WO1986003492A1 - Fuel additives and fuel containing soluble platinum group metal compounds and use in internal combusiton engines - Google Patents

Fuel additives and fuel containing soluble platinum group metal compounds and use in internal combusiton engines Download PDF

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Publication number
WO1986003492A1
WO1986003492A1 PCT/US1985/002387 US8502387W WO8603492A1 WO 1986003492 A1 WO1986003492 A1 WO 1986003492A1 US 8502387 W US8502387 W US 8502387W WO 8603492 A1 WO8603492 A1 WO 8603492A1
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Prior art keywords
composition according
group metal
platinum group
fuel
gasoline
Prior art date
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PCT/US1985/002387
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English (en)
French (fr)
Inventor
Wayne E. Bowers
Barry N. Sprague
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Fuel Tech, Inc.
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
Application filed by Fuel Tech, Inc. filed Critical Fuel Tech, Inc.
Priority to MC85US8502387D priority Critical patent/MC1758A1/xx
Priority to BR8507104A priority patent/BR8507104A/pt
Priority to HU85568Q priority patent/HUT44034A/hu
Priority to GB08617717A priority patent/GB2178757B/en
Priority to JP61500068A priority patent/JPH0653879B2/ja
Publication of WO1986003492A1 publication Critical patent/WO1986003492A1/en

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    • A—HUMAN NECESSITIES
    • A46—BRUSHWARE
    • A46B—BRUSHES
    • A46B9/00—Arrangements of the bristles in the brush body
    • A46B9/02—Position or arrangement of bristles in relation to surface of the brush body, e.g. inclined, in rows, in groups
    • A—HUMAN NECESSITIES
    • A46—BRUSHWARE
    • A46B—BRUSHES
    • A46B9/00—Arrangements of the bristles in the brush body
    • A46B9/06—Arrangement of mixed bristles or tufts of bristles, e.g. wire, fibre, rubber
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0086—Platinum compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1814—Chelates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/003—Additives for gaseous fuels
    • A—HUMAN NECESSITIES
    • A46—BRUSHWARE
    • A46B—BRUSHES
    • A46B2200/00—Brushes characterized by their functions, uses or applications
    • A46B2200/30—Brushes for cleaning or polishing
    • A46B2200/3066—Brush specifically designed for use with street cleaning machinery
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1608—Well defined compounds, e.g. hexane, benzene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C10L1/1855—Cyclic ethers, e.g. epoxides, lactides, lactones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1857—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
    • 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

  • the present invention relates to improving the performance of internal combustion engines, both gasoline and diesel; and, more particularly, to the formulation and use of fuel additives and fuels which burn more efficiently and with reduced noxious emissions.
  • 2,151,432 are selenium, antimony, arsenic, bismuth, cadmium, tellurium, thallium, tin, barium, boron, cesium, didymium, lanthanum, potassium, sodium, tantalum, titanium, tungsten and zinc.
  • the preferred organometallic compounds were beta diketone derivatives and their homologues, such as the metal acetylacetonates,, propionylacetonates, formylacetonates, and the like. Such compounds typically provide oxygen-to-metal ratios in the range of 1:1 to 1:10, and no essential feature linked to the presence of oxygen is disclosed.
  • the Lyons and McKone disclosures state that concentrations of from 0.001 to 0.04% (i.e., from 10 to 400 parts per million) are not effective to improve combustion efficiency as introduced, but may become so upon prolonged use as catalytically active deposits are built up in the combustion chamber.
  • the disclosure further states that about 0.01% (i.e., 100 ppm) of the organometallic compound is usually sufficient, once the requisite amount of catalytically active deposits has been built up, to perpetuate that amount of deposits by replacement of losses therefrom.
  • the compounds disclosed were, therefore, not capable of generating any instanta ⁇ neous catalytic effect at low concentrations.
  • U.S. Patent 2,460,780 to Lyons and Dempsey which relates principally to water-soluble catalysts, confirms this at column 1, lines 11-36. Further, no indication was made for preferred oxidation states for the metals disclosed.
  • Patent 2,460,780 to Lyons and Dempsey relates principally to employing catalysts which are soluble in water or other "internal liquid coolants" such as alcohol, water- soluble glycols or aqueous solutions of these. While catalyst levels based on the weight of metal compounds as low as 0.001% are disclosed, it is stated that for immediate catalytic effect the catalyst compounds for useful effect may be present at a level of at least 1% of the weight of the operating fuel charge. In some Examples, fuel- soluble cobalt, cerium and chromium catalysts are added to the fuel at total catalyst levels of 0.01%. No disclosure is given of fuel-soluble catalysts at levels below 0.01% or with oxygenated solvents.
  • the metal complexes of the metals scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, osmium, iridium, platinum, silver, gold, gallium, molybdenum, lead and mercury, with different ligands, can be added to the fuel individually or as a mixture.
  • platinum group metals osmium, iridium, and platinum broad concentrations of from 0.347 to 3.123 grams per liter of fuel are suggested for the various compositions listed in the disclosure, with the range for particularly favorable results being from 0.868 to 1.735 grams per liter of fuel.
  • the cost of these metals and the compositions containing them there is a negative incentive for employing them at the high levels stated by the disclosure to be effective.
  • the tetramethyl platinum compound is not known to exist.
  • Miller and Lieber disclose the use of certain diesel-fuel-soluble organic or organometallic compounds as ignition promoters at concentrations of from 0.02 to 3% (i.e., 200 to 30,000 parts per million). No platinum group metal compounds are identified and no indication is given that the disclosed compounds at the disclosed, or lower levels would improve combustion in a gasoline internal combustion engine.
  • the present invention comprises the application of certain platinum group metal compounds which are directly soluble in engine fuels, such as diesel fuel or gasoline, or solvents for use in internal combustion gasoline and diesel engines.
  • engine fuels such as diesel fuel or gasoline
  • solvents for use in internal combustion gasoline and diesel engines are employed at very small, but catalytically effective levels of from 0.01 to about 1.0 parts of. platinum group metal per one million parts of fuel (ppm).
  • ppm platinum group metal per one million parts of fuel
  • the invention provides gasoline and diesel fuel additive compositions comprising a solution of a fuel-soluble platinum group metal compound in a solvent miscible in the fuel, the platinum group metal compound being present in an amount sufficient to supply from 0.01 to 1.0 parts per million of the platinum group metal when added to a predetermined amount of fuel.
  • Preferred solvents are oxygenated hydrocarbons such as ethanol, tetrahydrofuran, and methyl tertiary butyl ether, and will preferably be employed in amounts of less than 5% of the weight of the fuel.
  • the oxygenated solvents will preferably be employed in amounts sufficient to supply oxygen at a weight ratio to the platinvun group metal of at least 1000:1.
  • platinum group metal compounds are platinum group metal coordination compounds comprising a platinum group metal having a +2 or +4 coordination state with at least one coordination site in the compound being occupied by a functional group containing at least one unsaturated carbon-to-carbon bond with an olefinic, acetylenic or aromatic pi bond configuration.
  • platinum group metal coordination compounds comprising a platinum group metal having a +2 or +4 coordination state with at least one coordination site in the compound being occupied by a functional group containing at least one unsaturated carbon-to-carbon bond with an olefinic, acetylenic or aromatic pi bond configuration.
  • platinum group metal coordination compounds comprising a platinum group metal having a +2 or +4 coordination state with at least one coordination site in the compound being occupied by a functional group containing at least one unsaturated carbon-to-carbon bond with an olefinic, acetylenic or aromatic pi bond configuration.
  • Especially preferred compounds are those of the formula:
  • gasoline and diesel fuel compositions of improved properties which comprises gasoline or diesel fuel and an additive composition dissolved therein, said additive composition comprising a fuel-soluble platinum group metal compound in an amount effective to supply from 0.01 to 1.0 parts of the platinum group metal per million parts of fuel.
  • a method of increasing the utilizable energy of gasoline or diesel fuel for powering internal combustion engines comprising admixing with said gasoline or diesel fuel an additive composition comprising a fuel-soluble platinum group metal compound in an amount effective to supply from 0.01 to 1.0 parts of the platinum group metal per million parts of fuel.
  • the additive compositions according to the invention improve operating efficiency of gasoline and diesel internal combustion engines in terms of increased power output per unit of gasoline burned and reduce the emissions of particulates and noxious gases such as carbon monoxide and nitrogen monoxide.
  • the additives provide beneficial results upon immediate use and over long periods of continuous use.
  • gasoline is defined as a mixture of volatile hydrocarbons for use in a spark-ignited internal combustion engine and having an octane rating [(Research + Motor)/2] of at least 80, typically about 87 to 89 or above, and according to * the more preferred aspects of the invention as having less than 1.4 grams per gallon of lead. Most preferably, the gasoline will be
  • gasoline additive compositions of this invention achieve the most reproducible effect in engines operated under lean conditions, namely an air to fuel ratio of about 14.7:1, and at compression ratios from about 7:1 to 9:1.
  • Diesel fuels for the purposes of this description, are defined as fuel oil number 2 petroleum distillates of volatility and cetane number characteristics effective for the purpose of fueling internal combustion diesel engines.
  • the preferred platinum group metal compounds are coordination compounds. These compounds, especially those coordinated with certain high molecular weight (preferably above 100 daltons) olefinic functional groups, are stable in the presence of moisture. This is extremely important due to the amounts of water present in gasoline and diesel fuels.
  • Gasoline for example, will typically contain dissolved water in amounts on the order of 30 ppm and frequently contains higher levels of dispersed and bulk water.
  • platinum group metal coordination compounds which are directly soluble in gasoline or diesel fuel are available commercially. Compounds which are available often contain objectionable functional groups containing halogen and phosphorus and, therefore, are less than preferred for many internal combustion applications. Preferably, the compounds according to the present invention will have no phosphorus or have low levels which are free of significant dis dvantages.
  • certain platinum group metal compounds can be prepared which are soluble and stable in the fuels and actively catalyze the combustion of gasoline and diesel fuel in internal combustion engines and reduce noxious emissions when introduced as an integral part of the fuel.
  • the preferred class of materials used include platinum group metal coordination states II and IV. Compounds in the lower (II) state of oxidation are preferred due to their function in generating the catalytic effect.
  • a significant feature of the invention is the use of platinum group metal II coordination compound having at least one coordination site occupied by a functional group containing an unsaturated carbon-to-carbon bond of the olefinic, acetylenic or aromatic pi bond configuration. Preferably, two or more of the coordination sites will be occupied by such functional groups since the stability and solubility in gasoline and diesel fuel of compounds having such multiple functional groups are improved. While wishing not to be bound to any particular theory, it is believed that such preferred compounds in the lowest possible oxidant state are the most beneficial for producing instantaneous catalytic effect.
  • Benzene and analogous aromatic compounds such as anthracene and naphthalene.
  • Cyclic dienes and homologues such as cyclooctadiene, methyl cyclopentadiene, and cyclohexadiene.
  • Olefins such as nonene, dodecene, and polyisobutenes.
  • Acetylenes such as nonyne and dodecyne. These unsaturated functional groups, in turn, can be substituted with nonhalogen-, substituents such as alkyl, carboxyl, amino, nitro, hydroxyl and alkoxyl groups. Other coordination sites can be directly occupied by such groups.
  • Platinum group metals include platinum, palladium, rhodium, ruthenium, osmium, and iridium. Compounds including platinum, palladium and rhodium are preferred in the practice of this invention. The most preferred platinum group coordination compounds are those represented by the following formula:
  • M is a platinum group metal and R is benzyl, phenyl or nitrobenzyl.
  • the platinum group metal compound will be added to gasoline or diesel fuel in an amount effective to improve engine performance in terms of operating efficiency or emissions reduction.
  • the compound will supply an amount of the metal within the range of from 0.01 to 1.0 parts of the platinum group metal per one million parts of gasoline (ppm w/v).
  • a more preferred range is from 0.05 to 0.5 ppm, and most preferably, the platinum group metal will be supplied at a level of from 0.10 to 0.30 ppm on this same basis.
  • the fuel additive composition will preferably include a solvent which is miscible in the intended fuel, be it gasoline or diesel fuel.
  • a solvent which is miscible in the intended fuel, be it gasoline or diesel fuel.
  • Certain of the solvents provide enhancements in the effectiveness of the platinum group metal compound and are preferred for this reason.
  • oxygenated hydrocarbons such as alcohols, heterocyclic oxygen compounds and ethers.
  • Particularly preferred compounds are: 1 to 4 carbon alcohols, especially ethanol; tetrahydrofuran; and methyl tertiary butyl ether.
  • the solvent will preferably be employed at a concentration of up to 5% of the fuel and typically greater than 0.25%. Solvent concentrations of from 0.25 to 2.5% are preferred, and are most preferably 1.0% or less, and in some cases show surprising improvements in additive performance when employed at these levels.
  • the preferred fuel additives will employ sufficient amounts of platinum group metal compounds and oxygenated solvent to provide a weight ratio of oxygen to platinum group metal of from 1,000:1 to 100,000:1, preferably greater than 3,500:1. More preferred oxygen to platinum group metal weight ratios are from 5,000:1 to 35,000:1.
  • the fuel additive compositions can contain other additives such as detergents, antioxidants and octane improvers which are known as beneficial, but the use of such is not an essential feature of the invention.
  • Example 1 The following examples are presented for the purpose of further illustrating and explaining the present invention and the best mode for carrying it out, and are not to be taken as limiting.
  • Example 1
  • Dibenzyl cyclooctadiene Pt II was used as a catalyst in unleaded gasoline supplied to an automobile engine.
  • Production of dibenzyl cyclooctadiene platinum II was accomplished by slurrying 24.0 grams (0.064 mole) cyclooctadienyl Pt II dichloride in 200 milliliters of xylene.
  • To the resultant mixture was added 0.5 mole benzyl magnesium chloride in diethyl ether (300 milliliters).
  • the Grignard reaction was continued overnight, followed by hydrolysis with saturated ammonium sulfate solution in an ice bath. Following hydrolysis, the mixture was shaken vigorously and the layers were then allowed to separate.
  • the organic phase was collected, dried over anhydrous sodium sulfate, and the residual diethyl ether was removed, leaving a solution of the product in xylene.
  • This product has the structure:
  • the xylene solution of the platinum compound (0.17% by weight platinum) was admixed with other fuel additive components set forth in Table 1A below.
  • Table 1A The xylene solution of the platinum compound (0.17% by weight platinum) was admixed with other fuel additive components set forth in Table 1A below.
  • a series of dynamometer tests were conducted, in which a 1984 Buick V-6 spark ignition engine was connected to and loaded by an eddy current dynamometer. The engine had the following specifications:
  • This platinum compound has the following elemental breakdown:
  • the engine was run under steady conditions for about ninety (90) minutes per run at about 1300 rpm and was loaded to about 79 ft. lb. torque by a dynamo ⁇ meter to develop, on an average, 19.6 horsepower throughout each run.
  • the consumption times for 900 milliliters of gasoline containing 0.1 ppm of platinum supplied by the platinum compound were generally longer than the consumption times without the platinum compound.
  • the average time with the platinum compound was 9.39 minutes, and without was 9.11 minutes. This improvement of fuel consumption due to the platinum compound was 3.1%.
  • Fuel flow measurements showed a range of fuel efficiency gains of three percent (3%) to six percent (6%) with the platinum-based additive compared to the fuel additive formulation minus the platinum-based compound in a series of similar tests.
  • Example 2 The procedure of Example 1 was repeated, but this time employing 5% ethanol in addition to the fuel additive of Example 1 (at 0.2 ppm of platinum w/v). Baseline data was collected for 2 days and test data was noted on 12 days after an initial five days of operation employing the additive. The test engine was run at three rpm's (1300, 1800 and 2100) in sequence on each test day, all at a torque of 55 lb. ft. The data collected for fuel flow and hydrocarbon and carbon monoxide emissions are summarized below in Table 2.
  • Additive testing was performed with a Buick engine having the specifications described in Example 1, mounted on a Superflow SF-901 water brake dynamometer.
  • Superflow data collection capabilities included automatic measuring and recording of rpm torque, horsepower, as well as various temperatures, pressures, and flow rates.
  • Kistler spark plug pressure adapters Model 640
  • Kistler high impedance pressure transducers Model 6001
  • An A.V.L. optical shaft encoder was mounted on the test engine which generated signals for bottom dead center and every half degree of crank angle.
  • the base fuel in each of the formulations tested was AMOCO unleaded regular gasoline having an octane rating of 87. In each case where ethanol (ETOH) or tetrahydrofuron (THF) was employed, its concentration was 0.25%.
  • the DIBENZYL PT(II) referred to in the table was dibenzyl cyclooctadiene platinum II as prepared in Example 1; and, the NITROBENZYL PT(II) was similarly prepared but having nitrobenzyl in place of the two benzyl groups shown in the formula set forth in Example 1.
  • Peak - The maximum pressure achieved in the cylinder during combustion.
  • the mean for the data at each factor level may differ, reflecting the various effects of the treatment.
  • a statistical test can be performed to determine whether the means of the two factors are equal. If they are not, then further analysis is required. This analysis involves the construction of an interval estimation of the mean response for a given factor, and comparison of mean responses for different factors. Statistical inferences can be made by using the interval estimation, i.e., it can be estimated with 80 or 90 percent confidence that the mean increase of the peak, dist or MIP are between the lower limit and the upper limit of the interval constructed. The interval estimation depends on the confidence level, the total number of points in the data as well as the variance of the difference of the two means. Thus conclusions can be made about the effect of the fuel treatment compared to nontreatment.
  • Example 3 Following the test procedure of Example 3, (1) osmium (II) tris (acetylacetonate) and (2) bis (cyclopentadienyl) osmium (II) were tested against the base fuel with no additive as set forth in Example 3. The effect of each compound on peak, MIP and distance compared to base fuel was evaluated with the results as set forth in Table 4:
  • This example evaluates the performance of a diesel fuel additive according to the invention in reducing light duty diesel emissions and improving fuel economy.
  • the fuel additive had the formulation set forth in Table 5A:
  • a 1984 Volvo GLE 760 diesel with five speed transmission and approximately 30,000 miles was selected as a test vehicle to provide data on a newer, but well broken-in, diesel engine.
  • the vehicle was driven to Scott Environmental Laboratories in Plumsteadville, Pennsylvania and allowed to stabilize for twelve hours prior to chassis dynamometer testing.
  • Baseline testing was conducted according to U.S. EPA Federal Test Procedures (urban cycle) and Highway Fuel Economy Test procedures. These procedures call for the dynamometer to be loaded to a prescribed setting and » the vehicle to be driven through a series of acceleration, shifting, braking - * . and stopping patterns as emissions and fuel economy data are collected. Data are collected over a series of runs and analyzed through a computer software program to arrive at a composite number for emissions and fuel economy performance.
  • Table 7A Analysis of the data collected on the first day presented in Table 7A indicate a reduction in fuel consumption of 3.1% to 5.3% when using the additive.
  • Treated data acquisition progressed from high load (420 kw) to low load (220 kw). Absolute reduction in fuel consumption is noted to improve from no reduction initially (first treated data point) to a 5.3% reduction at the end of the sequence.
  • Data presented in Table 7B represent a comparison of treated data collected on the second day versus the baseline data of the first day. Percentage reduction in fuel consumption ranged from 3.3% to 4.0% when using the additive.
  • Absolute reduction in fuel consumption is noted to improve from 2.4 kg/hr to 3.3 kg/hr, which follows the trend towards increased time of treatment during the progression from low load operation (275 kw) to high load operation (475 kw) on the second day.
  • treatment was maintained by the driver according to a treatment schedule which provided for a 1:400 dosage rate.
  • Product was supplied in one-gallon containers along with a graduated beaker for accurate measurement.
  • Daily record sheets were completed by the driver to record miles driven and fuel and additive consumed.
  • the combined rear wheel horsepower was found to be equal to factory specifications, i.e., 70% of rated 250 horsepower, equal to 175. Prior to testing the engine was checked by the manufacturer to be sure that the fuel flow and fuel pressure agreed with the manufacturer's specifications for the fuel pump. Two test runs were conducted on each test date to assure the repeatability of results. Each test consisted of three minutes of stabilized run time at each of the three rpm settings with one minute in between to allow for stabilization and transition to the next rpm level.
  • Table 8A The averages of three readings for each rpm setting are summarized in Table 8A for untreated and treated data.
  • Table 8A provides a comparison of horsepower (output) versus fuel flow (input) at a given engine rpm for untreated and treated data. Horsepower increases following additive treatment averaged 2.6% to 5.2% improvement over baseline.
  • Table 8B provides a comparison of actual horsepower increase using the additive versus untreated data. Actual horsepower increases ranged from 4.5 hp to 9.0 hp following additive treatment. Table 8A
  • BSFC brake specific fuel consumption
  • This test evaluates the effectiveness of the diesel fuel additive set forth in Table 5A in a high elevation test on large tractors presently used for hauling. Two tractors were selected — a new Kenworth with a 400 horsepower Caterpillar engine (31,000 total miles) and a Kenworth with a 475 horsepower Cummins twin-turbo engine (172,000 total miles) .
  • the tractors were driven onto the dynamometer such that the rear driving wheels of the tractor turned a set of rollers. These rollers are connected to a braking system.
  • the force required on the turning rollers to load the tractor's rear driving wheels is indicated on various meters located on the dynamometer's control panel.
  • the meters consisted of horsepower, torque, ' speed (calibrated in miles per hour) and also a separate panel with controls to adjust for barometric pressure, humidity, etc.
  • the test consisted of selecting three basic rpm's in the upper scale of the tractor's capability. The tractor was then fully loaded maintaining the specific rpm and the meters on the dynamometer were recorded every minute for 5 minutes.
  • Fuel flow was measured by filling a 20 gallon pail with diesel fuel from the tractor's saddle tanks.
  • the 20 gallon pail was placed on an accurate electronic scale. During the 5 minute load tests, minute readings were taken from the scale so an accurate accounting of the fuel usage in pounds of fuel per minute was recorded.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
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PCT/US1985/002387 1984-12-04 1985-12-03 Fuel additives and fuel containing soluble platinum group metal compounds and use in internal combusiton engines WO1986003492A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
MC85US8502387D MC1758A1 (fr) 1984-12-04 1985-12-03 Additifs pour carburants,carburant contenant des composes solubles formes avec un metal du groupe du platine et leur utilisation dans des moteurs a combustion interne
BR8507104A BR8507104A (pt) 1984-12-04 1985-12-03 Composicao de aditivo para combustivel,composicao de gasolina,composicao de combustivel diesel,metodo para aumentar a energia utilizavel de combustivel gasolina ou diesel e metodo para aumentar a eficiencia de um motor a gasolina ou diesel
HU85568Q HUT44034A (en) 1984-12-04 1985-12-03 Fuel containing fuel additives and soluable compounds of metals of platina group and application thereof by internal combustion engines
GB08617717A GB2178757B (en) 1984-12-04 1985-12-03 Fuel additives and fuel containing soluble platinum group metal compounds and use in internal combustion engines
JP61500068A JPH0653879B2 (ja) 1984-12-04 1985-12-03 可溶性白金族金属化合物を含む燃料添加組成物

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US67795484A 1984-12-04 1984-12-04
US677,954 1984-12-04
US79073885A 1985-10-24 1985-10-24
US790,738 1985-10-24
US79642885A 1985-11-08 1985-11-08
US796,428 1985-11-08

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Cited By (7)

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WO1991001361A1 (en) * 1989-07-17 1991-02-07 Fuel Tech, Inc. Method for catalyzing fuel for powering internal combustion engines
EP0451207A1 (en) * 1988-12-28 1991-10-16 Fuel Tech Inc METHOD FOR REDUCING EMISSIONS FROM OR ENLARGING THE USABLE ENERGY OF FUEL FOR OPERATING COMBUSTION ENGINES.
US5404841A (en) * 1993-08-30 1995-04-11 Valentine; James M. Reduction of nitrogen oxides emissions from diesel engines
US5584894A (en) * 1992-07-22 1996-12-17 Platinum Plus, Inc. Reduction of nitrogen oxides emissions from vehicular diesel engines
LT5161B (lt) 2003-12-12 2004-09-27 Rimvydas JASINAVIČIUS Degalų priedas taurinto etanolio pagrindu
EP1718394A1 (en) * 2004-02-09 2006-11-08 02Diesel Corporation Methods for reducing particulate matter emissions from diesel engine exhaust using ethanol/diesel fuel blends in combination with diesel oxidation catalysts
US7503944B2 (en) 2001-11-09 2009-03-17 Carroll Robert W Method and composition for improving fuel combustion

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US6948926B2 (en) * 2002-02-04 2005-09-27 Clean Diesel Technologies, Inc. Reduced-emissions combustion utilizing multiple-component metallic combustion catalyst
WO2010024478A1 (en) * 2008-08-25 2010-03-04 Tai Weon Choi The mixture for the diesel saving by nano-technology
WO2010024477A1 (en) * 2008-08-25 2010-03-04 Tai Weon Choi The mixture for the gasoline saving by nano-technology
CN103695051B (zh) * 2013-12-23 2015-04-01 山西华顿实业有限公司 用于改善甲醇汽油动力性的添加剂

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5034020A (en) * 1988-12-28 1991-07-23 Platinum Plus, Inc. Method for catalyzing fuel for powering internal combustion engines
EP0451207A1 (en) * 1988-12-28 1991-10-16 Fuel Tech Inc METHOD FOR REDUCING EMISSIONS FROM OR ENLARGING THE USABLE ENERGY OF FUEL FOR OPERATING COMBUSTION ENGINES.
EP0451207A4 (en) * 1988-12-28 1991-11-06 Fuel Tech, Inc. Method for reducing emissions from or increasing the utilizable energy of fuel for powering internal combustion engines
WO1991001361A1 (en) * 1989-07-17 1991-02-07 Fuel Tech, Inc. Method for catalyzing fuel for powering internal combustion engines
US5584894A (en) * 1992-07-22 1996-12-17 Platinum Plus, Inc. Reduction of nitrogen oxides emissions from vehicular diesel engines
US5535708A (en) * 1993-08-30 1996-07-16 Platinum Plus, Inc. Reduction of nitrogen oxides emissions from diesel engines
US5404841A (en) * 1993-08-30 1995-04-11 Valentine; James M. Reduction of nitrogen oxides emissions from diesel engines
US7503944B2 (en) 2001-11-09 2009-03-17 Carroll Robert W Method and composition for improving fuel combustion
US8287607B2 (en) 2001-11-09 2012-10-16 Robert Wilfred Carroll Method and composition for improving fuel combustion
US8945244B2 (en) 2001-11-09 2015-02-03 Robert W. Carroll Method and composition for improving fuel combustion
LT5161B (lt) 2003-12-12 2004-09-27 Rimvydas JASINAVIČIUS Degalų priedas taurinto etanolio pagrindu
EP1718394A1 (en) * 2004-02-09 2006-11-08 02Diesel Corporation Methods for reducing particulate matter emissions from diesel engine exhaust using ethanol/diesel fuel blends in combination with diesel oxidation catalysts
EP1718394A4 (en) * 2004-02-09 2008-05-28 O2Diesel Corp METHOD FOR REDUCING PARTICULAR EMISSIONS FROM DIESEL ENGINE EXHAUSTING USING ETHANOL / DIESEL FUEL MIXTURES COMBINED WITH DIOXIDE OXIDIZING CATALYSTS

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GB2178757B (en) 1988-10-19
DK527485A (da) 1986-06-05
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ES8900127A1 (es) 1989-01-01
IE58723B1 (en) 1993-11-03
CA1305607C (en) 1992-07-28
ES548951A0 (es) 1989-01-01
IL77176A0 (en) 1986-04-29
DK527485D0 (da) 1985-11-14
JPH0653879B2 (ja) 1994-07-20
FI854486A (fi) 1986-06-05
IE853043L (en) 1986-06-04
CN85109511A (zh) 1987-05-13
GB8617717D0 (en) 1986-08-28
AU583580B2 (en) 1989-05-04
MX169226B (es) 1993-06-25
PT81495A (en) 1985-12-01
AU5236286A (en) 1986-07-01
MA20584A1 (fr) 1986-07-01
HUT44034A (en) 1988-01-28
FI854486A0 (fi) 1985-11-14
BR8507104A (pt) 1987-03-31
GB2178757A (en) 1987-02-18

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