EP1918355A1 - Procédé et compositions pour réduire l'usure dans des moteurs de combustion de carburant contenant de l'éthanol - Google Patents
Procédé et compositions pour réduire l'usure dans des moteurs de combustion de carburant contenant de l'éthanol Download PDFInfo
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- EP1918355A1 EP1918355A1 EP07254000A EP07254000A EP1918355A1 EP 1918355 A1 EP1918355 A1 EP 1918355A1 EP 07254000 A EP07254000 A EP 07254000A EP 07254000 A EP07254000 A EP 07254000A EP 1918355 A1 EP1918355 A1 EP 1918355A1
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- C10L1/2283—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles containing one or more carbon to nitrogen double bonds, e.g. guanidine, hydrazone, semi-carbazone, azomethine
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Definitions
- the present disclosure relates to the use of fuel additives in fuels containing ethanol.
- the additives improve the properties of the resulting fuel and also enhance the benefits to the consumer and to the environment of utilizing varying amounts of ethanol as a fuel in combustion engines. More particularly, the present disclosure provides compositions and methods for reducing engine deposits and improving engine wear in engines combusting ethanol-containing gasoline fuel blends.
- E85 fuel 15 % gasoline and 85 % ethanol, often commonly referred to as “E85” fuel (hereinafter “E85”).
- Other ethanol fuels can comprise, for example 10% ethanol (E10) and 100% ethanol (E100).
- ethanol alone or in gasoline blends can create new problems for fuel equipment designed to handle the more non-polar hydrocarbonaceous petroleum fractions commonly known as gasolines.
- the polarity, corrosivity, adhesiveness, friction properties, and perhaps conductivity of ethanol or ethanol-containing fuel can create new problems and new needs in the fuel industry.
- E85, gasoline, and diesel are seasonally adjusted to ensure proper starting and performance in different geographic locations.
- E85 sold during colder months often contain only 70% ethanol and then 30% petroleum additives to produce the necessary vapor pressure for starting in cold temperatures.
- the petroleum additive content for E85 can often be, for example, 17% to about 20%.
- the need for better cold start performance and reliability will increase.
- So-called "driveability" of a vehicle is a function of the fuel combustion performance and poor driveability is manifested as slow starts, uneven combustion, and potential for misfires and stalling.
- Various techniques and fuel additives have been employed in the past to address this problem with gasoline fuels.
- Ethanol-containing fuels, from E100 to E5, and other gasoline-ethanol blends will produce additional problems with achieving improved driveability.
- engine wear can be a problem in engines combusting ethanol or ethanol-containing gasoline fuels, particularly in older engines designed and built before the introduction of ethanol-containing fuels. This engine wear can appear as corrosion or increased deposits. And will often result in decreased driveability, reduced fuel economy, or even catastrophic engine failure.
- ethanol is widely treated with additives designed to prevent human consumption.
- Such treated ethanol is called denatured alcohol, or denatured ethanol and common denaturants include gasoline, gasoline components, and kerosene.
- Other denaturants for rendering fuel alcohol unfit for beverage use are defined in 27 CFR 21.24.
- Fuel delivery systems in vehicles combusting gasoline fuels have increasingly complicated componentry, some of which is, can be or will be highly sensitive to variations in certain fuel parameters. Physical and chemical properties of the fuel can negatively impact the performance or life of these fuel delivery systems. Thus, certain components designed for use in traditional gasolines might be susceptible to fatigue, reduce performance or complete failure upon prolonged exposure to fuels containing ethanol, particularly fuels containing high percentages of ethanol, like E85 and E100. Therefore, a need exists to protect such older engines and well as improve the reliability of newer engines when all are exposed to prolonged combustion of ethanol-containing fuels.
- FFVs flexible fuel vehicles
- E85 ethanol concentrations of up to 85% by volume
- the FFV detects the ethanol/gasoline ratio and makes appropriate adjustments to the engine's ignition timing and air/fuel mixture ratios to account for the ethanol and optimize performance and maintain emissions control.
- the vehicle must be equipped with an air/fuel ratio map capable of handling the adjustments necessary for optimized performance on both gasoline and E85.
- Components of the fuel delivery systems on FFVs are also modified and upgraded to be resistant to the corrosive effects of alcohol in the fuel.
- Pure ethanol has broader flammability limits than gasoline and burns with lower flame luminosity.
- the vapor space flammability limits of ethanol approach those of gasoline and luminosity is increased.
- OGA-480 a polyetheramine available from Chevron Oronite, has been used in E100 fuel but has not been used in E85, nor have other amines been used in ethanol/gasoline blends, to the knowledge of the present inventors.
- An embodiment presented herein provides fuel additive agents for use in reducing wear and deposits in engines combusting ethanol-containing fuels, including but not limited to E100, E85, E50, and the like down to E10 and trace blends of ethanol in gasoline.
- Another embodiment provides a method to reduce wear and/or deposit formation in an internal combustion engine, said method comprising combusting in said engine a fuel composition comprising gasoline, ethanol and at least one fuel additive.
- a composition to improve wear protection and/or to reduce deposit formation in an internal combustion engine combusting an ethanol-containing fuel comprising gasoline, ethanol, and one or more materials selected from the group consisting of succinimide dispersants, succinamide dispersants, amides, Mannich base dispersants, polyetheramine dispersants, p-phenylenediamine, dicyclohexylamine phenolics, hindered phenolics, aryl amines, diphenyl amines, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, methyl cyclopentadienyl manganese tricarbonyl, cyclopentadienyl manganese tricarbonyl, azides, peroxides, alkyl nitrates, oxylated alkylphenolic resins, formaldehyde polymer with 4-(1,1-dimethylethyl)phenol, methyloxirane and
- ethanol herein is meant ethyl alcohol, the chemical compound C 2 H 5 OH. This can arise in or be provided in many qualities or grades, such a commercial of fuel grade, as well as pure or reagent grade ethanol, and can be derived from any source such as but not limited to petroleum refinery streams, distillation cuts, and bio-derived (e.g. bioethanol from corn).
- Fuels containing varying amounts of ethanol can, when evaporated or combusted, produce increased engine wear as well as increased engine deposits relative to deposits produced from evaporation or combustion of gasoline alone.
- the engine wear and deposits can be reduced or prevented by combusting a fuel composition containing the gasoline, ethanol and one or more fuel additive as described herein.
- a method to reduce wear and/or deposits in an internal combustion engine combusting an ethanol-containing fuel comprising combusting in said engine a fuel containing gasoline, ethanol, and one or more wear reducing agents selected from the group consisting of succinimide dispersants, succinamide dispersants, amides, Mannich base dispersants, polyetheramine dispersants, p-phenylenediamine, dicyclohexylamine, phenolics, hindered phenolics, aryl amines, diphenyl amines, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, methyl cyclopentadienyl manganese tricarbonyl, cyclopentadienyl manganese tricarbonyl, azides, peroxides, alkyl nitrates, oxylated alkylphenolic resins, formaldehyde polymer with 4-(1,1-dimethylethyl-dimethylethyl
- compositions herein can further comprise a fuel additive selected from the group consisting of lubricity additives, combustion improvers, detergents, dispersants, cold flow improvers, dehazers, demulsifiers, cetane improvers, antioxidants, scavengers, and pollution suppressants.
- a fuel additive selected from the group consisting of lubricity additives, combustion improvers, detergents, dispersants, cold flow improvers, dehazers, demulsifiers, cetane improvers, antioxidants, scavengers, and pollution suppressants.
- a deposit reducer fuel additive concentrate for gasoline engines combusting an ethanol-containing fuel, said concentrate comprising one or more deposit reducing agents and a diluent selected from the group consisting of an oil, a fuel, gasoline, ethanol, solvent, carrier fluid, and other liquid materials combustible in a gasoline engine.
- a wear reducer fuel additive concentrate for gasoline engines combusting an ethanol-containing fuel, said concentrate comprising one or more wear reducing agents and a diluent selected from the group consisting of an oil, a fuel, gasoline, ethanol, solvent, carrier fluid, and other liquid materials combustible in a gasoline engine.
- the wear or deposit reducer is selected from the group consisting of methyloxirane, oxiranes, peroxides, alkyl nitrates, C1-C8 aliphatic hydrocarbons, ketones, butylene oxides, propylene oxides, ethylene oxides, epoxides, butane, pentane, nitrous oxide, nitromethane, xylene, and diethyl ether.
- Particularly useful wear and/or deposit reducers herein are tall oil fatty acids, dodecenyl succinic acid, and oleic acid plus N,N dimethylcyclohexylamine.
- Also provided herein is a method to reduce deposit formation in an internal combustion engine combusting an ethanol-containing fuel comprising, or in another embodiment, consisting essentially of, combusting in said engine a fuel containing gasoline, ethanol, and one or more materials selected from the group consisting of succinimide dispersants, succinamide dispersants, amides, Mannich base dispersants, polyetheramine dispersants, p-phenylenediamine, dicyclohexylamine, phenolics, hindered phenolics, aryl amines, diphenyl amines, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, methyl cyclopentadienyl manganese tricarbonyl, cyclopentadienyl manganese tricarbonyl, azides, peroxides, alkyl nitrates, oxylated alkylphenolic resins, formaldehyde polymer with 4-(1,1-dimethyl)
- New Energy Ethanol 1.6 ADM Ethanol 10.8 New Energy Ethanol is a commercial ethanol with a denaturant ADM Ethanol is ethanol with a corrosion inhibitor (DCI-11, from Innospec) and a denaturant
- Table 1 shows the intake valve deposits generated on an Intake Valve Deposit simulator rig test using E85 fuels containing the ethanols indicated.
- the fuel blend is sprayed onto a hot surface and the resulting residue weighed.
- the base gasoline was Citgo RUL and without any additives the Intake Valve Deposit rating for the base gasoline in the rig test was 12.4 mg.
- the two different ethanol sources (New Energy and ADM) yielded significant differences, indicating a need for additives and a problem of non-uniformity across ethanol suppliers. While both ethanol products contain a denaturant, the ADM Ethanol is further believed to have 32 PTB of a corrosion inhibitor known commercially as DCI-11 from Innospec.
- Table 1 shows the intake valve deposits generated on the Intake Valve Deposit simulator rig test using E85 fuels containing the New Energy Ethanol. The dosage reported is the treat rate of the additive in the gasoline-ethanol fuel blend. As can be seen by comparing the rig test deposits from these additives when used in the E85 gasoline-ethanol fuel blend, the deposits varied. However, it must be noted that (a) this table used the ethanol contributing the lowest deposit level (New Energy Ethanol), so other ethanol sources, such as ADM Ethanol, will clearly have significantly more need for detergents, dispersants and other fuel additives, and (b) the deposits shown in Table 2 will include about 1.6 mg of deposits from the New Energy Ethanol in the E85 fuel.
- additives that generated deposits of about 2.7 mg or less, the total effective deposit not coming from the ethanol is essentially zero, that is, the present disclosure shows in at least these embodiments virtually complete prevention of deposits and the resulting wear on the engine.
- additives include 2,6-di t-butyl phenol antioxidant, methylcyclopentadienyl manganese tricarbonyl combustion improver and octane enhancer, oleic acid plus N,N dimethylcyclohexylamine, dodecenyl succinic acid, polyisobutylene amine dispersant, 1,2 propane diamine salicylaldehyde metal deactivator, cresol Mannich dispersant, diethanol amide of isostearic acid friction modifier, and 2-ethyl hexyl nitrate combustion improver.
- the alkyl nitrate, 2-ethyl hexyl nitrate was particularly effective in reducing deposits and hence improving wear in the engine combusting the E
- a method of reducing deposits formed in an internal combustion engine combusting an ethanol-gasoline blend comprising combining the blend with at least one additive selected from the group consisting of 2,6-di t-butyl phenol antioxidant, methylcyclopentadienyl manganese tricarbonyl combustion improver and octane enhancer, oleic acid plus N,N dimethylcyclohexylamine, dodecenyl succinic acid, polyisobutylene amine dispersant, 1,2 propane diamine salicylaldehyde metal deactivator, cresol Mannich base dispersant, diethanol amide of isostearic acid friction modifier, and 2-ethyl hexyl nitrate combustion improver, whereby the deposits formed in said engine are less than the deposits formed in the engine when combusting the blend without the at least one additive.
- at least one additive selected from the group consisting of 2,6-di t-butyl phenol antioxidant, methylcyclopent
- a Keep Clean Test was performed by driving a Chevrolet Impala for 5,000 miles using fuel containing gasoline without ethanol, and fuel containing E85 blend.
- the Intake Valve Deposits (IVD) and the Combustion Chamber Deposits (CCD) were then measured and are reported in Table 3.
- the ethanol used in the E85 blend was ADM Ethanol except for Test No 6 where New Energy Ethanol was used.
- Table 3 Keep Clean Test 5000 Miles Test No.
- Table 3 illustrates the effect on deposits of having no ethanol (Test No's 1 and 2) when used without and with (respectively) HiTEC® 6560, a Mannich dispersant with a polyol and polyisobutylene carriers.
- the use of the Mannich dispersant reduced the IVD deposits from 429 mg to 5 mg.
- Test No. 4 also shows that reducing the ethanol content in the fuel blend from 84% to 74% reduced the deposits from 299 mg to 265 mg. This further illustrates that gasoline ethanol blends will need better dispersancy and detergency.
- Test No. 6 used the New Energy Ethanol which as shown in Table 1 contributes much less to deposits than does the ADM Ethanol, so the IVD in Table 3 correspondingly shows only 99 mg of deposit.
- Test No. 7 shows the result from a higher treat rate (500 PTB) of a polyetheramine dispersant instead of the Mannich dispersant and the result when combusting the E85 fuel was an incredibly low 4 mg of deposit, at least a major portion of which can be attributed to the ethanol by comparing to Test No. 6.
- the present disclosure provides a method to reduce the Intake Valve Deposits and Combustion Chamber Deposits in an engine combusting an ethanol-containing fuel by adding to the fuel a polyetheramine dispersant or a Mannich dispersant. It is therefore expected that the combination thereof will have similar or even enhanced and synergistic results.
- the reduction of deposit formation is directly related to reduction in engine wear.
- each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Combustion & Propulsion (AREA)
- Liquid Carbonaceous Fuels (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US11/549,870 US20080086936A1 (en) | 2006-10-16 | 2006-10-16 | Method and compositions for reducing wear in engines combusting ethanol-containing fuels |
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Publication Number | Publication Date |
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EP1918355A1 true EP1918355A1 (fr) | 2008-05-07 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP07254000A Withdrawn EP1918355A1 (fr) | 2006-10-16 | 2007-10-09 | Procédé et compositions pour réduire l'usure dans des moteurs de combustion de carburant contenant de l'éthanol |
Country Status (3)
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US (1) | US20080086936A1 (fr) |
EP (1) | EP1918355A1 (fr) |
BR (1) | BRPI0704421A (fr) |
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GB2463994B (en) * | 2008-09-24 | 2012-05-23 | Afton Chemical Corp | Fuel compositions |
US8709108B2 (en) | 2008-09-24 | 2014-04-29 | Afton Chemical Corporation | Fuel compositions |
GB2463994A (en) * | 2008-09-24 | 2010-04-07 | Afton Chemical Corp | Fuel compositions |
CN103937535A (zh) * | 2013-01-22 | 2014-07-23 | 中石化洛阳工程有限公司 | 一种重质原油用破乳剂 |
CN103937535B (zh) * | 2013-01-22 | 2015-12-09 | 中石化洛阳工程有限公司 | 一种重质原油用破乳剂 |
US10457884B2 (en) | 2013-11-18 | 2019-10-29 | Afton Chemical Corporation | Mixed detergent composition for intake valve deposit control |
EP3071677A4 (fr) * | 2013-11-18 | 2016-12-28 | Afton Chemical Corp | Composition détergente mixte pour lutter contre la formation de dépôts sur les soupapes d'admission |
RU2712188C1 (ru) * | 2016-09-01 | 2020-01-24 | ТУНАП ГМБХ энд КО. КГ | Присадка к топливу для очистки двигателя внутреннего сгорания |
US10968409B2 (en) | 2016-09-01 | 2021-04-06 | Tunap Gmbh & Co. Kg | Fuel additive for cleaning an internal combustion engine |
CN109642172A (zh) * | 2016-09-01 | 2019-04-16 | 统耐保有限责任两合公司 | 用于清洁内燃发动机的燃料添加剂 |
WO2018041710A1 (fr) * | 2016-09-01 | 2018-03-08 | Tunap Gmbh & Co. Kg | Additif pour carburant permettant de nettoyer un moteur à combustion interne |
CN109642172B (zh) * | 2016-09-01 | 2021-06-04 | 统耐保有限责任两合公司 | 用于清洁内燃发动机的燃料添加剂 |
AU2017320601B2 (en) * | 2016-09-01 | 2020-02-27 | Tunap Gmbh & Co. Kg | Fuel additive for cleaning an internal combustion engine |
US10273425B2 (en) | 2017-03-13 | 2019-04-30 | Afton Chemical Corporation | Polyol carrier fluids and fuel compositions including polyol carrier fluids |
EP3604484A1 (fr) * | 2018-08-03 | 2020-02-05 | Afton Chemical Corporation | Additifs lubrifiants pour carburants |
CN110791338B (zh) * | 2018-08-03 | 2021-05-25 | 雅富顿化学公司 | 用于燃料的润滑性添加剂 |
CN110791338A (zh) * | 2018-08-03 | 2020-02-14 | 雅富顿化学公司 | 用于燃料的润滑性添加剂 |
US11873461B1 (en) | 2022-09-22 | 2024-01-16 | Afton Chemical Corporation | Extreme pressure additives with improved copper corrosion |
US12024686B2 (en) | 2022-09-30 | 2024-07-02 | Afton Chemical Corporation | Gasoline additive composition for improved engine performance |
US11884890B1 (en) | 2023-02-07 | 2024-01-30 | Afton Chemical Corporation | Gasoline additive composition for improved engine performance |
US11795412B1 (en) | 2023-03-03 | 2023-10-24 | Afton Chemical Corporation | Lubricating composition for industrial gear fluids |
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BRPI0704421A (pt) | 2008-06-03 |
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