EP0165776B1 - Korrosionsschutzmittel für Alkoholkraftstoffe - Google Patents

Korrosionsschutzmittel für Alkoholkraftstoffe Download PDF

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Publication number
EP0165776B1
EP0165776B1 EP19850304230 EP85304230A EP0165776B1 EP 0165776 B1 EP0165776 B1 EP 0165776B1 EP 19850304230 EP19850304230 EP 19850304230 EP 85304230 A EP85304230 A EP 85304230A EP 0165776 B1 EP0165776 B1 EP 0165776B1
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European Patent Office
Prior art keywords
fuel
acid
weight percent
liquid fuel
combination
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EP19850304230
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English (en)
French (fr)
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EP0165776A2 (de
EP0165776A3 (en
Inventor
Gordon Grayson Knapp
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Ethyl Corp
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Ethyl Corp
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Priority claimed from US06/619,977 external-priority patent/US4511367A/en
Priority claimed from US06/621,777 external-priority patent/US4511368A/en
Application filed by Ethyl Corp filed Critical Ethyl Corp
Priority to AT85304230T priority Critical patent/ATE52271T1/de
Publication of EP0165776A2 publication Critical patent/EP0165776A2/de
Publication of EP0165776A3 publication Critical patent/EP0165776A3/en
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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
    • 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
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • C10L1/1883—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
    • 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
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring

Definitions

  • alkenyl succinic acids as well as their anhydrides inhibit and/or prevent the deposit-forming tendency of hydrocarbon fuels during combustion and/or modify the deleterious effect of the formed deposits in both leaded and unleaded fuels particularly in gasoline and jet fuels. It has now also been discovered that a combination of certain substituted imidazolines with a monoalkenylsuccinic acid wherein the alkenyl group contains 8 to 30 carbon atoms provides corrosion inhibiting properties to fuels containing alcohols such as gasohol or straight alcohol fuels.
  • metal corrosion caused by alcohol-type motor fuels is inhibited by adding to the fuel a combination of (A) a member selected from (i) polymerized polyunsaturated aliphatic monocarboxylic acid or (ii) an alkenylsuccinic acid or its equivalent anhydride having effective solubility in said fuel, preferably at least one monoalkenylsuccinic acid wherein the alkenyl group contains 8 to 30 carbon atoms and (B) substituted imidazoline.
  • A a member selected from (i) polymerized polyunsaturated aliphatic monocarboxylic acid or (ii) an alkenylsuccinic acid or its equivalent anhydride having effective solubility in said fuel, preferably at least one monoalkenylsuccinic acid wherein the alkenyl group contains 8 to 30 carbon atoms and (B) substituted imidazoline.
  • the invention provides a liquid fuel adapted for use in an internal combustion engine, said fuel comprising from 5 to 100 weight percent of one or more alcohols, from 0 to 95 weight percent gasoline and as a corrosion inhibitor the combination of (A) a member selected from (i) a polymer of one or more C 16 to C 18 polyunsaturated aliphatic monocarboxylic acids, (ii) an alkenylsuccinic acid or its equivalent anhydride having effective solubility in said fuel, preferably at least one monoalkenylsuccinic acid wherein the alkenyl group contains 8 to 30 carbon atoms and (B) a substituted imidazole.
  • A a member selected from (i) a polymer of one or more C 16 to C 18 polyunsaturated aliphatic monocarboxylic acids, (ii) an alkenylsuccinic acid or its equivalent anhydride having effective solubility in said fuel, preferably at least one monoalkenylsuccinic acid wherein the alkeny
  • the additive combination of this invention can be beneficial in any engine fuel containing or consisting of an oxygenate.
  • fuels include gasoline-alcohol mixtures referred to as "gasohol" as well as straight alcohol fuels.
  • Useful alcohols are methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, t-butanol, 2-methyl-2-propanol, isobutanol or mixtures thereof such as methanol and t-butanol.
  • Gasohols usually contain 2 to 30 volume percent alcohol. At concentrations above 10 volume percent phase separation problems may be encountered especially in the presence of water.
  • Phase separation can be minimized by including co-solvents in the gasohol such as ethers, ketones or esters, for example.
  • co-solvents in the gasohol such as ethers, ketones or esters, for example.
  • An especially useful co-solvent is methyl tert-butyl ether which also serves to increase octane value.
  • the additive combination is used in a corrosion inhibiting amount.
  • a useful range of additive concentration is 2.8 to 1400 mg/litre [1 to 5000 pounds per thousand barrels (ptb)].
  • a more preferred range is 14 to 5600 mg/litre (5 to 2000 ptb) and the most preferred concentration is 14 to 1400 mg/litre (5 to 500 ptb).
  • Component A (i) is a polymer of one or more 16 to 18 carbon polyunsaturated aliphatic mono- carboxylic acids. Examples of these are tall oil fatty acid, oleic acid, linoleic acid and linolenic acid including mixtures thereof.
  • the polymers comprise mainly dimers and trimers of the polyunsaturated acids. Suitable polymers of linoleic acid are available commercially. Mixtures high in trimer content are most preferred.
  • the monoalkenylsuccinic acids are well known in the art. These acids may be readily prepared by the condensation of an olefin with maleic anhydride followed by hydrolysis (see U.S. Pat. No. 2,133,734 and U.S. Pat. No. 2,741,597).
  • Suitable monoalkenylsuccinic acids include octenylsuccinic acid, decenylsuccinic acid, undecenylsuccinic acid, dodecenylsuccinic acid, pentadecenylsuccinic acid, octa- decenylsuccinic acid and isomers thereof having alkenyl groups of various hydrocarbon structures.
  • the preferred monoalkenylsuccinic acid is dodecenylsuccinic acid, more preferably, dodecenylsuccinic acid prepared from propylene tetramer.
  • alkenyl group ranging from 8 to 30 carbon atoms is preferred as indicated above, it is contemplated that substantially any alkenylsuccinic acid or its equivalent anhydride may be employed in the fuels of the present invention provided it is sufficiently soluble in the fuel to be effective in combination with the substituted imidazoline compounds of the invention as a corrosion inhibitor.
  • alkenylsuccinic acids prepared as mixtures by reacting mixed olefins with maleic anhydride may be employed in this invention as well as relatively pure alkenyl succinic acids.
  • Mixed alkenylsuccinic acids wherein the alkenyl group averages 6-8, 8-10 and 10-12 carbon atoms are commercially available.
  • Component B of the combination is a substituted imidazoline.
  • the substituted imidazoline used in this invention can be represented by the following general formula (I): in which R is a hydrocarbon alkenyl group having from 7 to 24 carbon atoms.
  • the imidazolines having Formula I which are useful in this invention may be readily obtained by reacting suitable organic acids with N-(2-hydroxyethyl)ethylene diamine. This reaction involves the elimination of 2 molecules of water between the acid and the amine. This reaction is represented by the following equation: In addition to the imidazoline, small amounts of a corresponding linear amino amide are also obtained. This amino amide is the result of eliminating only one molecule of water between the acid and the amine. Methods of preparing the imidazolines are well known. Useful procedures are described in Wilson, U.S. 2,267,965, and Wilkes, U.S. 2,214,152. As can be seen from the reaction equation given above, the R group in the imidazoline is the alkenyl residue of the particular. acid which is used in its preparation. In other words, the R group will have one carbon atom less than the acid which is used to prepare the imidazoline.
  • Acids which are useful in preparing the imidazolines are hydrocarbon mono-carboxylic acids having up to about 20 carbon atoms.
  • the preferred acids are unsaturated organic acids such as 9,10 decylenic acid, octenoic acid, oleic acid, linoleic acid and the like.
  • Preferred acids are commonly obtained as hydrolysis products of natural materials. These acids thus obtained are mixtures.
  • acids obtained from olive oil typically, are a mixture of about 83 percent oleic acid, 6 percent palmitic acid, 4 percent stearic acid and 7 percent linoleic acid. This mixture is quite useful for preparing imidazolines to be used in this invention.
  • Organic acid mixtures obtained on saponifying and acidulating babassu oil, castor oil, peanut oil or palm oil are examples of useful acids.
  • imidazoline compounds which can be used in the present invention are available commercially.
  • a preferred imidazoline is 2-heptadecenyl-1-(2-hydroxyethyl)-imidazoline.
  • the weight ratio of component A to component B in the combination can vary over a wide range, typically 1 to 10 parts A to 1 to 10 parts B. In a preferred embodiment, the weight ratio is about 0.5-5 parts component A for each part component B. In a more preferred embodiment there are 0.6 ⁇ 4.0 parts component A per each part component B. The most preferred ratio is 1:1.
  • Components A and B can be separately added to the fuel. More preferably components A and B are pre-mixed to form a package and this package is added to the fuel in an amount sufficient to provide the required degrees of corrosion protection.
  • components A and B are also pre-mixed with a solvent to make handling and blending easier.
  • Suitable solvents include alcohols (e.g., methanol, ethanol, isopropanol), ketones (acetone, methyl ethyl ketone), esters (tert-butyl acetate) and ethers (e.g., methyl tert-butyl ether).
  • Aromatic hydrocarbons are very useful solvents. These include benzene, toluene, xylene and the like. Excellent results can be obtained using xylene.
  • the concentration of the active components A and B in the package can vary widely.
  • the active content can range from 5 weight percent up to the solubility limit of A or B in the solvent.
  • a total active content of 5-60 weight percent is generally used, especially about 50 weight percent.
  • Tests were conducted to measure the anticorrosion properties of the additive combination.
  • the corrosion of steel cylinder rods (1/8 in. x 3 in.) (0.3175 cm x 7.62 cm) semisubmersed in test fluid was measured under different test conditions.
  • the rods were first cleaned with carborundum 180, polished with crocus cloth, washed with acetone and then dried at room temperature.
  • Each rod was weighed and then semisubmersed in 10 milliliters of the test fluid in a sealed bottle for the specified time at the specified temperature.
  • the rods were removed from the fuel, and after loose deposits were removed with a light brush, the rods were washed and dried as at the start of the test and then reweighed. Any change in rod weight was recorded. Loss of weight indicated corrosion.
  • a series of three tests were carried out lasting 7 days, 14 days and 30 days, respectively.
  • the series of tests were conducted in fuels comprising 5 volume percent methanol and 5 volume percent t-butanol in gasoline (indolene) containing 0.5 weight percent of 5.0 percent acetic acid in water.
  • the tests were conducted at 25°C.
  • test additives added to the test fuels were equal weight mixtures [280 mg/litre (100 ptb)] of either (i) predominantly oleic acid dimer or predominantly oleic acid trimer or (ii) dodecenylsuccinic acid prepared from dodecene or propylene tetramer in combination with 2-heptadecenyl-1-(2-hydroxyethyl)imidazoline and 140 mg/litre (50 ptb) of each individual component.

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  • 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)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Claims (10)

1. Zur Verwendung in einem Verbrennungsmotor angepaßter flüssiger Kraftstoff, enthaltend 5 bis 100 Gew.% eines oder mehrerer Alkohole, 0 bis 95 Gew.% Benzin und als Korrosionsinhibitor eine Kombination von (A) einer Verbindung, ausgewählt aus (i) einem Polymer von einer oder mehreren C16 bis C18 polyungesättigter aliphatischer Monocarbonsäure(n) oder (ii) einer Alkenylbernsteinsäure oder ihrem equivalenten Anhydrid mit wirksamer Löslichkeit im Kraftstoff, vorzugsweise mindestens eine Monoalkenylbernsteinsäure, in der die Alkenylgruppe 8 bis 30 Kohlenstoffatome enthält und (B) mindestens ein substituiertes Imidazolin mit der folgenden Strukturformel:
Figure imgb0008
in der R eine Kohlenwasserstoffalkenylgruppe mit 7 bis 24 Kohlenstoffatomen bedeutet.
2. Flüssiger Kraftstoff nach Anspruch 1, in dem das Polymer von einer oder mehreren C16 bis C18 polyungesättigten aliphatischen Monocarbonsäure(n) Linolsäuredimer, -trimer oder deren Mischung enthält.
3. Flüssiger Kraftstoff nach Anspruch 1 oder 2, in dem die Monoalkenylbernsteinsäure Dodecenylbernsteinsäure ist.
4. Flüssiger Kraftstoff nach einem der Ansprüche 1 bis 3, in dem das substituierte Imidazolin 2-Heptadecenyl-1-(2-hydroxy-ethyl)imidazolin ist.
5. Flüssiger Kraftstoff nach einem der Ansprüche 1 bis 4, in dem das Gewichtsverhältnis der Komponente A zur Komponente B in der Kombination 1:10 bis 10:1, vorzugsweise 1:1, beträgt.
6. Flüssiger Kraftstoff nach einem der Ansprüche 1 bis 5, in dem der Korrosionsinhibitor in einer Menge im Bereich von 2,8 bis 14000 mg/l (1 bis 5000 Pfund pro 1000 Barrel), vorzugsweise 14 bis 1400 mg/I (5 bis 500 Pfund pro 1000 Barrel), vorhanden ist.
7. Flüssiger Kraftstoff nach einem der Ansprüche 1 bis 6, in dem der Kraftstoff eine wesentliche Menge eines Kohlenwasserstoffdestillats im Benzindestillationsbereich und 2 bis 30 Vol.% eines oder mehrerer Alkohole, die 1 bis 4 Kohlenstoffatome enthalten, enthält.
8. Verwendung eines Lösungsmittels, enthaltend 5 bis 60 Gew.% einer Kombination von (A) einem Polymer einer oder mehrerer C,6 bis C18 polyungesättigter aliphatischer Monocarbonsäure(n) und (B) mindestens ein substituiertes Imidazolin mit.der folgenden Strukturformel:
Figure imgb0009
in der R eine Kohlenwasserstoffalkenylgruppe mit 7 bis 24 Kohlenstoffatomen bedeutet, als Korrosionsinhibitorkonzentrat für Kraftstoffe, enthaltend 5 bis 100 Gew.% eines oder mehrerer Alkohole und 0 bis 95 Gew.% Benzin.
9. Verfahren zur Herstellung eines flüssigen Kraftstoffs, bei dem man einen Kraftstoff, der 5 bis 100 Gew.% eines oder mehrerer Alkohole und 0 bis 95 Gew.% Benzin enthält mit, als Korrosionsinhibitor, einer Kombination, wie in einem der Ansprüche 1 bis 5 beansprucht, wobei die Komponenten der Kombination entweder vorgemischt sind oder separat zugegeben werden, vermischt.
10. Verfahren nach Anspruch 9, bei dem der Korrosionsinhibitor in einer Menge im Bereich von 2,8 bis 14000 mg/I (1 bis 5000 Pfund pro 1000 Barrel), vorzugsweise 14 bis 1400 mg/I (5 bis 500 Pfund pro 1000 Barrel), eines Kraftstoffs, wie in Anspruch 7 definiert, vorhanden ist.
EP19850304230 1984-06-13 1985-06-13 Korrosionsschutzmittel für Alkoholkraftstoffe Expired EP0165776B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85304230T ATE52271T1 (de) 1984-06-13 1985-06-13 Korrosionsschutzmittel fuer alkoholkraftstoffe.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US06/619,977 US4511367A (en) 1984-06-13 1984-06-13 Corrosion inhibitors for alcohol containing motor fuel
US619977 1984-06-13
US06/621,777 US4511368A (en) 1984-06-18 1984-06-18 Corrosion inhibitors for alcohol-based fuels
US621777 1984-06-18

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EP0165776A2 EP0165776A2 (de) 1985-12-27
EP0165776A3 EP0165776A3 (en) 1986-12-17
EP0165776B1 true EP0165776B1 (de) 1990-04-25

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EP (1) EP0165776B1 (de)
BR (1) BR8502798A (de)
CA (1) CA1263913A (de)
DE (1) DE3577327D1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3624767A1 (de) * 1986-07-22 1988-06-01 Sandoz Ag Korrosionsinhibitor fuer treibstoffe
US4684373A (en) * 1986-07-31 1987-08-04 Wynn Oil Company Gasoline additive composition
US4857073A (en) * 1987-08-27 1989-08-15 Wynn Oil Company Diesel fuel additive
FR2679151B1 (fr) * 1991-07-18 1994-01-14 Elf Aquitaine Prod Ste Nale Additifs dispersants pour produits petroliers.
US20070193110A1 (en) * 2006-02-21 2007-08-23 Schwab Scott D Fuel lubricity additives

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2907646A (en) * 1955-09-29 1959-10-06 American Oil Co Rust inhibitor for fuel fractions of mineral oil
US3036902A (en) * 1958-03-03 1962-05-29 Standard Oil Co Motor fuel composition
US3098727A (en) * 1958-03-03 1963-07-23 Standard Oil Co Motor fuel composition
US2993772A (en) * 1959-02-02 1961-07-25 Petrolite Corp Acid additives
US3582295A (en) * 1967-04-07 1971-06-01 Ethyl Corp Gasoline anti-icing
US4185594A (en) * 1978-12-18 1980-01-29 Ethyl Corporation Diesel fuel compositions having anti-wear properties
US4305730A (en) * 1980-02-19 1981-12-15 Texaco Inc. Corrosion-inhibited alcohol motor fuel composition
US4431430A (en) * 1980-11-14 1984-02-14 Texaco Inc. Composition containing a water soluble alcohol and a corrosion inhibiting additive
US4448586A (en) * 1981-11-02 1984-05-15 Ethyl Corporation Corrosion inhibitor compositions for alcohol-based fuels

Also Published As

Publication number Publication date
EP0165776A2 (de) 1985-12-27
DE3577327D1 (de) 1990-05-31
EP0165776A3 (en) 1986-12-17
BR8502798A (pt) 1986-02-18
CA1263913A (en) 1989-12-19

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