US3794473A - Rare earth beta-ketoenolate anti-knock additives in gasolines - Google Patents

Rare earth beta-ketoenolate anti-knock additives in gasolines Download PDF

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Publication number
US3794473A
US3794473A US00290604A US3794473DA US3794473A US 3794473 A US3794473 A US 3794473A US 00290604 A US00290604 A US 00290604A US 3794473D A US3794473D A US 3794473DA US 3794473 A US3794473 A US 3794473A
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rare earth
tris
iii
ketoenolate
thd
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R Sievers
K Eisentraut
R Tischer
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    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/92—Ketonic chelates
    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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

Definitions

  • This invention relates to an improved fuel composition for spark ignition internal combustion engines.
  • the invention relates to a method for improving the antiknock properties of aviation and automotive fuels.
  • Another object of the invention is to provide a fuel composition for use in spark ignition internal combustion engines.
  • a further object of the invention is to provide a fuel composition containing, as the sole antiknock agent, a rare earth -ketoenolate.
  • Still another object of the invention is to provide a method for upgrading gasoline so as to obtain automotive and aviation fuels having performance numbers of up to 145.
  • the present invention resides in a fuel composition consisting essentially of gasoline and a knock-inhibiting amount of a rare earth -ketoenolate which is soluble in the gasoline.
  • the invention is concerned with a method for upgrading gasoline to provide a performance number of up to which comprises adding to a petroleum fraction boiling in the gasoline range an antiknockelfective amount of a rare earth -.ketoenolate.
  • the rare earth -ketoenolates that are used in the cornposition of this invention have the following general formulae:
  • M is a rare earth element selected from the group consisting of lanthanum (La), cerium (Ce), praseodymium '(Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), yttrium y(Y) and mixtures thereof
  • R1 is selected from the group consisting of hydrogen, alkyl, phenyl, fluorine, chlorine, bromine and iodine, the alkyl radical preferably containing from l to 16 carbon atoms;
  • R2 and R3 are individually selected from the group consisting of alkyl, halogen-substituted alkyl,v aryl, halogen-substituted,
  • groups that can be substituted for R2 and R3 in Formula V1 include methyl, triiiuoromethyl, ethyl, propyl, isopropyl, hepatuoropropyl, butyl, tertiary butyl, pentyl, heptyl, octyl, dodecyl, hexadecyl, eicosyl, hexacosyl, triacontyl, tritriacontyl, phenyl, biphenyl, phenoyl, naphthyl, naphthoyl toluyl, p-iuorobenzoyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, triethylamino, tetramethylamino, pyridyl, pyrirnidyl, pyroyl, pyroy
  • B in the formulae is water or a compound containing a donor group.
  • the adducting agent can also be dened as a compound having a moiety containing an electron pair capable of bonding to the rare earth element ion.
  • Examples of compounds containing donor groups include ammonia; alcohols, such as methanol, ethanol, isopropanol, and butanol; esters, such as ethyl acetate, n-butyl acetate, ethyl propionate, methyl nbutyrate, ethyl isovalerate, and dimethyl succinate;
  • amines such'as ethylamine, aniline, diethylarnine, ethylphenylamine, triethylamine, methyldiethylamine, tripropylamine, triethanolamine, diphenylbenzylamine, pyridine and piperidine; phosphates, such as tricresylphosphate and tributylphosphate; amides, such as formamide, dimethylformarnide, acetamide, ethylacetamide and dibenzamide; ethers, such as ethyl ether, dimethyl ether, methylethyl ether, dimethoxymethane, and dimethoxypropane; sulfoxides, such as dimethylsulfoxide, diethylsulfoxide, dipropylsulfoxide; suldes, such as dimethylsulfide, diethylsulde, dibenzylsulide and diphenylsulde; ketones, such as
  • the -ketoenolates in which R1 and R2 are d-camphor and R@ is, for example, a fluoroalkyl can be synthesized by preparing an alcohol solution of triuoroacetyl-d-camphor- [H(facam)] and adding this solution to an aqueous solution of a chloride of one of the aforementioned rare earth elements.
  • H(facam) triuoroacetyl-d-camphor-
  • a first solution is prepared by stirring 15 millimoles (3.70 grams) of H(facam) in milliliters of a 50 percent alcohol solution.
  • a l0 percent ammonium hydroxide solution is slowly added until all of the H(facam) is dissolved.
  • a second solution is prepared by adding 5 milliliters of a 1 molar aqueous solution of praseodymium chloride (5 mllimols) to 30 milliliters of alcohol. The rst solution is then added dropwise to the second solution while stirring vigorously. The precipitate that forms is stirred in the mother liquor for an additional time, e.g., for about one hour, after all of the first solution has been added. The mixture is then filtered and the precipitate is washed with 100 milliliters of a 50 percent alcohol solution. After the precipitate is air dried overnight, it is recovered and the product obtained is determined by analysis to be Pr(facam)3.
  • the rare earth element is cerium.
  • cerium tetrakis(2,2,6,6 tetramethyl-3,Seheptanedionato) cerium(IV) has been found to be a particularly effective antiknock agent.
  • M in the foregoing formula is a mixture of rare earth elements.
  • the following table shows the weight percent of oxides of rare earth elements in an ore that is rich in cerium:
  • the rare earth ketoenolates are added to a hydrocarbon fuel'which is usually used in spark ignition internal combustion engines.
  • a hydrocarbon fuel which is usually used in spark ignition internal combustion engines.
  • Such fuels which are conventionally classified as automotive or aviation fuels, usually comprise a petroleum fraction boiling in the gasoline hydrocarbon range, eg., between about 50 and 450 F., and which is comparatively stable as regards gum formation or oxidation.
  • gasoline as used herein covers such Well known fuels which may contain in addition to the antiknock agent of this invention other materials, such as conventional anti-icing additives, pre-ignition inhibitors, dyes and oxidation inhibitors.
  • the amount of the antiknock agent that is added generally is in the range of about 0.001 to 50 millimols per gallon of gasoline.
  • rare earth -ketoenolates are generally used as the sole antiknock agent, it is within the scope of the invention to use them in conjunction with conventional'agents, s'uch as lead alkyls, particularly tetraethyllead, and tricresylphosphate.
  • lead alkyls particularly tetraethyllead
  • tricresylphosphate When included in the composition, the amount of the latter compounds that are added is. usually in the range of about 0.01 to 2 grams per gallon of gasoline.
  • Ce(thd)4 tetrakis(2,2,6,6-tetramethyl3,5-heptanedionato) cerium(1V) [Ce(thd)4]
  • the Ce(thd)4 used in this example was synthesized as described hereinafter.
  • To a 2-liter Pyrex resin vessel containing 0.6 mol of 2,2,6,6tetramethyl3,S-heptanedione [H(thd)] there was added 300 milliliters of 95 percent ethanol. The resulting solution was stirred continually during the remainder of the procedure. There was then introduced 0.6 mol of NaOH dissolved in 50 milliliters of distilled water.
  • TEL tetraethyllead
  • the present invention provides a lead-free antiknock agent which is capable of furnishing the required performance or octane numbers for fuels used in aviation and automotive engines.
  • the fact that the present antiknock agent is lead- Yfree is particularly significant in view of the fact that lead acts as a poison in catalytic exhaust devices.
  • the rare earth -ketoenolates function so effectively as antiknock agents. While the theory as to why the rare earth -ketoenolates function so effectively as antiknock agents is not completely understood, it is known to be critical that the R1, R2 and R3 of the compounds of Formula 1 contain a total of at least 4 carbon atoms. Compounds in which the R1, R2 and -R3 groups contain less than a total of 4 carbon atoms are much less soluble in hydrocarbon fuels, a factor which renders them ineffective as antiknock agents. Furthermore, the rare earth -ketoenolates volatilize readily during the combustion process so that they readily alter the combustion process in the vapor state. There are also indications that the combustion products of the antiknock agents function as catalysts to promote oxidation of unburned hydrocarbons, thereby reducing pollutants in the exhaust gases.
  • a fuel composition consisting essentially of a gasoline and a 4knock-inhibiting amount of a -ketoenolate having the following general formulae:
  • M is a rare earth element selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinum, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, yttrium, and mixtures thereof;
  • R1 is selected from the group consisting of hydrogen, alkyl, phenyl, fluorine, chlorine, bromine and iodine;
  • R3 and R3 are individually selected from the group consisting of alkyl, halogen-substituted alkyl, aryl, halogen-substituted aryl, cycloalkyl, hetero atom-substituted alkyl and hetero atomsubstituted aryl;
  • R1 and R2 together are d-camphor and R3 is as indicated, where the total number of carbon atoms in the
  • ketoenolate is tris(2,2,6,6 tetramethyl-3,S-heptanedionato neodymium (1]1) 11.
  • the amount of ,@ketoenolate is in the range of about 0.001 t0 50 millimols per gallon of gasoline.
  • the fuel composition of claim 13 which contains 0.01 to 2 grams of an alkyllead or tricrescylphosphate per gallon of gasoline.
  • M is a rare earth element selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, yttrium, and mixtures thereof;
  • R1 is selected from the group consisting of hydrogen, alkyl, phenyl, iiuorine, chlorine, bromine and iodine;
  • R3 and R3 are individually selected from the group consisting of alkyl, halogen-substituted alkyl, aryl, halogen-substituted aryl, cycloalkyl, hetero atom-substituted alkyl and hetero atom-substituted aryl;
  • R1 and R2 together are d-camphor and R3 is as indicated, where the total number of carbon

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Liquid Carbonaceous Fuels (AREA)
US00290604A 1972-09-20 1972-09-20 Rare earth beta-ketoenolate anti-knock additives in gasolines Expired - Lifetime US3794473A (en)

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US29060472A 1972-09-20 1972-09-20
JP49009647A JPS50103505A (enExample) 1972-09-20 1974-01-22

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JP (1) JPS50103505A (enExample)
BE (1) BE809274A (enExample)
CA (1) CA1016357A (enExample)
GB (1) GB1452783A (enExample)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976440A (en) * 1975-09-24 1976-08-24 Standard Oil Company Non-leaded gasoline having improved anti-knock quality
US3976439A (en) * 1975-09-24 1976-08-24 Standard Oil Company Non-leaded gasoline having improved anti-knock quality
US4211535A (en) * 1978-08-07 1980-07-08 Gulf Research And Development Company Gasoline fuel compositions containing antiknock additive
US4251233A (en) * 1979-03-05 1981-02-17 University Patents, Inc. Liquid hydrocarbon-soluble rare earth chelates prepared from the novel ligand 2,2,7-trimethyl-3,5-octanedione and fuels containing same
US4474580A (en) * 1982-03-16 1984-10-02 Mackenzie Chemical Works, Inc. Combustion fuel additives comprising metal enolates
US4836830A (en) * 1986-09-19 1989-06-06 Rhone-Poulenc Inc. Rare earth compositions for diesel fuel stabilization
WO1995004119A1 (en) * 1993-08-02 1995-02-09 The Associated Octel Company Limited Fuel additives
WO2005087901A3 (en) * 2004-03-09 2006-03-23 Ass Octel Fuel additive composition having antiknock properties
FR3046611A1 (fr) * 2016-01-12 2017-07-14 Inoventeam Utilisation de complexes de terres rares comme marqueurs de produits petroliers, de petroles bruts, de biocarburants ou de lubrifiants

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4180386A (en) * 1978-05-19 1979-12-25 E. I. Du Pont De Nemours & Company Hexacoordinated transition metal compounds containing at least one polyfluoroalkyl substituent
FR2537593B1 (fr) * 1982-12-10 1986-04-11 Raffinage Cie Francaise Compositions organometalliques mixtes comprenant des elements des groupes du fer et des lanthanides, procede de preparation et application desdites compositions comme additifs pour combustibles ou carburants
JPH02182783A (ja) * 1989-01-09 1990-07-17 Nippon Mining Co Ltd 高残炭燃料の燃焼方法
JPH0413798A (ja) * 1990-05-02 1992-01-17 Taiho Ind Co Ltd 燃料添加剤
GB0126663D0 (en) * 2001-11-06 2002-01-02 Oxonica Ltd Cerium oxide nanoparticles

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976440A (en) * 1975-09-24 1976-08-24 Standard Oil Company Non-leaded gasoline having improved anti-knock quality
US3976439A (en) * 1975-09-24 1976-08-24 Standard Oil Company Non-leaded gasoline having improved anti-knock quality
US4211535A (en) * 1978-08-07 1980-07-08 Gulf Research And Development Company Gasoline fuel compositions containing antiknock additive
US4251233A (en) * 1979-03-05 1981-02-17 University Patents, Inc. Liquid hydrocarbon-soluble rare earth chelates prepared from the novel ligand 2,2,7-trimethyl-3,5-octanedione and fuels containing same
US4474580A (en) * 1982-03-16 1984-10-02 Mackenzie Chemical Works, Inc. Combustion fuel additives comprising metal enolates
US4836830A (en) * 1986-09-19 1989-06-06 Rhone-Poulenc Inc. Rare earth compositions for diesel fuel stabilization
WO1995004119A1 (en) * 1993-08-02 1995-02-09 The Associated Octel Company Limited Fuel additives
GB2285451A (en) * 1993-08-02 1995-07-12 Ass Octel Fuel additives
US5593464A (en) * 1993-08-02 1997-01-14 The Associated Octel Company Limited Fuel additives
GB2285451B (en) * 1993-08-02 1997-12-17 Ass Octel Fuel additives
WO2005087901A3 (en) * 2004-03-09 2006-03-23 Ass Octel Fuel additive composition having antiknock properties
FR3046611A1 (fr) * 2016-01-12 2017-07-14 Inoventeam Utilisation de complexes de terres rares comme marqueurs de produits petroliers, de petroles bruts, de biocarburants ou de lubrifiants
WO2017121958A1 (fr) * 2016-01-12 2017-07-20 Inoventeam Utilisation de complexes de terres rares comme marqueurs de produits pétroliers, de pétroles bruts, de biocarburants ou de lubrifiants
US10975318B2 (en) 2016-01-12 2021-04-13 Inoventeam Use of rare earth complexes as markers of petroleum products, crude oils, biofuels or lubricants

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Publication number Publication date
CA1016357A (en) 1977-08-30
BE809274A (fr) 1974-04-16
GB1452783A (en) 1976-10-13
JPS50103505A (enExample) 1975-08-15

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