Method for reducing pollution emissions from a diesel engine

• US 5,266,083 A
• Filed: 12/16/1991
• Issued: 11/30/1993
• Est. Priority Date: 12/28/1988
• Status: Expired due to Term

• Current Assignee: Platinum Plus, Inc.
• Original Assignee: Platinum Plus, Inc.
• Inventors: Peter-Hoblyn, Jeremy D., Sprague, Barry N., Valentine, James M., Epperly, W. Robert
• Primary Examiner(s): MEDLEY, MARGARET B
• Application Number:
  US07/808,436
• Time in Patent Office: 715 Days
• Field of Search: 44/358, 44/359, 44/361, 44/363, 44/367, 556/32, 556/136, 556/137, 123/1 A, 123/321, 123/347
• US Class Current: 44/358
• CPC Class Codes: B01D 2255/102 Platinum group metals
• CPC Class Codes: B01D 2255/705 Ligands for metal-organic catalysts
• CPC Class Codes: B01D 2255/906 Catalyst dispersed in the gas
• CPC Class Codes: B01D 2258/012 Diesel engines and lean burn gasoline engines
• CPC Class Codes: B01D 53/9413 Processes characterised by a specific catalyst
• CPC Class Codes: C07F 15/0033 Iridium compounds
• CPC Class Codes: C07F 15/006 Palladium compounds
• CPC Class Codes: C07F 15/0073 Rhodium compounds
• CPC Class Codes: C07F 15/0086 Platinum compounds
• CPC Class Codes: C07F 17/02 of metals of Groups 8, 9 or 10 of the Periodic System
• CPC Class Codes: C10L 1/10 containing additives
• 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 1/1814 Chelates
• CPC Class Codes: C10L 1/1824 mono-hydroxy
• 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 1/2227 urea; derivatives thereof; urethane C10L1/221 takes 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 1/231 : nitro compounds; nitrates; nitrites C10L1/221 takes precedence
• 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: C10L 3/003 : Additives for gaseous fuels
• CPC Class Codes: F01N 2430/04 : by adding non-fuel substances to combustion air or fuel, e.g. additives
• 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 3/035 : 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: F02M 27/02 : by catalysts
• CPC Class Codes: Y02T 10/12 : Improving ICE efficiencies

Abstract

The invention presented relates to a method for reducing the emission of nitrogen oxides from a diesel engine without significant loss of fuel efficiency and without significant increases in carbon monoxide and hydrocarbon emissions. The method involves preparing a diesel engine such that the injection timing thereof is set at a point sufficient to obtain reductions in the nitrogen oxides emissions from the engine; and firing the diesel engine with a diesel fuel having admixed therein an additive which comprises a fuel soluble organometallic platinum group metal coordination composition.

Claims

1. A method for increasing the combustion efficiency of a diesel engine comprising

a) preparing a diesel engine such that the injection timing thereof is set before top dead center at a level sufficient to obtain reductions in the nitrogen oxides emissions from the engine;

and

b) firing the diesel engine with a diesel fuel having admixed therein an additive which comprises a fuel soluble organometallic platinum group metal coordination composition selected from the group consisting of

i) a composition of the general formula

space="preserve" listing-type="equation">L.sup.1 PtR.sup.1 R.sup.2

wherein L¹ is either a single cyclic polyolefin or nitrogenous bidentate ligand or a pair of nitrogenous or acetylenic monodentate ligands; and

R¹ and R² are each, independently, substituted or unsubstituted methyl, benzyl, aryl, cyclooc-tadiene or pentamethyl cyclopentadiene;

ii) a composition of the general formula

space="preserve" listing-type="equation">L.sup.2 M.sup.1 R.sup.3

wherein L² is either a single cyclic polyolefin or nitrogenous bidentate ligand or a pair of nitrogenous or acetylenic monodentate ligands;

M¹ is rhodium or iridium; and

R³ is cyclooctadiene or pentamethyl cyclopentadiene;

iii) a composition of the general formula

space="preserve" listing-type="equation">L.sup.3 M.sup.2 (C.sub.r R.sup.4.sub.4)

wherein L³ is either a single cyclic polyolefin or nitrogenous bidentate ligand or a pair of nitrogenous monodentate ligands;

M² is a platinum, palladium, rhodium or iridium; and

R⁴ is COOR⁵, wherein R⁵ is hydrogen or alkyl having from 1 to 10 carbons;

iv) a composition of the general formula

space="preserve" listing-type="equation">L.sup.4 M.sup.3 (COOR.sup.6).sub.2

or a dimer thereof, wherein L⁴ is a non-nitrogenous cyclic polyolefin ligand;

M³ is platinum or iridium; and

R⁶ is alkyl;

v) a composition comprising the reaction product of L⁵ RhX and R⁷ MgX wherein L⁵ is a non-nitrogenous cyclic polyolefin ligand;

R⁷ is methyl, benzyl, aryl, cyclooctadiene or pentamethyl cyclopentadiene; and

X is a halide, wherein said platinum group metal compound is provided in an amount effective to supply from 0.01 to 1.0 parts per million of platinum group metal per part of fuel.

vi) palladium acetylene complexes having the general formula ##STR4## wherein R⁸ is aryl or alkyl; and

R⁹ is aryl;

vii) metal allyl complexes having the general formula

space="preserve" listing-type="equation">M.sup.r (C.sub.3 H.sub.5).sub.3

wherein M⁴ is rhodium or iridium;

viii) platinum (IV) compositions having the general formula

space="preserve" listing-type="equation">R.sup.9.sub.3 PtR.sup.10

wherein R⁹ is aryl, alkyl or mixtures thereof; and

R¹⁰ is hydroxyl, acetylacetonate, cyclopentadiene or pentamethyl cyclopentadiene; and

ix) a composition of the general formula

space="preserve" listing-type="equation">L.sup.6 M.sup.5 R.sup.13

wherein L⁶ is substituted or unsubstituted butadiene or cyclohexadiene;

M⁵ is rhodium or iridium; and

R¹³ is cyclopentadiene or pentamethyl cyclopentadiene, wherein said composition

A. is resistant to breakdown under ambient temperatures;

B. contains no more than about 500 ppm phosphorus, arsenic, antimony or halides; and

C. has a partition ratio sufficient to maintain preferential solubility in the fuel.

2. The method of claim 1, wherein said injection timing is retarded between about 0.5°

and about 8°

before top dead center.

3. The method of claim 2, wherein said injection timing is retarded between about 2°

and about 6°

before top dead center.

4. The method of claim 1, wherein said composition has a breakdown temperature at least about 50°

C.

5. The method of claim 1, wherein the partition ratio of said composition is at least about 25.

6. The method of claim 5, wherein said composition has at least one platinum group metal-to-carbon covalent bond.

7. The method of claim 1, wherein L¹, L², and L³ are selected from the group consisting of cyclopentadiene, cyclooctadiene, pentamethyl cyclopentadiene, cyclooctatetrene, o-phenantholine, o-toluidine, norbornadiene, pyridine, and bipyridine.

8. The method of claim 1, wherein L⁴ and L⁵ are selected from the group consisting of cyclooctadiene and pentamethyl cyclopentadiene.

9. The method of claim 1, wherein said additive further comprises a fuel-soluble solvent for said composition comprising octyl nitrate.

10. The method of claim 1 which further comprises disposing a diesel engine particulate trap in the exhaust stream of said engine.

11. The method of claim 10, wherein said diesel engine particulate trap is made of ceramic, metal, glass fibers, or mixtures thereof.

12. The method of claim 11, wherein said diesel engine particulate trap further comprises an auxiliary heater to raise the temperature of the diesel engine particulate trap at programmed times in the engine operation cycle.