of a catalyst for reducing the quantity and/or size of particulates in diesel exhaust Abandoned US20030202926A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/440,936 US20030202926A1 (en) 1992-08-07 2003-05-19 Use of a catalyst for reducing the quantity and/or size of particulates in diesel exhaust

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4226112A DE4226112B4 (en) 1992-08-07 1992-08-07 Use of a catalyst for reducing the amount and / or size of particles in diesel exhaust
DEP4226112.0 1992-08-07
US09/967,452 US20020114751A1 (en) 1992-08-07 2001-09-28 Use of a catalyst for reducing the quantity and/or size of particulates in diesel exhaust
US10/440,936 US20030202926A1 (en) 1992-08-07 2003-05-19 Use of a catalyst for reducing the quantity and/or size of particulates in diesel exhaust

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US09/967,452 Continuation US20020114751A1 (en) 1992-08-07 2001-09-28 Use of a catalyst for reducing the quantity and/or size of particulates in diesel exhaust

Publications (1)

Publication Number Publication Date
US20030202926A1 true US20030202926A1 (en) 2003-10-30

Family

ID=6465035

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/440,936 Abandoned US20030202926A1 (en) 1992-08-07 2003-05-19 Use of a catalyst for reducing the quantity and/or size of particulates in diesel exhaust

Country Status (4)

Country Link
US (1) US20030202926A1 (en)
JP (1) JPH06170173A (en)
DE (1) DE4226112B4 (en)
FR (1) FR2694598B1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090076673A1 (en) * 2007-09-19 2009-03-19 Topcon Positioning Systems, Inc. Partial manual control state for automated vehicle navigation system
US8119075B2 (en) 2005-11-10 2012-02-21 Basf Corporation Diesel particulate filters having ultra-thin catalyzed oxidation coatings

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5804155A (en) * 1992-11-19 1998-09-08 Engelhard Corporation Basic zeolites as hydrocarbon traps for diesel oxidation catalysts
US6248684B1 (en) 1992-11-19 2001-06-19 Englehard Corporation Zeolite-containing oxidation catalyst and method of use
DE19653910A1 (en) 1996-12-21 1998-06-25 Daimler Benz Ag Process and catalyst for reducing pollutants in gases
US6093378A (en) * 1997-05-07 2000-07-25 Engelhard Corporation Four-way diesel exhaust catalyst and method of use
DE19806062A1 (en) * 1998-02-13 1999-08-19 Siemens Ag Reduction catalyst for reducing pollutants from diesel engine exhaust gases
US6074973A (en) * 1998-03-20 2000-06-13 Engelhard Corporation Catalyzed hydrocarbon trap material and method of making the same
FR2779072B1 (en) * 1998-05-28 2000-07-13 Inst Francais Du Petrole CATALYST INCLUDING A ZEOLITH CHOSEN FROM THE GROUP FORMED BY ZEOLITHES NU-85, NU-86 AND NU-87, AN ELEMENT OF GROUP VB AND ITS USE IN HYDROCONVERSION OF HYDROCARBON OIL FEEDS
AU5626100A (en) 1999-07-02 2001-01-22 Engelhard Corporation Oxidation catalyst for treating diesel engine exhaust gases
JP5076192B2 (en) * 2007-01-12 2012-11-21 国立大学法人 岡山大学 Catalyst and method for purifying nitrogen oxides in diesel engine exhaust gas using unburned carbon

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4303552A (en) * 1980-05-27 1981-12-01 W. R. Grace & Co. Diesel exhaust catalyst
US4331644A (en) * 1977-12-27 1982-05-25 Union Carbide Corporation Combustion catalyst and process for using same
US4515758A (en) * 1982-09-03 1985-05-07 Degussa Aktiengesellschaft Process and catalyst for the reduction of the ignition temperature of diesel soot filtered out of the exhaust gas of diesel engines
US4929581A (en) * 1987-05-16 1990-05-29 Dornier-System Gmbh Catalytic diesel soot filter
US5270024A (en) * 1989-08-31 1993-12-14 Tosoh Corporation Process for reducing nitrogen oxides from exhaust gas
US5279997A (en) * 1991-10-07 1994-01-18 Ford Motor Company Selective reduction of NOx
US5290530A (en) * 1991-05-31 1994-03-01 Kabushiki Kaisha Riken Method of cleaning exhaust gas
US5312608A (en) * 1990-10-31 1994-05-17 Idemitsu Kosan Company Limited Exhaust gas purifying catalyst and an exhaust gas purifying method using the catalyst
US6287527B1 (en) * 1996-12-26 2001-09-11 Ict Co., Ltd. Method for controlling exhaust emission

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3940758A1 (en) * 1989-12-09 1991-06-13 Degussa METHOD FOR PURIFYING THE EXHAUST GAS FROM DIESEL ENGINES
JP3113662B2 (en) * 1990-02-26 2000-12-04 株式会社日本触媒 Catalyst for exhaust gas purification of diesel engines
DE69125649T2 (en) * 1990-05-28 1997-09-04 Agency Ind Science Techn Process for removing nitrogen oxides from exhaust gases
JP2771321B2 (en) * 1990-11-09 1998-07-02 日本碍子株式会社 Exhaust gas purifying catalyst composition, exhaust gas purifying catalyst and method for producing the same
DE4105534C2 (en) * 1991-02-22 1994-12-22 Bayer Ag Use of a catalyst to reduce the amount and / or size of particles in the diesel exhaust

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4331644A (en) * 1977-12-27 1982-05-25 Union Carbide Corporation Combustion catalyst and process for using same
US4303552A (en) * 1980-05-27 1981-12-01 W. R. Grace & Co. Diesel exhaust catalyst
US4515758A (en) * 1982-09-03 1985-05-07 Degussa Aktiengesellschaft Process and catalyst for the reduction of the ignition temperature of diesel soot filtered out of the exhaust gas of diesel engines
US4929581A (en) * 1987-05-16 1990-05-29 Dornier-System Gmbh Catalytic diesel soot filter
US5270024A (en) * 1989-08-31 1993-12-14 Tosoh Corporation Process for reducing nitrogen oxides from exhaust gas
US5312608A (en) * 1990-10-31 1994-05-17 Idemitsu Kosan Company Limited Exhaust gas purifying catalyst and an exhaust gas purifying method using the catalyst
US5290530A (en) * 1991-05-31 1994-03-01 Kabushiki Kaisha Riken Method of cleaning exhaust gas
US5279997A (en) * 1991-10-07 1994-01-18 Ford Motor Company Selective reduction of NOx
US6287527B1 (en) * 1996-12-26 2001-09-11 Ict Co., Ltd. Method for controlling exhaust emission

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8119075B2 (en) 2005-11-10 2012-02-21 Basf Corporation Diesel particulate filters having ultra-thin catalyzed oxidation coatings
US20090076673A1 (en) * 2007-09-19 2009-03-19 Topcon Positioning Systems, Inc. Partial manual control state for automated vehicle navigation system

Also Published As

Publication number Publication date
FR2694598B1 (en) 1994-12-23
DE4226112A1 (en) 1994-02-10
FR2694598A1 (en) 1994-02-11
DE4226112B4 (en) 2006-01-12
JPH06170173A (en) 1994-06-21

Similar Documents

Publication Publication Date Title
KR100237260B1 (en) Application of a catalyst to decrease quantity and dimension of particles in diesel exhaust gas
US5330732A (en) Method for purifying exhaust gases
EP0526896B1 (en) Catalyst for purifying exhaust gas
EP0800856B1 (en) Catalyst for treating exhaust gases from diesel engines
US9486792B2 (en) Mixed metal 8-ring small pore molecular sieve catalyst compositions, catalytic articles, systems, and methods
US6033641A (en) Catalyst for purifying the exhaust gas from the combustion in an engine or gas turbines and method of making and using the same
US20030202926A1 (en) Use of a catalyst for reducing the quantity and/or size of particulates in diesel exhaust
EP1721665A1 (en) Catalyst for the treatment of exhaust gas and a process for its preparation
JPH0763631B2 (en) Exhaust gas purification catalyst manufacturing method
US7141526B2 (en) Exhaust gas purifying catalyst and process for purifying exhaust gas by use of the catalyst
KR100520320B1 (en) Exhaust gas purifying catalyst and method for purifying exhaust gas
EP0462598A2 (en) Transition metal-containing zeolite having high hydrothermal stability, production method thereof and method of using same
US20020016252A1 (en) Adsorbent for exhaust gas purification
EP1609962B1 (en) Exhaust system for improving the NOx reduction efficiency in vehicles
US20020114751A1 (en) Use of a catalyst for reducing the quantity and/or size of particulates in diesel exhaust
JPH06182157A (en) Use of catalyst for decreasing amount and/or size of particle in diesel exhaust gas
EP0467363B1 (en) Method for catalytically purifying exhaust gas
US20040067184A1 (en) Use of a catalyst for reducing the quantity and/or size of particles in diesel exhaust
US20020028169A1 (en) Use of a catalyst for reducing the quantity and/or size of particulates in diesel exhaust
JP3511638B2 (en) Exhaust gas purification method
JP4105302B2 (en) Method for producing exhaust gas purifying catalyst
JP3197711B2 (en) Exhaust gas purification catalyst
JP3511637B2 (en) Exhaust gas purification method
JPH0639292A (en) Purifying catalyst for exhaust gas and production thereof
JPH04271843A (en) Production of catalyst for purification of exhaust gas

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION