EP0107723A1 - Melanges lubrifiants et additifs pour combustibles a base d'alcool et leur procede de preparation - Google Patents

Melanges lubrifiants et additifs pour combustibles a base d'alcool et leur procede de preparation

Info

Publication number
EP0107723A1
EP0107723A1 EP83901877A EP83901877A EP0107723A1 EP 0107723 A1 EP0107723 A1 EP 0107723A1 EP 83901877 A EP83901877 A EP 83901877A EP 83901877 A EP83901877 A EP 83901877A EP 0107723 A1 EP0107723 A1 EP 0107723A1
Authority
EP
European Patent Office
Prior art keywords
volume
additive
fuel
lubricating additive
consists essentially
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP83901877A
Other languages
German (de)
English (en)
Other versions
EP0107723A4 (fr
Inventor
Earl J. Smith
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
XPCL Corp
Original Assignee
XPCL Corp
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 XPCL Corp filed Critical XPCL Corp
Publication of EP0107723A1 publication Critical patent/EP0107723A1/fr
Publication of EP0107723A4 publication Critical patent/EP0107723A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular 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
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • 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
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters

Definitions

  • the present invention basically comprises a lubricating additive which may be added to alcohol fuels to result in a stable alcohol fuel- lubricating additive solution for use as a fuel in internal combustion engines. Also disclosed and claimed are methods for preparing such fuel mixtures.
  • gasohol fuel is, at best, a stopgap solution to the petroleum dependence of both industrialized and developing nations.
  • a more satisfactory solution to this problem would be the development of a fuel source containing only very minor amounts such as, for example, significantly less than 10 percent, of petroleum-derived ingredients.
  • Alcohols have been identified as the alternative fuel source having the greatest potential for use in both spark ignited and compression ignited engines.
  • actual testing of alcohols such as ethanol and methanol as alternative fuels has revealed a substantial problem resulting from their use. Because such alcohol fuel compositions are substantially devoid of any petroleum derived products, they are notably deficient in lubricating properties with the result that engine wear from the use of these alcohol fuels in internal combustion engines will normally result in unacceptable premature failure of the engines.
  • similar wear problems occur not only in the engine, but also in fuel delivery and injection systems. Briefly stated, then, the primary difficulty with using alcohol fuels resides in efficiently and economically enhancing the lubricating properties of such fuels.
  • this copolymer might be effective in obtaining alcohol-lubricating oil fuel mixtures having stable solution characteristics.
  • Further searching of the prior art reveals numerous anti-wear compression ignition fuels for use in diesel engines assigned to Ethyl Corporation. Illustrative of these are the following U.S. Patents:
  • a primary purpose of the present invention is to provide a lubricating additive for use in combination with alcohol fuels for internal combustion engines whereby significant lubricating characteristics are provided for protection of the internal components of the engine and its fuel delivery and injection systems.
  • the present invention comprises a lubricating additive formulated by the mixture of a petroleum base stock lubricant, an emulsifier, ethylene-vinyl acetate copolymer, and organic solvents.
  • the organic solvents comprise a mixture of aliphatic solvents and aromatic solvents.
  • the lubricant may be selected from the class consisting of paraffinic hydrocarbons, napthenic hydrocarbons, alkylated aromatics, polyalphaolefins, polybutenes, dibasic acid esters, polyol esters, polyesters, halogenated hydrocarbons, phosphate esters, polyglycols, polyphenyl esters, silicate esters, and silicones.
  • the preferred lubricant is 120 SUS (Saybolt Universal Seconds) paraffinic bright stock derived from a paraffinic petroleum crude oil.
  • the emulsifier may be selected from virtually any of the commercially available emulsifiers commonly used to manufacture soluble oils, potassium carboxylate emulsifiers appear to work best.
  • the aliphatic solvents may be selected from the class consisting of mineral spirits, naptha, cyclohexane, hexane, heptane, pentane, and isopentane.
  • the preferred aliphatic solvent is mineral spirits.
  • the aromatic solvent may be selected from the class consisting of toluene, xylene, and benzene.
  • the ethylene-vinyl acetate copolymer utilized in the preferred embodiment is commercially available under the brand name Paradyne 25.
  • a preferred formulation for providing lubricity in 180-200 proof ethanol comprises, by volume, about 94.6% solvent, about 1.25% emulsifier, about 3.75% lubricant, and about 0.4% ethylene-vinyl acetate copolymer.
  • This lubricating additive is mixed with the 180-200 proof ethanol at about 4%, by volume, lubricating additive.
  • a preferred formulation for methanol consists, by volume, of about 95.6% solvent, about 1.0% emulsifier, about 3.0% lubricant, and about 0.4% ethylene-vinyl acetate copolymer.
  • This lubricating additive is mixed to the methanol at about 5% additive, by volume.
  • the invention accordingly comprises the composition possessing the features, properties, and the relation of components which are exemplified in the following detailed disclosure, and the several steps and the relation of one or more of such steps with respect to each of the others, and the scope of the invention will be indicated in the claims.
  • the present invention relates to unique lubricating, corrosion inhibiting and rust inhibiting additives for alcohol fuels in compression ignited and spark ignited internal combustion engines.
  • the lubricating additive of this invention is suitable for use in combination with monohydroxy alcohol fuels having from 1-5 carbon atoms and the scope of the invention includes not only the additive, but also alcohol fuel-lubricating additive mixtures and their method of preparation.
  • the lubricating additive of this invention consists essentially of, by volume, about 94-97% organic solvent, about 0.2-1.5% emulsifier, about 3-4% lubricant, and about 0.3-0.5% ethylene-vinyl acetate copolymer.
  • the lubricating additive is mixed with alcohol at about 3-6%, by volume, of the alcohol fuel-lubricating additive mixture.
  • the organic solvent constitutent of the lubricating additive normally comprises a mixture of aliphatic solvents and aromatic solvents.
  • the aliphatic solvents may be selected from the class consisting of mineral spirits, naptha, cyclohexane, hexane, heptane, pentane, and isopentane.
  • the aromatic solvents are selected from the class consisting of toluene, xylene, and benzene.
  • the lubricant component of the lubricating additive may be a petroleum base stock consisting of paraffinic, napthenic or mixed base hydrocarbons, or it may be a synthetic base stock consisting of alkylated aromatics, polyalphaolefins, polybutenes, dibasic acid esters, polyol esters, polyesters, halogenated hydrocarbons, phosphate esters, polyglycols, polyphenyl esters, silicate esters, or silicones.
  • the emulsifier may consist essentially of any of the commercially available emulsifiers commonly used to manufacture soluble oils, with the emulsifier comprising potassium carboxylate being preferred.
  • Emulsifiers containing sodium sulfonate are also effective, but will result in slight sodium precipitate.
  • the following examples, then, are set forth in order to describe more fully the composition and method of the present invention. In the following examples all component quantities are expressed as percent, by volume.
  • Emulsifier comprising Potassium Carboxylate 1.25% Paraffinic bright stock
  • the resulting lubricating additive had a specific gravity of about 0.796 g/ml at 20°C, which is substantially equivalent to the specific gravity of 190 proof ethanol.
  • EXAMPLE II The lubricating additive of Example I was added to 180-200 proof ethanol at the rate of about one gallon additive per 25 gallons ethanol (about 4% additive and 96% ethanol). Initially, an emulsion formed. This emulsion was allowed to sit, and within about 48 hours a stable ethanol-lubricating additive solution suitable for use as a fuel for internal combustion engines resulted.
  • EXAMPLE III A lubricating additive intended for use in combination with 180-200 proof ethanol as a fuel mixture was prepared by mixing together the following components:
  • EXAMPLE V A lubricating additive intended for use in combination with 180-200 proof ethanol as a fuel mixture was prepared by mixing together the following components:
  • Emulsifier comprising Potassium carboxylate 1.25% Paraffinic bright stock
  • a lubricating additive intended for use in combination with methanol as a fuel mixture was prepared by mixing together the following components: Toluene 23. %
  • Emulsifier comprising
  • the resulting lubricating additive had a specific gravity of about 0.792 g/ml at 20°C, which is substantially equivalent to the specific gravity of methanol.
  • EXAMPLE VIII The lubricating additive of Example VII was admixed to methanol at a ratio of about 5% additive to about 95% methanol. Initially, an emulsion formed. After being allowed to sit for about 24 hours the emulsion was observed to contain a lubricant residue at the bottom of the container. The methanol-lubricating additive emulsion was decanted from the lubricant residue and allowed to sit further. After about 48 hours a stable methanol-lubricating additive solution suitable for use as a fuel for internal combustion engines resulted. Further observation of sample portions of this solution did reveal that separation of the methanol and the lubricating additive will occur if the water content of the methanol becomes too high.
  • a lubricating additive intended for use in combination with 180-200 proof ethanol as a fuel mixture was prepared by mixing together the following components:
  • Emulsifier comprising . Potassium carboxylate 2.5 %
  • Example IX The lubricating additive of Example IX was added to 190 proof ethanol in accord with the method of Example II and resulted in a stable ethanol- lubricating additive solution having only very minor amounts of lubricant residue after 24 hours.
  • Emulsifier comprising
  • Example XII The lubricating additive of Example XI was added to methanol containing about 3% isopentane in accord with the method of Example VIII with the exception that about 6% additive was admixed to about 94% methanol-isopentane solution resulting in a final methanol content of about 91%.
  • the final result of this example was equivalent to that obtained in Example VIII.
  • Emulsifier comprising
  • Example XIII The lubricating additive of Example XIII was added to methanol containing about 3% isopentane in accord with the method of Example XII with substantially identical results.
  • Emulsifier comprising
  • Example XVI The lubricating additive of Example XV was added to methanol containing about 3% isopentane in accord with the method of Example XII with substantially identical results.
  • a lubricating additive concentrate intended for use in preparing lubricating additives for alcohol fuels or for use as a lubricating additive in gasoline-alcohol and diesel fuel-alcohol mixtures was prepared by mixing together the following components:
  • Emulsifier comprising Potassium carboxylate 8.125%
  • Example XVIII The lubricating concentrate of Example XVII was mixed with appropriate quantities of aliphatic and aromatic solvents to yield various lubricating additives as set forth in Examples I, III, V and VII. These additives were then mixed with alcohols in accord with the methods of Examples II and VIII with substantially identical results.
  • Example XIX The lubricating concentrate of Example XVII was added to gasohol at a ratio of about 0.6% concentrate to about 99.4% gasohol for the purposes of reducing acid blowby in the engine, reducing rust corrosion and wear in fuel delivery systems and in the upper cylinder area of the engine, reducing fuel consumption by improving engine sealing and increasing engine compression, and perhaps most importantly inhibiting the phase separation tendancies of gasohol and other petroleum-alcohol fuel mixtures.
  • EXAMLE XX A modified Timpken test was conducted for the purpose of comparing the lubricity of the methanollubricating additive fuel mixture of Example VIII with the lubricity of #2 diesel fuel. At the conclusion of the test measurement of scars on the steel balls confirmed that the lubricity of the mixture of Example VIII was from about 7% to about 17% greater than that of the #2 diesel fuel.
  • the preferred emulsifier comprises potassium carboxylate
  • it also includes a rust inhibitor of an amine type plus minor amounts of other materials such as, for example, fungicides.
  • lubricants including known additives for enhancing lubricating characteristics are compatible with the composition and method of this invention. Such lubricant materials are commonly referred to in the art as fully formulated lubricants.
  • the lubricating additive of this invention is especially efficacious for the purpose of imparting desirable characteristics to alcohol fuels of 1-5 carbon atoms.
  • Alcohol-lubricating additive fuel mixtures prepared in accord with the method of this invention are furthermore unique in that they maintain the physical characteristic of a stable solution for extremely long periods of time.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

Additifs uniques de lubrification et d'inhibition de la corrosion et de la rouille pour combustibles à base d'alcool possédant de 1 à 5 atomes de carbone. L'additif lubrifiant comprend un mélange se composant essentiellement d'un lubrifiant, d'un émulsifiant, d'un copolymère d'acétate d'éthylène-vinyle et de solvants organiques formulés de manière à obtenir un mélange possédant une gravité spécifique sensiblement équivalente à celle de l'alcool auquel l'additif lubrifiant doit être mélangé. L'invention comprend en outre un mélange d'additifs lubrifiants et de combustible à base d'alcool destiné à être utilisé en tant que carburant dans des moteurs à combustion interne ainsi que des procédés de préparation de ces mélanges.
EP19830901877 1982-05-06 1983-05-04 Melanges lubrifiants et additifs pour combustibles a base d'alcool et leur procede de preparation. Withdrawn EP0107723A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US37576282A 1982-05-06 1982-05-06
US375762 1995-01-20

Publications (2)

Publication Number Publication Date
EP0107723A1 true EP0107723A1 (fr) 1984-05-09
EP0107723A4 EP0107723A4 (fr) 1984-09-14

Family

ID=23482232

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19830901877 Withdrawn EP0107723A4 (fr) 1982-05-06 1983-05-04 Melanges lubrifiants et additifs pour combustibles a base d'alcool et leur procede de preparation.

Country Status (5)

Country Link
EP (1) EP0107723A4 (fr)
BR (1) BR8206717A (fr)
FI (1) FI840037A0 (fr)
WO (1) WO1983004043A1 (fr)
ZA (1) ZA833236B (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0257149A1 (fr) * 1986-08-21 1988-03-02 Exxon Research And Engineering Company Compositions de combustibles alcanol
GB9315205D0 (en) * 1993-07-22 1993-09-08 Exxon Chemical Patents Inc Additives and fuel compositions
CN104232183B (zh) * 2014-10-17 2016-03-23 广西丰泰能源防爆科技有限公司 一种汽车燃料添加剂

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1366733A (fr) * 1961-10-17 1964-07-17 Exxon Research Engineering Co Produits améliorés abaissant le point de congélation des distillats moyens
US3840352A (en) * 1972-05-30 1974-10-08 Union Oil Co Method and composition for treating high pour point oils under low ambient temperature conditions

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1420007A (en) * 1919-11-12 1922-06-20 Us Ind Alcohol Co Fuel for internal-combustion engines
US2404094A (en) * 1944-01-01 1946-07-16 Standard Oil Dev Co Motor fuels
US3048479A (en) * 1959-08-03 1962-08-07 Exxon Research Engineering Co Ethylene-vinyl ester pour depressant for middle distillates
US4231756A (en) * 1979-05-11 1980-11-04 King Samuel B Gasoline and petroleum fuel supplement
US4333739A (en) * 1979-10-23 1982-06-08 Neves Alan M Blended ethanol fuel

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1366733A (fr) * 1961-10-17 1964-07-17 Exxon Research Engineering Co Produits améliorés abaissant le point de congélation des distillats moyens
US3840352A (en) * 1972-05-30 1974-10-08 Union Oil Co Method and composition for treating high pour point oils under low ambient temperature conditions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO8304043A1 *

Also Published As

Publication number Publication date
ZA833236B (en) 1984-02-29
BR8206717A (pt) 1984-01-03
EP0107723A4 (fr) 1984-09-14
FI840037A (fi) 1984-01-05
FI840037A0 (fi) 1984-01-05
WO1983004043A1 (fr) 1983-11-24

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Inventor name: SMITH, EARL J.