US20060260185A1 - Fuel Additive and Catalyst Treatment Process - Google Patents

Fuel Additive and Catalyst Treatment Process Download PDF

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Publication number
US20060260185A1
US20060260185A1 US11/380,674 US38067406A US2006260185A1 US 20060260185 A1 US20060260185 A1 US 20060260185A1 US 38067406 A US38067406 A US 38067406A US 2006260185 A1 US2006260185 A1 US 2006260185A1
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Prior art keywords
platinum
cerium
composition comprises
composition
ppm
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Abandoned
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US11/380,674
Inventor
James Valentine
Barry Sprague
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Clean Diesel Technologies Inc
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Clean Diesel Technologies Inc
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Priority to US67644505P priority Critical
Application filed by Clean Diesel Technologies Inc filed Critical Clean Diesel Technologies Inc
Priority to US11/380,674 priority patent/US20060260185A1/en
Assigned to CLEAN DIESEL TECHNOLOGIES, INC. reassignment CLEAN DIESEL TECHNOLOGIES, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SPRAGUE, BARRY N., VALENTINE, JAMES M.
Publication of US20060260185A1 publication Critical patent/US20060260185A1/en
Application status is Abandoned legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/30Organic compounds compounds not mentioned before (complexes)
    • C10L1/301Organic compounds compounds not mentioned before (complexes) derived from metals
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/12Inorganic compounds
    • C10L1/1216Inorganic compounds metal compounds, e.g. hydrides, carbides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/02Use of additives to fuels or fires for particular purposes for reducing smoke development
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/182Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy

Abstract

Described are a gasoline fuel additive which meets the needs of the art with regard to the problems associated with inactivation of catalytic converters. The fuel additive will comprise platinum, preferably as platinum COD and cerium, preferably in a form dispersible or soluble in gasoline, e.g., cerium octoate, cerium oleate and/or cerium stearate. Dosage rates for the gasoline will provide from about 0.05 to about 2.0 ppm platinum and from about 1 to about 100 ppm cerium. Ratios of the platinum to cerium are preferably within the range of from 1:5 to 1:100.

Description

    RELATED APPLICATION AND PRIORITY CLAIM
  • This claims priority to pending U.S. Provisional Patent Application Ser. No. 60/676,445, filed Apr. 28, 2005, the disclosure of which is hereby incorporated by reference.
  • BACKGROUND OF THE INVENTION
  • Gasoline engines produce pollutants in the form or carbon monoxide (CO), unburned hydrocarbons (HC) and nitrogen oxides (NOx). The advent and development of catalytic converters has provided significant reductions in these pollutants.
  • However, as noted in U.S. Pat. No. 4,891,050, and others, these converters often lose their initial strong activity. The use of platinum group metal containing fuel borne catalysts is suggested by the above noted U.S. Pat. No. 4,891,050, but not all causes of reduced activity can be addressed by the presence of platinum alone.
  • Significant development over many years has failed to fully address problems such as the loss of active cites on supported platinum catalysts due possibly to inactivation. Possible causes of inactivation are sulfur, phosphorous, hydrocarbons and/or carbon or partially carbonized hydrocarbons.
  • There is a present need for a treatment for the catalysts and/or a fuel additive or fuel composition that would moderate, control or prevent such inactivation.
  • SUMMARY OF THE INVENTION
  • The present invention provides a gasoline fuel additive which meets the needs of the art with regard to the above-noted problems. The fuel additive of the invention will comprise platinum, preferably as platinum COD and cerium, preferably in a form dispersible or soluble in gasoline, e.g., cerium octoate, cerium oleate and/or cerium stearate. Dosage rates for the gasoline will provide from about 0.05 to about 2.0 ppm platinum and from about 1 to about 100 ppm cerium. Ratios of the platinum to cerium preferably being within the range of from 1:5 to 1:100. High concentrations of platinum within this range are preferred, e.g., from 1.0 to 2.0. ppm platinum. High ratios of platinum to cerium are also preferred, e.g., from 1:5 to 1:25.
  • The preferred fuels for treatment according to the invention are well known to those skilled in the art and usually contain a major portion of a normally-liquid fuel such as hydrocarbonaceous petroleum distillate fuel, e.g., motor gasoline as defined by ASTM Specification D-439-73, and suitable additives. Such fuels can also contain non-hydrocarbonaceous materials such as alcohols, ethers, organo-nitro compounds and the like (e.g., methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane). These are also within the scope of this invention, as are liquid fuels derived from vegetable or mineral sources such as corn, alfalfa, shale, and coal. Examples of such fuel mixtures are combinations of gasoline and ethanol, (i.e., gasohol) diesel fuel and ether, gasoline and nitromethane, etc. Particularly preferred fuels are gasoline combined with from 1 to 25% of ethanol.
  • Any of the fuel-soluble platinum group metal compositions, e.g., 1,5-cyclooctadiene platinum diphenyl (platinum COD), described in U.S. Pat. No. 4,891,050 to Bowers, et al., U.S. Pat. No. 5,034,020 to Epperly, et al., and U.S. Pat. No. 5,266,083 to Peter-Hoblyn, et al., can be employed as the platinum source. Other suitable platinum group metal catalyst compositions include commercially-available or easily-synthesized platinum group metal acetylacetonates (acac), platinum group metal dibenzylidene acetonates, and fatty acid soaps of tetramine platinum metal complexes, e.g., tetramine platinum oleate. The platinum group metal is preferred at concentrations of 0.01-2.0 ppm platinum w/v, i.e., weight of platinum group metal in mg per volume of fuel in liters. Preferred levels are toward the lower end of this range, e.g., 0.1-0.5 ppm. Platinum COD is the preferred form of platinum for addition to the fuel.
  • Dosage rates will be lower for continuous treatment and lower within the above range where the doses are intermittent and intended for immediate effect.
  • The following example provides a formulation of a fuel additive and indicates the dosage level for use in a gasoline engine having an exhaust system including a catalytic converter. These formulations are representative and not limiting.
  • EXAMPLE
  • grams/liter 1 ppm Pt and 15 1 ppm Pt ppm Cerium Pt COD concentrate— 39.33 39.33 2% Pt metal as Pt COD (42.6 wt. % Pt) in toluene: 4.7% Pt COD and 95.3% toluene Cerium Octoate 0.00 98.67 12 wt. % Ce A150 Aromatic naphtha, balance balance flash point of 150° F.
  • This is an all Pt or all Pt+Ce formulation. The additive can also be made to provide 0.85/0.15 ppmw Pt/Rh by using a proportionate amount of concentrate (0.3% Rh from Rh(acac)3 in toluene). The compositions above are designed to provide either 1.0 ppm Pt only or 1.0 ppmw Pt+15 ppm Ce in 20 gallons of gasoline from a single 75 ml dose.
  • The additive of the invention can be blended with gasoline before, during or after fueling an engine. When used as a treatment to reactivate a catalytic converter but not used as part of the routine fueling of the vehicle, it is preferably applied in several high dosages, e.g., for from 2 to 5 tanks full of gasoline.
  • The above description is for the purpose of teaching the person of ordinary skill in the art how to practice the present invention, and it is not intended to detail all of those obvious modifications and variations of it which will become apparent to the skilled worker upon reading this description. It is intended, however, that all such obvious modifications and variations be included within the scope of the present invention which is defined by the following claims. The claims cover the indicated components and steps in all arrangements and sequences which are effective to meet the objectives intended for the invention, unless the context specifically indicates the contrary.

Claims (17)

1. A composition comprising gasoline and a fuel additive comprising a platinum group metal compostion, and a cerium composition which contains from about 0.05 to about 2.0 ppm platinum and from about 1 to about 100 ppm cerium.
2. A composition according to claim 1 wherein the ratio of the platinum to cerium is within the range of from 1:5 to 1:100.
3. A composition according to claim 1 wherein the platinum composition comprises a member selected from the group consisting of 1,5-cyclooctadiene platinum diphenyl, platinum group metal acetylacetonate, platinum group metal dibenzylidene acetonates, and fatty acid soaps of tetramine platinum metal complexes.
4. A composition according to claim 1 wherein the platinum composition comprises a member selected from the group consisting of 1,5-cyclooctadiene platinum diphenyl and the cerium composition comprises cerium octoate, cerium oleate and/or cerium stearate.
5. A composition according to claim 1 wherein the ratio of the platinum to cerium is within the range of from 1:5 to 1:100 and the platinum composition comprises a member selected from the group consisting of 1,5-cyclooctadiene platinum diphenyl and the cerium composition comprises cerium octoate, cerium oleate and/or cerium stearate.
6. A composition according to claim 1 wherein the gasoline comprises from 1 to 25% ethanol.
7. A process for rejuvenating a catalytic converter, comprising adding to gasoline an additive comprising a platinum group metal compostion, and a cerium composition which contains from about 0.05 to about 2.0 ppm platinum and from about 1 to about 100 ppm cerium.
8. A process according to claim 7 wherein the ratio of the platinum to cerium is within the range of from 1:5 to 1:100.
9. A process according to claim 7 wherein the platinum composition comprises a member selected from the group consisting of 1,5-cyclooctadiene platinum diphenyl, platinum group metal acetylacetonate, platinum group metal dibenzylidene acetonates, and fatty acid soaps of tetramine platinum metal complexes.
10. A process according to claim 7 wherein the platinum composition comprises a member selected from the group consisting of 1,5-cyclooctadiene platinum diphenyl and the cerium composition comprises cerium octoate, cerium oleate and/or cerium stearate.
11. A process according to claim 7 wherein the ratio of the platinum to cerium is within the range of from 1:5 to 1:100 and the platinum composition comprises a member selected from the group consisting of 1,5-cyclooctadiene platinum diphenyl and the cerium composition comprises cerium octoate, cerium oleate and/or cerium stearate.
12. A process according to claim 7 wherein the gasoline comprises from 1 to 25% ethanol.
13. A fuel additive comprising a platinum group metal compostion, and a cerium composition which contains from about 0.05 to about 2.0 ppm platinum and from about 1 to about 100 ppm cerium.
14. A fuel additive according to claim 13 wherein the ratio of the platinum to cerium is within the range of from 1:5 to 1:100.
15. A fuel additive according to claim 13 wherein the platinum composition comprises a member selected from the group consisting of 1,5-cyclooctadiene platinum diphenyl, platinum group metal acetylacetonate, platinum group metal dibenzylidene acetonates, and fatty acid soaps of tetramine platinum metal complexes.
16. A fuel additive according to claim 13 wherein the platinum composition comprises a member selected from the group consisting of 1,5-cyclooctadiene platinum diphenyl and the cerium composition comprises cerium octoate, cerium oleate and/or cerium stearate.
17. A fuel additive according to claim 13 wherein the ratio of the platinum to cerium is within the range of from 1:5 to 1:100 and the platinum composition comprises a member selected from the group consisting of 1,5-cyclooctadiene platinum diphenyl and the cerium composition comprises cerium octoate, cerium oleate and/or cerium stearate.
US11/380,674 2005-04-28 2006-04-28 Fuel Additive and Catalyst Treatment Process Abandoned US20060260185A1 (en)

Priority Applications (2)

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US67644505P true 2005-04-28 2005-04-28
US11/380,674 US20060260185A1 (en) 2005-04-28 2006-04-28 Fuel Additive and Catalyst Treatment Process

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9475004B2 (en) 2014-06-06 2016-10-25 Clean Diesel Technologies, Inc. Rhodium-iron catalysts
US9511358B2 (en) 2013-11-26 2016-12-06 Clean Diesel Technologies, Inc. Spinel compositions and applications thereof
US9511353B2 (en) 2013-03-15 2016-12-06 Clean Diesel Technologies, Inc. (Cdti) Firing (calcination) process and method related to metallic substrates coated with ZPGM catalyst
US9511350B2 (en) 2013-05-10 2016-12-06 Clean Diesel Technologies, Inc. (Cdti) ZPGM Diesel Oxidation Catalysts and methods of making and using same
US9545626B2 (en) 2013-07-12 2017-01-17 Clean Diesel Technologies, Inc. Optimization of Zero-PGM washcoat and overcoat loadings on metallic substrate
US9555400B2 (en) 2013-11-26 2017-01-31 Clean Diesel Technologies, Inc. Synergized PGM catalyst systems including platinum for TWC application
US9700841B2 (en) 2015-03-13 2017-07-11 Byd Company Limited Synergized PGM close-coupled catalysts for TWC applications
US9731279B2 (en) 2014-10-30 2017-08-15 Clean Diesel Technologies, Inc. Thermal stability of copper-manganese spinel as Zero PGM catalyst for TWC application
US9771534B2 (en) 2013-06-06 2017-09-26 Clean Diesel Technologies, Inc. (Cdti) Diesel exhaust treatment systems and methods
US9861964B1 (en) 2016-12-13 2018-01-09 Clean Diesel Technologies, Inc. Enhanced catalytic activity at the stoichiometric condition of zero-PGM catalysts for TWC applications
US9951706B2 (en) 2015-04-21 2018-04-24 Clean Diesel Technologies, Inc. Calibration strategies to improve spinel mixed metal oxides catalytic converters
US10265684B2 (en) 2017-05-04 2019-04-23 Cdti Advanced Materials, Inc. Highly active and thermally stable coated gasoline particulate filters

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4981050A (en) * 1987-07-27 1991-01-01 Kurtossy Csaba G Continuously variable power converter
US5034020A (en) * 1988-12-28 1991-07-23 Platinum Plus, Inc. Method for catalyzing fuel for powering internal combustion engines
US5266083A (en) * 1988-12-28 1993-11-30 Platinum Plus, Inc. Method for reducing pollution emissions from a diesel engine
US5749928A (en) * 1984-12-04 1998-05-12 Platinum Plus, Inc. Method for reducing emissions from or increasing the utilizable energy of fuel for powering internal combustion engines
US20030094397A1 (en) * 2001-08-15 2003-05-22 Fortum Oyj Clean-burning MTBE-free gasoline fuel
US20030148235A1 (en) * 2002-02-04 2003-08-07 Valentine James M. Reduced-emissions combustion utilizing multiple-component metallic combustion catalyst

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5749928A (en) * 1984-12-04 1998-05-12 Platinum Plus, Inc. Method for reducing emissions from or increasing the utilizable energy of fuel for powering internal combustion engines
US4981050A (en) * 1987-07-27 1991-01-01 Kurtossy Csaba G Continuously variable power converter
US5034020A (en) * 1988-12-28 1991-07-23 Platinum Plus, Inc. Method for catalyzing fuel for powering internal combustion engines
US5266083A (en) * 1988-12-28 1993-11-30 Platinum Plus, Inc. Method for reducing pollution emissions from a diesel engine
US20030094397A1 (en) * 2001-08-15 2003-05-22 Fortum Oyj Clean-burning MTBE-free gasoline fuel
US20030148235A1 (en) * 2002-02-04 2003-08-07 Valentine James M. Reduced-emissions combustion utilizing multiple-component metallic combustion catalyst

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9511353B2 (en) 2013-03-15 2016-12-06 Clean Diesel Technologies, Inc. (Cdti) Firing (calcination) process and method related to metallic substrates coated with ZPGM catalyst
US9511350B2 (en) 2013-05-10 2016-12-06 Clean Diesel Technologies, Inc. (Cdti) ZPGM Diesel Oxidation Catalysts and methods of making and using same
US9771534B2 (en) 2013-06-06 2017-09-26 Clean Diesel Technologies, Inc. (Cdti) Diesel exhaust treatment systems and methods
US9545626B2 (en) 2013-07-12 2017-01-17 Clean Diesel Technologies, Inc. Optimization of Zero-PGM washcoat and overcoat loadings on metallic substrate
US9511358B2 (en) 2013-11-26 2016-12-06 Clean Diesel Technologies, Inc. Spinel compositions and applications thereof
US9555400B2 (en) 2013-11-26 2017-01-31 Clean Diesel Technologies, Inc. Synergized PGM catalyst systems including platinum for TWC application
US9475005B2 (en) 2014-06-06 2016-10-25 Clean Diesel Technologies, Inc. Three-way catalyst systems including Fe-activated Rh and Ba-Pd material compositions
US9579604B2 (en) 2014-06-06 2017-02-28 Clean Diesel Technologies, Inc. Base metal activated rhodium coatings for catalysts in three-way catalyst (TWC) applications
US9475004B2 (en) 2014-06-06 2016-10-25 Clean Diesel Technologies, Inc. Rhodium-iron catalysts
US9731279B2 (en) 2014-10-30 2017-08-15 Clean Diesel Technologies, Inc. Thermal stability of copper-manganese spinel as Zero PGM catalyst for TWC application
US9700841B2 (en) 2015-03-13 2017-07-11 Byd Company Limited Synergized PGM close-coupled catalysts for TWC applications
US9951706B2 (en) 2015-04-21 2018-04-24 Clean Diesel Technologies, Inc. Calibration strategies to improve spinel mixed metal oxides catalytic converters
US9861964B1 (en) 2016-12-13 2018-01-09 Clean Diesel Technologies, Inc. Enhanced catalytic activity at the stoichiometric condition of zero-PGM catalysts for TWC applications
US10265684B2 (en) 2017-05-04 2019-04-23 Cdti Advanced Materials, Inc. Highly active and thermally stable coated gasoline particulate filters

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Owner name: CLEAN DIESEL TECHNOLOGIES, INC., CONNECTICUT

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:VALENTINE, JAMES M.;SPRAGUE, BARRY N.;REEL/FRAME:017979/0184;SIGNING DATES FROM 20060709 TO 20060710

STCB Information on status: application discontinuation

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