Methods for reducing harmful emissions from a diesel engine

• US 6,003,303 A
• Filed: 08/14/1995
• Issued: 12/21/1999
• Est. Priority Date: 01/11/1993
• Status: Expired due to Term

• Current Assignee: Clean Diesel Technologies, Inc.
• Original Assignee: Clean Diesel Technologies, Inc.
• Inventors: Sprague, Barry N., Peter-Hoblyn, Jeremy D., Epperly, W. Robert, Valentine, James M.
• Primary Examiner(s): Denion, Thomas E.
• Application Number:
  US08/514,978
• Time in Patent Office: 1,590 Days
• Field of Search: 60/295, 60/274, 60/299, 60/278
• US Class Current: 60/274
• CPC Class Codes: B01D 2255/1021 Platinum
• CPC Class Codes: B01D 2255/2065 Cerium
• CPC Class Codes: B01D 2255/20761 Copper
• CPC Class Codes: B01D 2255/906 Catalyst dispersed in the gas
• CPC Class Codes: B01D 53/944 Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts three-way-catalysts [TWC] B01D53/9445
• CPC Class Codes: C10L 1/10 containing additives
• CPC Class Codes: C10L 1/1208 elements
• CPC Class Codes: C10L 1/1225 halogen containing compounds
• CPC Class Codes: C10L 1/1233 oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
• CPC Class Codes: C10L 1/1241 metal carbonyls
• CPC Class Codes: C10L 1/125 water
• CPC Class Codes: C10L 1/1266 nitrogen containing compounds, (e.g. NH3)
• CPC Class Codes: C10L 1/1275 sulfur, tellurium, selenium containing compounds
• CPC Class Codes: C10L 1/14 Organic compounds
• CPC Class Codes: C10L 1/1608 Well defined compounds, e.g. hexane, benzene
• CPC Class Codes: C10L 1/1616 fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
• CPC Class Codes: C10L 1/1691 petroleum waxes, mineral waxes; paraffines; alkylation products; Friedel-Crafts condensation products; petroleum resins; modified waxes (oxidised)
• CPC Class Codes: C10L 1/1814 Chelates
• CPC Class Codes: C10L 1/1824 mono-hydroxy
• CPC Class Codes: C10L 1/1828 Salts thereof
• CPC Class Codes: C10L 1/1852 : Ethers; Acetals; Ketals; Orthoesters
• CPC Class Codes: C10L 1/1855 : Cyclic ethers, e.g. epoxides, lactides, lactones
• CPC Class Codes: C10L 1/1857 : Aldehydes; Ketones
• CPC Class Codes: C10L 1/188 : Carboxylic acids; metal salts thereof C10L1/1802, C10L1/1805, C10L1/1808, C10L1/1811, C10L1/1814, C10L1/1817 take precedence
• CPC Class Codes: C10L 1/1881 : carboxylic group attached to an aliphatic carbon atom
• CPC Class Codes: C10L 1/1883 : polycarboxylic acid
• CPC Class Codes: C10L 1/1886 : naphthenic acid
• CPC Class Codes: C10L 1/1888 : tall oil
• CPC Class Codes: C10L 1/191 : of di- or polyhydroxyalcohols
• CPC Class Codes: C10L 1/198 : obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
• CPC Class Codes: C10L 1/1985 : polyethers, e.g. di- polygylcols and derivatives; ethers - esters
• CPC Class Codes: C10L 1/2222 : (cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates C10L1/221 takes precedence
• CPC Class Codes: C10L 1/2225 : hydroxy containing C10L1/221 takes precedence
• CPC Class Codes: C10L 1/2227 : urea; derivatives thereof; urethane C10L1/221 takes precedence
• CPC Class Codes: C10L 1/224 : Amides; Imides carboxylic acid amides, imides C10L1/221, C10L1/2227 take precedence
• CPC Class Codes: C10L 1/2286 : containing one or more carbon to nitrogen triple bonds, e.g. nitriles C10L1/221, C10L1/226 take precedence
• CPC Class Codes: C10L 1/23 : containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites C10L1/221 takes precedence
• CPC Class Codes: C10L 1/231 : nitro compounds; nitrates; nitrites C10L1/221 takes precedence
• CPC Class Codes: C10L 1/232 : containing nitrogen in a heterocyclic ring C10L1/221 takes precedence
• CPC Class Codes: C10L 1/238 : obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds C10L1/221 takes precedence
• CPC Class Codes: C10L 1/2437 : Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
• CPC Class Codes: C10L 1/26 : containing phosphorus
• CPC Class Codes: C10L 1/2608 : containing a phosphorus-carbon bond
• CPC Class Codes: C10L 1/301 : derived from metals
• CPC Class Codes: C10L 1/305 : organo-metallic compounds (containing a metal to carbon bond)
• CPC Class Codes: C10L 10/02 : for reducing smoke development
• CPC Class Codes: C10L 10/06 : for facilitating soot removal
• CPC Class Codes: F01N 2430/04 : by adding non-fuel substances to combustion air or fuel, e.g. additives
• CPC Class Codes: F01N 2610/02 : the substance being ammonia or urea
• CPC Class Codes: F01N 3/023 : using means for regenerating the filters, e.g. by burning trapped particles by electrically controlling the supply of combustible mixture or its constituents only F02D41/0235
• CPC Class Codes: F01N 3/029 : by adding non-fuel substances to exhaust
• CPC Class Codes: F01N 3/035 : with catalytic reactors , e.g. catalysed diesel particulate filters
• CPC Class Codes: F01N 3/037 : by means of inertial or centrifugal separators, e.g. of cyclone type, optionally combined or associated with agglomerators
• CPC Class Codes: F01N 3/206 : Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents F01N3/2066 takes precedence
• CPC Class Codes: F02B 3/06 : with compression ignition compression ignition engines using air or gas for blowing fuel into compressed air in cylinder F02B13/02
• CPC Class Codes: F02B 51/02 : involving catalysts
• CPC Class Codes: F02D 41/0047 : Controlling exhaust gas recirculation [EGR] temperature control with cooler in recirculation circuit F02M26/33
• CPC Class Codes: F02M 25/00 : Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture adding secondary air to fuel-air mixture F02M23/00; adding exhaust gases F02M26/00; fuel-injection apparatus operating simultaneously on two or more fuels or on a liquid fuel and another liquid F02M43/00
• CPC Class Codes: F02M 26/15 : in relation to engine exhaust purifying apparatus
• CPC Class Codes: F05C 2201/0427 : Platinum group, e.g. Pt, Ir
• CPC Class Codes: Y02A 50/20 : Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
• CPC Class Codes: Y02T 10/12 : Improving ICE efficiencies

Abstract

Emissions of pollutants from diesel engines are reduced by a combination of mechanical devices and fuel additives. In one series of embodiments, diesel emissions of NO_x and particulates are reduced, simultaneously with gaseous hydrocarbons and carbon monoxide, by the combined use of exhaust gas recirculation or engine timing modification, with a particulate trap and a platinum group metal catalyst composition. In another embodiment, a multi-metal catalyst composition, comprising a combination of a platinum metal catalyst composition and at least one auxiliary catalyst metal composition, especially cerium or copper, is employed to provide catalyst metal to the exhaust system including a diesel trap to lower the balance point of the particulate trap (the temperature at which the rate of trap loading equals the rate of regeneration) while also lowering the emissions of carbon monoxide and unburned hydrocarbons. Data for platinum, copper and cerium catalysts establishes effective amounts. Tests also show selective maintenance of low oxidation of SO₂ to SO₃.

Claims

1. A method for improving the operation of a diesel engine equipped with a diesel trap, comprising:

adding a platinum group metal composition and a cerium compound to a diesel fuel in an effective amount to lower the emissions of unburned hydrocarbons and carbon monoxide and to lower the temperature at which particulates are burned from the trap;

operating the diesel engine by burning the fuel over a sufficient period of time to produce exhaust gases and achieve a sustained reduction in unburned hydrocarbons and carbon monoxide; and

passing the exhaust gases from the operation of the engine through the diesel trap whereby particulates are collected in the trap and burned therein at a temperature lower than could be achieved in the absence of the platinum group metal and the cerium.

2. A method according to claim 1 wherein platinum group metal catalyst is present in the fuel in amounts effective to reduce the balance point temperature of the trap by at least 50°

C.

3. A method according to claim 1 wherein the platinum group metal catalyst composition is employed at a level sufficient to supply 0.05 to about 1.0 ppm of platinum group metal and the cerium compound is employed at a level effective to supply from about 1 to about 100 ppm of cerium metal, both based on the fuel combusted.

4. A method of claim 1 wherein said diesel engine is modified by retarding engine timing or recirculating exhaust gas effectively to reduce NO_x emissions.

5. A method for improving the operation of a diesel engine by lowering the emissions of unburned hydrocarbons and carbon monoxide, comprising:

providing a diesel fuel and combustion air;

providing a platinum group metal catalyst composition selected from the group consisting of alcoholates, sulfonates, beta-diketonates, soaps, and mixtures of these;

combusting the fuel in a diesel engine to produce exhaust gases;

and, directing exhaust gases into an exhaust system,

wherein the platinum group metal catalyst composition is introduced into the fuel, exhaust gases or.combustion air, in amounts effective to provide platinum group metal in the exhaust system at a level of up to 1 ppm based on the volume of fuel burned to produce the exhaust gases.

6. A method of claim 5, wherein the platinum group metal composition comprises a soap of a fatty acid, selected from the group consisting of stearates, palmitates, laurates, tallates, napthanates, and mixtures of these.

7. A method according to claim 5 wherein the platinum group metal catalyst composition is employed at a level sufficient to supply 0.05 to about 1.0 ppm of platinum group metal, and also provided is a cerium compound employed at a level effective to supply from about 1 to about 100 ppm of cerium metal, both concentrations based on the fuel combusted.

8. A method according to claim 7 wherein the exhaust system includes a trap and the platinum group metal catalyst and the cerium metal are present in the fuel in amounts effective to reduce the balance point temperature of the trap by at least 500°

C., the platinum group metal catalyst composition being employed at a level sufficient to supply 0.10 to 0.5 ppm of platinum group metal and the auxiliary catalyst metal composition being employed at a level effective to supply from 20 to 60 ppm of cerium in the fuel.

9. A method of claim 5 wherein said diesel engine is modified by retarding engine timing or recirculating exhaust gas effectively to reduce NO_x emissions.

10. A method for operating a diesel engine with reduced emissions of NO_x, particulates, gaseous hydrocarbons and carbon monoxide, comprising:

providing a diesel engine and a source of diesel fuel;

providing a combustion air mixture including incoming air and exhaust gases from a previous combustion cycle of the engine;

providing a platinum group metal catalyst composition and an auxiliary catalytic metal composition comprising cerium;

introducing the combustion air mixture into the cylinder of a diesel engine;

compressing the combustion air within the cylinder;

injecting the diesel fuel into the cylinder of a diesel engine;

combusting the fuel to produce exhaust gases;

directing the exhaust gases into an exhaust system including a diesel trap to remove particulates from the exhaust gases; and

,

mixing a portion of the exhaust gases with incoming combustion air to provide a combustion air mixture for a subsequent combustion cycle;

wherein the amount of exhaust gases present in the combustion air mixture in the cylinder of the diesel engine is effective to lower the production of NO_x by the engine utilizing said combustion air mixture as compared to combustion air not containing exhaust gases; and

wherein a platinum group metal catalyst composition and the auxiliary catalytic metal composition are present in the fuel, combustion air mixture, or exhaust gases in amounts effective to provide sufficient platinum group metal and auxiliary catalyst metal in the exhaust system to lower the emissions of unburned hydrocarbons and carbon monoxide and to lower the balance point of the trap.

11. A method according to claim 10 wherein said portion of the exhaust gases that is mixed with incoming combustion air, is so mixed after passing through the particulate trap.

12. A method according to claim 10 wherein said platinum group metal catalyst composition is an alcoholate, sulfonate, beta-diketonate or a soap selected from the group consisting of stearates, palmitates, laurates, tallates, napthanates, other fatty acid soaps, and mixtures of two or more of these.

13. A method according to claim 10 wherein said platinum group metal catalyst composition is a fuel-soluble composition and is employed in the fuel at a level sufficient to supply 0.05 to about 1.0 ppm of platinum group metal, and the auxiliary catalytic metal composition is employed in the fuel in an amount to provide a concentration of from about 1 to 100 ppm cerium.

14. A method according to claim 13 wherein platinum group metal catalyst and the auxiliary catalytic metal are present in the fuel in amounts effective to reduce the balance point temperature of the trap by at least 50°

C., the platinum group metal catalyst composition being employed at a level sufficient to supply 0.10 to 0.5 ppm of platinum group metal and the auxiliary catalyst metal composition being employed at a level effective to supply from 20 to 60 ppm of cerium in the fuel.

15. A method for improving the operation of a diesel engine including a diesel trap by lowering the emissions of NO_x, unburned hydrocarbons and carbon monoxide, while also reducing the balance point of the trap, the method comprising:

providing a diesel engine and a source of diesel fuel;

providing a platinum group metal catalyst composition and an auxiliary catalytic metal composition containing at least one of copper and cerium;

introducing combustion air into the cylinder of a diesel engine;

compressing the combustion air within the cylinder;

injecting the diesel fuel into the cylinder of a diesel engine, the injection timing of the diesel engine being set in a manner designed to reduce the nitrogen oxides emissions from the engine after combustion of a diesel fuel;

combusting the fuel to produce exhaust gases containing particulates and platinum group metal catalyst and the auxiliary catalytic metal;

and, directing exhaust gases into an exhaust system including a diesel trap which removes at least a portion of the particulates from the exhaust gases,

wherein the platinum group metal catalyst composition and the auxiliary catalytic metal composition are introduced into the fuel, exhaust gases or combustion air, in amounts effective to provide sufficient platinum group metal and auxiliary catalyst metal in the exhaust system to lower the balance point temperature of particulates in the trap and to reduce emissions of unburned hydrocarbons and carbon monoxide.

16. A method for according to claim 15 wherein:

said auxiliary catalytic metal composition contains at least one metal metal selected from the group consisting of calcium, magnesium, manganese, iron, sodium, lithium, potassium, and mixtures thereof.

17. A method according to claim 15 wherein the platinum group metal catalyst composition is employed at a level sufficient to supply 0.05 to 1.0 ppm of platinum group metal and the auxiliary catalyst metal composition is employed at a level effective to supply from 1 to 100 ppm of the auxiliary catalyst metal, based on the fuel combusted.

18. A method of claim 15, wherein said platinum group metal composition has a breakdown temperature of at least about 50°

C., and a partition ratio of said platinum metal composition of at least about 25.

19. A method according to claim 15 wherein said platinum group metal catalyst composition is an alcoholate, sulfonate, beta-diketonate or a soap selected from the group consisting of stearates, palmitates, laurates, tallates, napthanates, other fatty acid soaps, and mixtures of two or more of these.

20. A method for improving the operation of a diesel engine exhaust system comprising:

adding a platinum group metal composition and at one least auxiliary catalytic metal composition selected from the group consisting of compounds of sodium, lithium, potassium, cerium, iron, copper, calcium, magnesium, manganese, and mixtures of these, to a diesel fuel in effective amount such that exhaust produced by combustion catalyzes the exhaust system including a diesel trap effectively to lower the emissions of unburned hydrocarbons and carbon monoxide;

operating a diesel engine by burning the fuel; and

passing the exhaust from the operation of the engine through the exhaust system including the diesel trap to reduce the emissions of particulates, hydrocarbons and carbon monoxide and reduce the balance point for the trap.

21. A method for improving the operation of a diesel engine including a diesel trap by lowering the emissions of NO_x, unburned hydrocarbons and carbon monoxide, while also reducing the balance point of the trap, the method comprising:

providing a diesel engine and a source of diesel fuel;

providing a platinum group metal catalyst composition and an auxiliary catalytic metal composition containing cerium;

introducing combustion air into the cylinder of a diesel engine;

compressing the combustion air within the cylinder;

injecting the diesel fuel into the cylinder of a diesel engine, thereby combusting the fuel to produce exhaust gases containing particulates and platinum group metal catalyst and cerium catalyst;

and, directing exhaust gases into an exhaust system including a diesel trap which removes at least a portion of the particulates from the exhaust gases,

wherein the platinum group metal catalyst composition and the auxiliary catalytic metal composition are introduced into the fuel, exhaust gases or combustion air, in amounts effective to provide sufficient platinum group metal and cerium catalyst in the exhaust system to lower the balance point temperature of particulates in the trap and to reduce emissions of particulates, unburned hydrocarbons and carbon monoxide.

22. A method for improving the operation of a diesel engine including a diesel trap by lowering the emissions of NO_x, unburned hydrocarbons and carbon monoxide, while also reducing the balance point of the trap, the method comprising:

providing a diesel engine and a source of diesel fuel;

providing a platinum group metal catalyst composition and an auxiliary catalytic metal composition selected from the group consisting of compounds of sodium, lithium, potassium, cerium, iron, copper, calcium, magnesium, manganese, and mixtures;

introducing combustion air into the cylinder of a diesel engine;

compressing the combustion air within the cylinder;

injecting the diesel fuel into the cylinder of a diesel engine, thereby combusting the fuel to produce exhaust gases containing particulates and platinum group metal catalyst and auxiliary catalytic metal;

and, directing exhaust gases into an exhaust system including a diesel trap which removes at least a portion of the particulates from the exhaust gases,

wherein the platinum group metal catalyst composition and the auxiliary catalytic metal composition are introduced.into the fuel, exhaust gases or combustion air, in amounts effective to provide sufficient platinum group metal and auxiliary catalytic metal in the exhaust system to lower the balance point temperature of particulates in the trap and to reduce emissions of particulates, unburned hydrocarbons and carbon monoxide.