Patent Application
20080086934
By “ethanol” herein is meant ethyl alcohol, the chemical compound C2H5OH. This can arise in or be provided in many qualities or grades, such as a commercial blend or 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).
By the present disclosure herein is provided a method for improving the protection of internal combustion engines and the fuel delivery system used to convey and deliver the fuel to the combustion engine. In particular, the problems that can arise in the delivery and combustion of fuels containing ethanol, and especially high levels of ethanol are addressed by the embodiments within the present claims. The more polar nature of the ethanol as compared to the less polar hydrocarbonaceous gasoline can have a negative impact on, for example, the parts of the engine's combustion surfaces, fuel tank, valves, seals, gaskets, injectors, liners, pumps, hoses, liners, filters, and other components. In addition, the ethanol used in the ethanol-gasoline blends of the present disclosure is not necessarily or always pure ethyl alcohol but can and will often contain certain varying amounts of sulfur and sulfur-containing chemicals, acidic or basic components or contaminants, water, possibly ethylene glycol, other alcohols, and petrochemical fractions boiling near ethanol. In addition, when the ethanol is bio-derived, the bio-source can contribute other natural products and bio-derivatives which can accumulate in or on vulnerable engine and fuel delivery parts. The present disclosure provides fuel compositions and methods for reducing or eliminating the negative impact on the engine or its delivery system from these natural products and bio-derivatives. The present disclosure also provides improved protection of the fuel delivery system by the incorporation of certain fuel additives in the gasoline-ethanol fuel composition.
In one embodiment is provided a method to improve protection of a fuel delivery system in an internal combustion engine, said method comprising delivering to or combusting in said engine a fuel composition comprising gasoline, ethanol and at least one fuel additive, said additive being selected from the group consisting of succinimide dispersants, succinamide dispersants, amides, Mannich base dispersants, and polyetheramine dispersants. Polyetheramines are particularly effective in the compositions and methods of the present disclosure.
In another example the fuel additive is further selected from the group consisting of phenolics, hindered phenolics, aryl amines, and diphenyl amines.
In yet another aspect herein, the fuel additive is further selected from the group consisting of monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, p-phenylenediamine and dicyclohexylamine. Particularly useful herein as the acid fuel additives are tall oil fatty acids and/or the diacid dodecenyl succinic acid.
In yet another embodiment the fuel additive can be further selected from the group consisting of oxylated alkylphenolic resins, and formaldehyde polymer with 4-(1,1-dimethylethyl)phenol, methyloxirane and oxirane.
The fuel additive can be further selected from the group consisting of methyl cyclopentadienyl manganese tricarbonyl (“MMT”), cyclopentadienyl manganese tricarbonyl, azides, tetraethyl lead, peroxides and alkyl nitrates.
The fuel additive can further be selected from ethylene oxide, propylene oxide, butylene oxide, epoxides, C1-C8 aliphatic hydrocarbons, nitrous oxide, nitromethane and xylene.
The fuel additive is also further selected from the group consisting of monoesters, diesters, ethers, diethyl ether, ketones, diethers, polyethers, glymes and glycols.
In still another aspect the fuel additive is selected from the group consisting of monocarboxylic acids, dicarboxylic acids, and polycarboxylic acids.
Also provided herein is a method of improving the protection of an engine combusting a fuel composition containing gasoline and ethanol, said method consisting essentially of combining the fuel and an additive selected from the group consisting of driveability enhancing materials that include monoesters, diesters, ethers, ketones, diethers, polyethers, glymes and glycols, wherein the driveability of said engine is improved relative to the driveability of the engine combusting a gasoline fuel without ethanol.
In another embodiment the fuel additive is selected from the group consisting of phenates, salicylates, sulfonates, nonylphenol ethoxylates, fuel-soluble alkali detergents and alkaline earth metal-containing detergents. Particularly effective detergents herein include phenates, salicylates, sulfonates, and nonylphenol ethoxylates.
Thus the present disclosure can be practiced by producing, conveying, or combusting a fuel composition comprising, or in another embodiment consisting essentially of, gasoline, ethanol and at least one fuel delivery system protecting agent, said agent being selected from the group consisting of succinimide dispersants, succinamide dispersants, amides, Mannich base dispersants, polyetheramine dispersants, phenolics, hindered phenolics, aryl amines, diphenyl amines, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, p-phenylenediamine and dicyclohexylarnine, oxylated alkylphenolic resins, formaldehyde polymer with 4-(1,1-dimethylethyl)phenol, methyloxirane and oxirane, methyl cyclopentadienyl manganese tricarbonyl, cyclopentadienyl manganese tricarbonyl, azides, tetraethyl lead, peroxides, alkyl nitrates, monoesters, diesters, ethers, diethers, diethyl ether, ketones, polyethers, glycols, glymes, oxiranes, C1-C8 aliphatic hydrocarbons, butylene oxide, propylene oxide, ethylene oxide, epoxides, butane, pentane, xylene, nitrous oxide, nitromethane, phenates, salicylates, sulfonates, nonylphenol ethoxylates, and fuel-soluble alkali detergents and an alkaline earth metal-containing detergents.
Also provided herein is a fuel delivery system protecting agent concentrate for gasoline engines combusting an ethanol-containing fuel, said concentrate comprising one or more fuel delivery system protecting 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 one embodiment, the ethanol content of the fuel composition is from about 74% to about 85%. In another embodiment of the disclosure herein the ethanol content of the fuel composition is from about 50% to about 74%.
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 from the New Energy Ethanol. Such an E85 fuel will therefore need more detergents, dispersants and other additives than E85 fuels utilizing other ethanol sources to prolong the useful life of the engine and fuel delivery system.
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 the protection of a fuel delivery system in the engine combusting the E85 fuel blend.
Thus, there is provided herein a method of improving protection of a fuel delivery system 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 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.
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 dispersant reduced the IVD deposits from 429 mg to 5 mg. 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 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 the Mannich dispersant) and Test No. 5 (E85 without the 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 improve protection of a fuel delivery system 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 increased longevity of the useful life of engine combustion surfaces, injectors, valves, gaskets, liners, seals, hoses, pumps, filters, and other fuel delivery system parts.
A fuel composition is prepared by combining gasoline (15% by volume) and ethanol (85% by volume) and a Mannich base fuel additive (HiTEC® 6560 available from Afton Chemical Corporation, and having a PIB group with a MW of 950, and a cresol group reacted with dibutylamine). The fuel additive is present in the fuel composition at 200 ppm. The composition is fed to and combusted in a direct injection gasoline engine. The resulting fuel will demonstrate improved protection provided in the combustion engine and fuel delivery system compared to the protection resulting before and after combustion of a fuel composition not containing ethanol, as well as compared to the combustion of a fuel composition containing ethanol and gasoline but no Mannich base fuel additive.
A fuel composition is prepared by combining gasoline (15% by volume) and ethanol (85% by volume) and an alkylated succinimide dispersant (HiTEC® 4249 available from Afton Chemical Corporation, and having a PIB group with a MW of 950, and a maleic anhydride reacted with tetraethylene pentamine). The dispersant is present in the fuel composition at 100 ppm. The composition is fed to and combusted in a spark ignited internal combustion engine. The resulting fuel demonstrates improved protection in an internal combustion engine and its delivery system compared to the combustion of a fuel composition not containing ethanol, as well as compared to the combustion of a fuel composition containing ethanol and gasoline but no alkylated succinimide dispersant.
A fuel composition is prepared by combining gasoline (15% by volume) and ethanol (85% by volume) and a phenolic driveability agent (HiTEC® 4733 available from Afton Chemical Corporation and containing 2,4 di-t-butyl phenol). The antioxidant is present in the fuel composition at 100 ppm. The composition is fed to and combusted in a gasoline engine. The resulting fuel improves protection in an internal combustion engine and its fuel delivery system compared to the combustion of a fuel composition not containing ethanol, as well as compared to the delivery and combustion of a fuel composition containing ethanol and gasoline but no phenolic antioxidant.
A fuel composition is prepared by combining gasoline (15% by volume) and ethanol (85% by volume) and a demulsifier agent (Baker Petrolite's Tolad 9372). The demulsifier agent is present in the fuel composition at 30 ppm. The composition is fed to and combusted in an internal combustion gasoline spark ignited engine. The resulting fuel improves the protection in an internal combustion engine and its fuel delivery system compared to the combustion and delivery of a fuel composition not containing ethanol, as well as compared to the combustion and delivery of a fuel composition containing ethanol and gasoline but no demulsifier.
A fuel composition is prepared by combining gasoline (15% by volume) and ethanol (85% by volume) and a dehazer agent (2-ethyl hexanol available from BASF). The dehazer agent is present in the fuel composition at 5 weight percent. The composition is fed to and combusted in an internal combustion gasoline spark ignited engine. The resulting fuel improves protection in an internal combustion engine and its delivery system compared to the combustion and delivery of a fuel composition not containing ethanol, as well as compared to the combustion and delivery of a fuel composition containing ethanol and gasoline but no dehazer.
A fuel composition is prepared by combining gasoline (15% by volume) and ethanol (85% by volume) and a MMT octane improver (HiTEC® 3000 available from Afton Chemical Corporation). The octane improver is present in the fuel composition at 300 ppm. The composition is fed to and combusted in an internal combustion engine. The resulting fuel improves protection in an internal combustion engine and its delivery system compared to the combustion and delivery of a fuel composition not containing ethanol, as well as compared to the combustion and delivery of a fuel composition containing ethanol and gasoline but no MMT.
A fuel composition is prepared by combining gasoline (15% by volume) and ethanol (85% by volume) and a volatility improving agent (2-ethyl hexyl nitrate, HiTEC® 4103 available from Afton Chemical Corporation. The volatility improving agent is present in the fuel composition at 8 weight percent. The composition is fed to and combusted in a gasoline engine. The resulting fuel improves protection in an internal combustion engine and its delivery system compared to the combustion and delivery of a fuel composition not containing ethanol, as well as compared to the delivery and combustion of a fuel composition containing ethanol and gasoline but no volatility improving agent.
A fuel composition is prepared by combining gasoline (15% by volume) and ethanol (85% by volume) and a detergent agent (HiTEC® 611 available from Afton Chemical Corporation, and having an overbased calcium sulfonate). The detergent agent is present in the fuel composition at 2.5 weight percent. The composition is fed to and combusted in an internal combustion engine. The resulting fuel improves protection in an internal combustion engine and its delivery system compared to the delivery and combustion of a fuel composition not containing ethanol, as well as compared to the delivery and combustion of a fuel composition containing ethanol and gasoline but no detergent agent.
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.
