Patent Application
20080086936
By “ethanol” herein is meant ethyl alcohol, the chemical compound C2H5OH. 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. By the present disclosure 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.
By the present disclosure is provided in one embodiment a method to reduce wear and/or deposits in an internal combustion engine combusting an ethanol-containing fuel, said method 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)phenol, methyloxirane and oxirane, octane enhancer materials, monoesters, diesters, ethers, diethers, methyloxirane, oxiranes, peroxides, alkyl nitrates, C1-C8 aliphatic hydrocarbons (such as alkanes), ketones, butylene oxides, propylene oxides, ethylene oxides, epoxides, butane, pentane, nitrous oxide, nitromethane, xylene, diethyl ether, polyethers, glycols, phenates, salicylates, sulfonates, nonylphenol ethoxylates, alkali detergents and an alkaline earth metal-containing detergents.
The 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.
Also provided herein is 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.
Further provided herein is 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.
In another embodiment 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, said method 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-dimethylethyl)phenol, methyloxirane and oxirane, octane enhancer materials, monoesters, diesters, ethers, methyloxirane, oxiranes, peroxides, alkyl nitrates, C1-C8 aliphatic hydrocarbons, ketones, butylene oxides, propylene oxides, ethylene oxides, epoxides, butane, pentane, nitrous oxide, nitromethane, xylene, diethyl ether, diethers, polyethers, glycols, phenates, salicylates, sulfonates, nonylphenol ethoxylates, alkali detergents and an alkaline earth metal-containing detergents.
Table 1 shows the intake valve deposits generated on an Intake Valve Deposit simulator rig test using E85 fuels containing the ethanols indicated. In this rig test, 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. As can be seen, 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. As can be seen by comparing the rig test deposits from these two ethanols when used in E85 gasoline-ethanol fuel blend, the ADM Ethanol generated a 10-fold increase in deposits relative to the deposits produced by the New Energy Ethanol in the rig test. Such an E85 fuel will therefore need more detergents, dispersants and other additives than E85 fuels utilizing other ethanol sources.
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. Thus, for at least those 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. These 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 E85 fuel blend.
Thus, there is provided herein a method of reducing deposits formed in an internal combustion engine combusting an ethanol-gasoline blend, said method 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 dimethylcyclohexylarnine, 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.
In another example, 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 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. In the E85 fuel blend of Test No. 3 at a 5 PTB treat rate of the Mannich dispersant in the finished fuel had a IVD deposit of 191 mg but when the dispersant was lacking from the E85 blend (Test No. 5), the IVD deposit went up to 227, due in part to the contribution from the ethanol. Comparing Test No. 3 and 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 amazingly low 4 mg of deposit, at least a major portion of which can be attributed to the ethanol by comparing to Test No. 6.
For the CCD results of Table 3, comparing Test No. 3 (E85 plus Mannich dispersant) and Test No. 5 (E85 without the Mannich dispersant) one sees an improvement in reducing Combustion Chamber Deposits from 299 mg to 184 mg and using the cleaner New Energy Ethanol of Test No. 6 reduced the Combustion Chamber Deposit even further to 176 mg.
In this manner it is clear that 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.
Table 4 shows the results of wear scar testing in which a median wear scar diameter MWSD) is reported. Run 1 was E85 using New Energy Ethanol and this baseline MWSD was 605. When HiTEC® 4142 (oleic acid plus N,N dimethylcyclohexylamine) was added as a corrosion inhibitor, the MWSD was reduced to 445. Changing the corrosion inhibitor in the E85 fuel to DDSA (50% in A150 solvent) gave a slightly higher value of 540 but still improved over the baseline for E85. Using ADM Ethanol in the E85 produced even further reduction in the wear scar, probably due to the corrosion inhibitor (DCI-11) in the ethanol. This Table shows the benefit in wear scar reduction and hence in reducing wear in an engine achieved by incorporation of dodecenyl succinic acid and/or oleic acid plus N,N dimethylcyclohexylamine into an ethanol-containing gasoline fuel blend.
Other embodiments of the present disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed herein. As used throughout the specification and claims, “a” and/or “an” may refer to one or more than one. Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, percent, ratio, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, 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.
