AU2011271224B2 - Fuel composition and its use - Google Patents

Abstract

A method for increasing flamespeed of an internal combustion engine by burning a certain gasoline composition is provided. The gasoline composition contains (a) a major amount of a mixture of hydrocarbons in the gasoline boiling range and (b) a minor amount of at least one hydrocarbon having 5 to 12 carbon atoms and containing at least one cyclopropyl group and at least one acetylenic group.

Description

WO 2011/163122 PCT/US2011/041063 FUEL COMPOSITION AND ITS USE Field of the Invention The present invention relates to a gasoline composition 5 and its use, particularly, in combustion engines. Background of the Invention Spark initiated internal combustion gasoline engines require fuel of a minimum octane level which depends upon the design of the engine. Petroleum refineries are constantly 10 faced with the challenge of continually improving their products to meet increasingly severe governmental efficiency and emission requirements, and consumers' desires for enhanced performance. For example, in producing a fuel suitable for use in an internal combustion engine, petroleum 15 producers blend a plurality of hydrocarbon containing streams to produce a product that will meet governmental combustion emission regulations and the engine manufacturers performance fuel criteria, such as research octane number (RON). Similarly, engine manufacturers conventionally design spark 20 ignition type internal combustion engines around the properties of the fuel. For example, engine manufacturers endeavor to inhibit to the maximum extent possible the phenomenon of auto-ignition which typically results in knocking and, potentially engine damage, when a fuel with 25 insufficient knock-resistance is combusted in the engine. Under typical driving situations, engines operate under a wide range of conditions depending on many factors including ambient conditions (air temperature, humidity, etc.), vehicle load, speed, rate of acceleration, and the 30 like. Fuel blenders have to design products which perform well under such diverse conditions. This naturally requires compromise, as often times fuel properties or engine parameters that are desirable under certain speed/load 1 WO 2011/163122 PCT/US2011/041063 conditions prove detrimental to overall performance at other speed/load conditions. It is desirable to provide high burn velocity fuel, particularly for use under lean conditions to shorten the burn duration and thereby improve the 5 thermodynamic efficiency. A faster burn velocity also serves to maximize conversion of the fuel, thereby increasing the overall fuel economy and reducing emissions. Thus, the flame speed (related to burning velocity) of combustible fuel plays an important role in fuels chemistry and in the performance 10 of engines (power) and emissions from spark-ignition engines. Summary of the Invention In accordance with certain of its aspects, in one embodiment of the present invention provides a gasoline composition comprising (a) a major amount of a mixture of 15 hydrocarbons in the gasoline boiling range and (b) a minor amount of at least one hydrocarbon having 5 to 12 carbon atoms and containing at least one cyclopropyl group and at least one acetylenic group. In another embodiment, the present invention provides a 20 method of improving the flame speed of a gasoline which comprises adding to a major portion of a gasoline mixture, minor amount of the additive described above. Yet in another embodiment, the present invention provides a method for operating a spark ignition engine which 25 comprises burning in said engine such fuel composition described above. Brief Description of the Drawing Fig. 1 represents the Schlieren images of single combustion event 30ms after ignition of Base Fuel-i plus 20% 30 Cyclopropylacetylene. Fig. 2 represents the Schlieren images of single combustion event 30ms after ignition of Base Fuel-i only. 2 WO 2011/163122 PCT/US2011/041063 Fig. 3 represents improvement in Hyundai Acceleration Performance of the Faster Flame Speed fuel blends versus Base Fuel - 2 (reference fuel); all additive concentrations in ppmw. 5 Detailed Description of the Invention We have found that the blended fuel composition described above significantly enhance the flame speed of gasoline fuels without compromise in RON. In an ideal case, flame speed is the measured rate of expansion of the flame 10 front, generally measured in meters/second (m/s). In a spark engine, flame speed depends on gas pressure, temperature, and density change as a result of changes in volume due to piston motion (see Internal Combustion Engine Fundamentals, John B. Heywood. McGraw-Hill Book Co.,1988). Thus, "rate of 15 expansion of the flame front" can also be measured by the increase in the pressure. Early pressure rise after spark (at 0 seconds) is also a measure of high burning velocity. The gasoline composition of the present invention contains component (b) of at least one hydrocarbon having 5 20 to 12 carbon atoms and containing at least one cyclopropyl group and at least one acetylenic group. The term "acetylenic group" refers to unsaturated hydrocarbons that have carbon atoms in chains linked by one or more triple bonds. The component (b) can be a compound having the 25 formula: Formula I

R

5 R 6 R4 R3

(CH

2 )nC- C-R 1 R2 30 wherein n is an integer from 0 to 7; R 1 to R 6 are independently hydrogen, alkyl group having 1 to 7 carbon 3 WO 2011/163122 PCT/US2011/041063 atoms, alkenyl group having 1 to 7 carbon atoms, alkynyl group having 1 to 7 carbon atoms, cyclic group having 1 to 7 carbon atome, with the proviso that the total number of carbon atoms in the compound are from 5 to 12. Preferably n 5 is an integer from 0 to 5, more preferably 0 to 3. Preferably R 1 to R 6 are independently hydrogen, alkyl group having 1 to 5, more preferably 1 to 3 carbon atoms, with the proviso that the total number of carbon atoms in the compound are from 5 to 12. 10 Some of these cyclopropyl group-containing acetylenic compounds are available from GSF Chemicals Corporation and Sigma-Aldrich Company Ltd. Various synthetic routes can be used in the preparation of the cyclopropyl group-containing acetylenic compounds useful in the invention. For example, 15 cyclopropylacetylene can be prepared by chlorination of acetylcyclopropane with PCl 5 in the presence of an org. base in a chlorinated hydrocarbon with dehydrochlorination of the mixt. of alpha,-alpha dichlorocyclopropane and alpha chlorovinylcyclopropane (with base at reflux in a solvent) 20 and simultaneous distillation. (see Dolgii, I. E.; Shvedova, I. B.; Shavrin, K. N.; Nefedov, 0. M. (Zelinskii, N. D., Institute of Organic Chemistry, USSR). U.S.S.R. (1977)) Dicyclopropylacetylenic derivatives can be prepared using Favorskii reaction and common organic systhesis procedure 25 (Nefedov, 0. M.; Dolgii, I. E.; Shvedova, I. B.; Baidzhigitova, E. A. Inst. Org. Khim. Im. Zelinskogo, Moscow, USSR. Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya (1978), (6), 1339-44.) Cycopropyl Cyanide can be prepared by the reaction of sodium amide with 30 chlorobutyronitrile (Organic Syntheses, Volume 3, page 223. John Wiley & Sons, Inc. Submitted by M. J. Schlatter and checked by R. L. Shriner and Chris Best). Other methods can be used to prepare the cyclopropyl group-containing 4 WO 2011/163122 PCT/US2011/041063 acetylenic compounds useful in the invention as are known to one who is skilled in the art of organic synthesis. The preferred cyclopropyl group-containing acetylenic compounds maybe, for example, cyclopropyl acetylene; 1-cyclopropyl-1 5 propyne; 1-cyclopropyl-2-propyne; 1-methyl-1-ethynyl cyclopropane; 2-methyl-1-ethynyl-cyclopropane; 1,1-(3 methylene-1-propyne-1,3-diyl)bis-; 1,1-bicyclopropyl, 2,2 diethynyl-; 1-cyclopropylpenta-1,3-diyne; cyclopropane, 1,1 (1,3-butadiyne-1,4-diyl)bis-; cyclopropane, 1,1-(3-methyl-1 10 propyne-1,3-diyl)bis-; and 1,4-dicyclopropylbuta-1,3-diyne. The fuel composition of the present invention comprises a major amount of a mixture of hydrocarbons in the gasoline boiling range and a minor amount of component (b). As used herein for component (b), the term "minor amount" means less 15 than 50% by weight of the total fuel composition, preferably less than 30% by weight of the total fuel composition. However, the term "minor amount" will contain at least some amount, preferably at least 0.001% by weight of the total fuel composition. 20 An effective amount of one or more compounds of component (b), more particularly Formula I, are introduced into the combustion zone of the engine in a variety of ways to improve flame speed. As mentioned, a preferred method is to add a minor amount of one or more compounds of component 25 (b) to the fuel. For example, one or more compounds of component (b) may be added directly to the fuel or blended with one or more carriers to form an additive concentrate which may then be added at a later date to the fuel. The amount of component (b) used will depend on the 30 particular variation of Formula I used, the engine, the fuel, and the presence or absence of carriers and additional detergents. Generally, each compound of component (b) is added in an amount up to 20% by weight, especially from 5 WO 2011/163122 PCT/US2011/041063 0.005% by weight, more preferably from 0.05% by weight, even more preferably from 0.5% by weight, most preferably from 1% by weight, based on the total weight of the fuel composition. Suitable liquid hydrocarbon fuels of the gasoline 5 boiling range are mixtures of hydrocarbons having a boiling range of from 250C to 2320C and comprise mixtures of saturated hydrocarbons, olefinic hydrocarbons and aromatic hydrocarbons. Preferred are gasoline mixtures having a saturated hydrocarbon content ranging from 40% to 80% by 10 volume, an olefinic hydrocarbon content from 0% to 30% by volume and an aromatic hydrocarbon content from 10% to 60% by volume. The base fuel is derived from straight run gasoline, polymer gasoline, natural gasoline, dimer and trimerized olefins, synthetically produced aromatic hydrocarbon 15 mixtures, or from catalytically cracked or thermally cracked petroleum stocks, and mixtures of these. The hydrocarbon composition and octane level of the base fuel are not critical. The octane level, (R+M)/2, will generally be above 85. Any conventional motor fuel base can be employed in the 20 practice of the present invention. For example, hydrocarbons in the gasoline can be replaced by up to a substantial amount of conventional alcohols or ethers, conventionally known for use in fuels. The base fuels are desirably substantially free of water since water could impede a smooth combustion. 25 The word major amount is used herein because the amount of hydrocarbons in the gasoline boiling range is often 50 weight or volume percent or more. Normally, the hydrocarbon fuel mixtures to which the invention is applied are substantially lead-free, but may 30 contain minor amounts of blending agents such as methanol, ethanol, ethyl tertiary butyl ether, methyl tertiary butyl ether,tert-amyl methyl ether and the like, at from 0.1% by volume to 15% by volume of the base fuel, although larger 6 WO 2011/163122 PCT/US2011/041063 amounts may be utilized. The fuels can also contain conventional additives including antioxidants such as phenolics, e.g., 2,6-di-tertbutylphenol or phenylenediamines, e.g., N,N'-di-sec-butyl-p-phenylenediamine, dyes, metal 5 deactivators, dehazers such as polyester-type ethoxylated alkylphenol-formaldehyde resins. Corrosion inhibitors, such as a polyhydric alcohol ester of a succinic acid derivative having on at least one of its alpha-carbon atoms an unsubstituted or substituted aliphatic hydrocarbon group 10 having from 20 to 50 carbon atoms, for example, pentaerythritol diester of polyisobutylene-substituted succinic acid, the polyisobutylene group having an average molecular weight of about 950, in an amount from 1 ppm (parts per million) by weight to 1000 ppm by weight, may also be 15 present. The fuel compositions of the present invention may also contain one or more detergents. When detergents are utilized, the fuel composition will comprise a mixture of a major amount of hydrocarbons in the gasoline boiling range as 20 described hereinbefore, a minor amount of one or more compounds of component (b) as described hereinbefore and a minor amount of one or more detergents. As noted above, a carrier as described hereinbefore may also be included. As used herein for detergents, the term "minor amount" means 25 less than 10% by weight of the total fuel composition, preferably less than 1% by weight of the total fuel composition and more preferably less than 0.1% by weight of the total fuel composition. The one or more detergents are added directly to the hydrocarbons, blended with one or more 30 carriers, blended with one or more compounds of component (b), or blended with one or more compounds of component (b) and one or more carriers before being added to the hydrocarbon. The compounds of component (b) can be added at 7 WO 2011/163122 PCT/US2011/041063 the refinery, at a terminal, at a depot, at a retail site, or by the consumer. The treat rate of the fuel additive detergent packages that contains one or more detergents in the final fuel 5 composition is generally in the range of from 0.007 weight percent to 0.76 weight percent based on the final fuel composition. The fuel additive detergent package may contain one or more detergents, dehazer, corrosion inhibitor and solvent. In addition a carrier fluidizer may sometimes be 10 added to help in preventing intake valve sticking at low temperature. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of examples herein described in 15 detail. It should be understood, that the detailed description thereto are not intended to limit the invention to the particular form disclosed, but on the contrary, the intention is to cover all modifications, equivalents and alternatives falling within the spirit and scope of the 20 present invention as defined by the appended claims. The present invention will be illustrated by the following illustrative embodiment, which is provided for illustration only and is not to be construed as limiting the claimed invention in any way. 25 Octane Test Methods The Research Octane Number (RON) (ASTM D2699) and Motor Octane Number (MON) (ASTM D2700) will be the techniques used in determining the R+M/2 octane of the fuel. The RON and MON of a spark-ignition engine fuel is determined using a 30 standard test engine and operating conditions to compare its knock characteristic with those of primary reference fuel blends of known octane number. Compression ratio and fuel-air ratio are adjusted to produce standard knock intensity for 8 WO 2011/163122 PCT/US2011/041063 the sample fuel, as measured by a specific electronic detonation meter instrument system. A standard knock intensity guide table relates engine compression ratio to octane number level for this specific method. The specific 5 procedure for the RON can be found in ASTM D-2699 and the MON can be found in ASTM D-2700. Table I contains the engine conditions necessary in determine the RON and MON of a fuel. 10 Table I RON and MON Test Conditions Test Engine Conditions Research Octane Number Motor Octane Number Test Method ASTM D-2699-92 ASTM D-2700-92 Engine Cooperative Fuels Research (CFR) Cooperative Fuels Engine Research (CFR) Engine 600 RPM 900 RPM Engine RPM Intake Air Varies with Barometric Pressure 38 0 C Temperature (eq 88kPA=19.4 0 C, 101.6kPa=52.2 0 C) Intake Air 3.56 - 7.12 g H 2 0/kg dry air 3.56 - 7.12 g Humidity H 2 0/kg dry air Intake mixture not specified 149 0 C temperature Coolant 100 0 C 100 0 C Temperature Oil 57 0 C 57 0 C Temperature Ignition 13 degrees BTDC Varies with Advance-fixed compression ratio (eq 14-26 degrees BTDC) Carburetor Set according to engine altitude 14.3 mm Venture (eq 0-500m=14.3, 500-1000m=15.1 mm) 9 WO 2011/163122 PCT/US2011/041063 Flame Speed Test Method Flame Speed of the fuels were tested with Leeds Combustion Bomb Method as described in SAE Technical Paper Series 2000-01-0192, Aspects of Laminar and Turbulent Burning 5 Velocity relevant to SI Engines, by L.Gillespie, M. Lawes, C.G.W. Sheppard and R. Woolley, SAE 2000 World Congress, Detroit, Michigan, March 6-9, 2000. Fuels were tested under laminar conditions with initial conditions of 5 bar absolute pressure and 360K. All the burning velocities were measured 10 at an equivalence ratio 'P = 1 (i.e., stoichiometric). The tests were conducted using the Leeds Mk2 fan stirred combustion vessel (bomb) a stainless sphere of 30 liter volume and with extensive optical access. The fuels were injected into the bomb and allowed to vaporize fully, than a 15 stoichiometric amount of air was added. The gases were mixed with stirring fans inside the vessel and the contents were heated to the desired temperature. The fans were turned off prior to ignition. Mixtures were ignited using a spark plug. Pressure transducers were flush mounted inside the bob and 20 recorded the pressure rise as a function of time. Base Fuel The base fuel physical properties used in the tests can be found in Table II. 25 10 WO 2011/163122 PCT/US2011/041063 Table II Base Fuel Physical Properties Base Base Parameter Method Units Fuel-i Fuel-2 RON ASTM D2699 95.4 95.3 MON ASTM D2700 86.6 86.4 Density @ 15 0C IP 365 g cm- 3 0.7300 0.7293 Oxidation Stability IP 40 mins > 1440 (induction) Unwashed gum IP 131 mg/100ml 6 8 Distillation IP 123 IBP 0C 34.9 35.7 10% rec 0C 51.8 54.9 20% rec 0C 59.9 62.5 30% rec 0C 68.1 70.6 40% rec 0C 77.8 80.6 50% rec 0C 89.7 92.7 60% rec 0C 103.1 105.7 70% rec 0C 115.6 118.4 80% rec 0C 126.7 129.6 90% rec 0C 139.6 141.3 95% rec 0C 146.9 147.9 FBP 0C 167.1 171.4 Residue % vol 1.0 1.0 Recovery % vol 95.5 97.8 Loss % vol 3.5 1.2 E70 % vol 32.0 29.1 E100 % vol 57.9 55.7 E120 % vol 74.0 71.4 E150 % vol 96.3 95.7 RVP IP 394/ASTM 519 kPa 59.8 56.0 GC LTP/26 C 6.60 6.61 H 12.51 12.56 0 0.00 0.00 Paraffins % vol 7.41 7.29 Isoparaffins % vol 53.84 53.90 Olefins (including % vol 3.06 3.76 dienes) Dienes % vol 0.01 0.01 Napthenes % vol 6.28 6.14 Aromatics % vol 29.07 28.79 Oxygenates % vol 0.00 0.00 Unknowns % vol 0.35 0.13 Total % vol 100.01 100.01 Benzene (+Me Cyc5 ene) % vol 0.48 0.52 Sulphur - WD XRF ISO 20884 mg/kg 10 Sulphur - Antek ISO 20846 mg/kg 5 11 WO 2011/163122 PCT/US2011/041063 Examples 1-8 For examples 1-3, the additives were each added to Base Fuel 1 (Octane 91) at 20% in weight. These samples were then tested thrice for RON, MON, and flame speed. The average of 5 three runs was tabulated in Table III. Similar blending method was used for examples 4-8 with Base Fuel 2 (Octane 91) at concentrations indicated in Table III. Table III 10 Additive (in weight %) Flamespeed RON MON (R+M) Example Base in Gasoline Pressure in /2 # blend bomb(bar) at 0.1s after ignition 1 Base None 17.35 95.4 86.6 91.0 Fuel 1 2 Base 20% of 32.33 97.0 81.8 89.4 Fuel 1 Cyclopropylacetylene 3 Base 20% of 1-Pentyne 26.59 93.2 81.8 87.5 Fuel 1 4 Base None 21.66 95.2 86.9 91.0 Fuel 2 5 Base 5% of 25.09 96.1 85.3 90.7 Fuel 2 Cyclopropylacetylene 6 Base 10% of 32.74 96.3 84.6 90.4 Fuel 2 Cyclopropylacetylene 7 Base 5% of 1-Pentyne 24.22 95.3 85.6 90.4 Fuel 2 8 Base 10% of 1-Pentyne 24.36 94.9 84.9 89.9 Fuel 2 Addition of molecules containing cyclopropyl and acetylenic group significantly enhanced the flame speed of 15 the given fuel composition. The increase in cylinder pressure compared to the reference fuel after 0.1 seconds after ignition is used as the measure of the laminar flame speed. Results showed that Cyclopropylacetylene and 1 Pentyne at blend concentrations of 10% and 5% produced a 20 statistically significant (at99%) improvement in chamber pressure compared to the reference fuel. We chose another molecule with three member ring, without acetylene moiety (carbon triple bond carbon), for example, Carene. Carene was tested at 20% in Base Fuel 2. This blend showed no 12 WO 2011/163122 PCT/US2011/041063 statistically significant improvement in pressure difference compared to the Base Fuel 2 (reference fuel). At a concentration of 20 wt.% Cyclopropylacetylene in the Base Fuel-i shows the pressure increase in the combustion 5 chamber 0.1 seconds after ignition of the homogeneous charge is statistically (>95%) significantly greater than the Base Fuel-i (reference fuel). For example, Schlieren images of the combustion, 30ms after the ignition event shown in the Figures clearly show a large difference in both the flame 10 size and structure (Cyclopropylacetylene being more cellular). It is noted that at nearly 33ms the flame for the fuel blend containing cyclopropylacetylene fills the viewing window; the Base Fuel-i (reference fuel) takes nearly 38.5ms to fill the viewing window, so it is not possible to show 15 differences in flame size after this point. Hence the images are not shown at 100ms (0.1 seconds) after ignition to help corroborate the pressure data. However, pressure at 0.1 seconds been tabulated in Table III. Cyclopropylacetylene, 1-Pentyne were blended at 0.5% and 20 1.0% into Base Fuel - 2. Each fuel blend was tested in a single day along with the reference fuel (base fuel without the additive) in an A-B-A-B..... type test design on the chassis dynamometer. A Hyundai Coupe was used for the testing. As this vehicle has shown to be insensitive to 25 changes in fuel octane the improvements in acceleration performance achieved between the test and reference fuel are attributed to changes in the laminar flame speed of the fuel. A standard chassis dynamometer power and acceleration test procedure on a Hyundai Coupe was used to obtain these results 30 as shown in Figure 3. The figure shows over 0.2% acceleration performance improvements with 1% cyclopropylacetylene as an additive as compared to the base fuel without the additive. 13 WO 2011/163122 PCT/US2011/041063 The benefit of this increase in flame speed is best utilized in performance a applications such as racing fuel and premium fuel. Addition of such molecules in fuels typically results in less pollution, more power and better 5 efficiency. Faster burning fuels allow engines to run on lean mixtures of gasoline and air, potentially reducing nitrogen oxide and hydrocarbon emissions. As seen in the above Table, the flame speed of the cyclopropyl acetylene in gasoline is greatly increased without lowering the RON value. 10 Further, the fuel composition of the invention increases fuel sensitivity. There are industry reports that indicate fuel with higher sensitivity (lower MON) has better anti-knock quality. (see SAE Technical Paper Series 2001-01-3584, Fuel Anti-Knock quality-Part I. Engine Studies, by G.T. Kalghatgi 15 and SAE Technical Paper Series 2001-01-3585, Fuel Anti-Knock Quality-Part II. Vehicle Studies -How Relevant is Motor Octane Number (MON) in Modern Engines, by G.T. Kalghatgi.) An increase in fuel sensitivity increases the "octane index" of the fuel which is a better measure of the anti-knock 20 quality of the fuel, and leads to improved power and acceleration performance. As seen from the above Table III, while RON value of the cyclopropyl acetylene containing formulation is higher than the reference fuel without the cyclopropyl acetylene, MON value of the cyclopropyl acetylene 25 containing formulation is lower than the reference fuel without the cyclopropyl acetylene. 14

Claims (10)

1. A gasoline composition comprising (a) a major amount of a mixture of hydrocarbons in the gasoline boiling 5 range and (b) a minor amount of cyclopropyl acetylene.

2. A gasoline composition according to claim 1 wherein component (b) is present in an amount from 0.005% by weight to 20% by weight based on the total weight of the 10 gasoline composition.

3. A gasoline composition according to claim 1 or claim 2 further comprising (c) a minor amount of a fuel detergent. 15

4. A method of improving the flame speed of a gasoline which comprises adding to a major portion of a gasoline mixture minor amounts of cyclopropyl acetylene. 20

5. A method for increasing sensitivity of a gasoline which method involves adding to a major portion of a gasoline mixture minor amounts of a cyclopropyl acetylene. 25

6. The use of cyclopropyl acetylene in a gasoline composition to improve flame speed of an internal combustion engine into which the gasoline composition is introduced. 30

7. A gasoline composition substantially as herein described with reference to Figures 1 to 3 and/or the examples. 16

8. A method of improving the flame speed of a gasoline which comprises the steps substantially as herein described with reference to Figures 1 to 3 and/or the examples. 5

9. A method for increasing sensitivity of a gasoline which which comprises the steps substantially as herein described with reference to Figures 1 to 3 and/or the examples. 10

10. The use of cyclopropyl acetylene in a gasoline composition to improve flame speed of an internal combustion engine substantially as herein described with reference to Figures 1 to 3 and/or the examples.