(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`
`(19) World Intellectual Property Organization
`International Bureau
`
`(43) International Publication Date
`31 May 2007 (31.05.2007)
`
` (10) International Publication Number
`
`WO 2007/061903 A1
`
`(51) International Patent Classification:
`C10L 1/182 (2006.01)
`C10L 1/185 (2006.01)
`
`(21) International Application Number:
`PCT/U82006/044789
`
`(22) International Filing Date:
`17 November 2006 (17.11.2006)
`
`(25) Filing Language:
`
`(26) Publication Language:
`
`English
`
`English
`
`(30) Priority Data:
`60/737,790
`60/798,558
`60/798,579
`
`17 November 2005 (17.11.2005)
`8 May 2006 (08.05.2006)
`8 May 2006 (08.05.2006)
`
`US
`US
`US
`
`(71) Applicant (for all designated States except US): CPS
`BIOFUELS, INC. [US/US]; 314 Stromer Drive, Cary,
`NC 27513 (US).
`
`(72) Inventors; and
`(75) Inventors/Applicants (for US only): BRADIN, David
`[US/US]; 314 Stromer Drive, Cary, NC 27513 (US).
`GRUNE, Guerry, L. [US/US]; 784 S. Villier Ct., Vlrginia
`Beach, VA 23452 (US). TRIVETTE, Martin [US/US];
`139 Kenyon St., Hartford, CT 06105 (US).
`
`(74) Agent: GRUNE, Guerry, L.; 784 S. Villier Ct., Vlrginia
`Beach, VA 23452 (US).
`
`(81) Designated States (unless otherwise indicated, for every
`kind of national protection available): AE, AG, AL, AM,
`AT, AU, AZ, BA, BB, BG, BR, BW, BY, BZ, CA, CH, CN,
`CO, CR, CU, CZ, DE, DK, DM, DZ, EC, EE, EG, ES, FI,
`GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL, IN, IS,
`JP, KE, KG, KM, KN, KP, KR, KZ, LA, LC, LK, LR, LS,
`LT, LU, LV, LY, MA, MD, MG, MK, MN, MW, MX, MY,
`MZ, NA, NG, NI, NO, NZ, OM, PG, PH, PL, PT, RO, RS,
`RU, SC, SD, SE, SG, SK, SL, SM, SV, SY, TJ, TM, TN,
`TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
`
`(84) Designated States (unless otherwise indicated, for every
`kind of regional protection available): ARIPO (BW, GH,
`GM, KE, LS, MW, lVIZ, NA, SD, SL, SZ, TZ, UG, ZM,
`ZW), Eurasian (AlVI, AZ, BY, KG, KZ, MD, RU, TJ, TM),
`European (AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI,
`FR, GB, GR, HU, IE, IS, IT, LT, LU, LV, MC, NL, PL, PT,
`RO, SE, SI, SK, TR), OAPI (BF, B], CF, CG, CI, CM, GA,
`GN, GQ, GW, ML, MR, NE, SN, TD, TG).
`
`Published:
`
`with international search report
`before the expiration of the time limit for amending the
`claims and to be republished in the event of receipt of
`amendments
`
`For two—letter codes and other abbreviations, refer to the ”Guid—
`ance Notes on Codes and Abbreviations ” appearing at the begin—
`ning of each regular issue of the PCT Gazette.
`
`(54) Title: ALTERNATIVE FUEL AND FUEL ADDITIVE COMPOSITIONS
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`A1|||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
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`m (57) Abstract: Alternative gasoline, diesel fuel, marine diesel fuel, jet fuel, and flexible fuel compositions are disclosed. The
`compositions include an alcohol and/or a glycerol ether or mixture of glycerol ethers, which can be derived from renewable resources.
`
`H When combined with gasoline/ethanol blends, the glycerol ethers can reduce the vapor pressure of the ethanol and increaseing the
`\9 fuel economy. When added to diesel fuel/alcohol blends, glycerol ethers improve the cetane value of the blends. All or part of the
`C diesel fuel in the compositions described herein can be biodiesel fuel and/or synthetic fuel derived from aFischer—Tropsch synthesis
`1: process. Fischer—Tropsch synthesis can also use feedstocks derived from sources other than crude oil, such as methane, methanol,
`c ethanol, lignin and glycerol, which can further reduce reliance on foreign sources of crude oil. When used in jet fuel, glycerol
`9 ethers can replace all or part of conventional deicing additives, thus lowering skin toxicity, and glycerol ethers ability to reduce
`N particulate emissions can lower the appearance of contrails. When used in marine diesel, the reduction in particulate emissions can
`be environmentally significant In another embodiment, the alternative compositions comprise gasoline, ethanol, and n—butanol, and
`in one aspect, the ethanol and/or n—butanol can be derived from renewable resources. Fuel additive compositions, including glycerol
`g ethers and hydrocarbons and/0r alcohols, are also disclosed.
`
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`ALTERNATIVE FUEL AND FUEL ADDITIVE COMPOSITIONS
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`FIELD OF THE INVENTION
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`The present invention relates to alternative fuel and fuel additive compositions,
`
`including blends of alcohols such as methanol, ethanol and/or butanol, with fuels such as
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`gasoline, diesel, marine diesel, jet fuel, and/or biodiesel fuels.
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`BACKGROUND OF THE INVENTION .
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`Diesel fuel, jet fuel, and gasoline are petroleum products derived from crude oil.
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`Crude oil is, of course, a non-renewable resource of finite supply. Accordingly, extensive
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`research etfort is now being directed toward replacing some or all petroleum—based diesel
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`fuel with either a fuel derived from a renewable source such as farm cr0ps (biodiesel) or a
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`fiiel derived from Fischer-Tropsch synthesis (syntroleum). For example, research is being
`
`conducted on replacing gasoline and diesel fire] with gasoline/ethanol and diesel fuel/ethanol
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`blends;
`
`There are problems associated with gasoline/ethanol and diesel fuel/ethanol blends.
`
`With gasoline/ethanol blends, the relatively high vapor pressure of the ethanol can be
`problematic, particularly when starting a car in the wintertime. With diesel/ethanol blends,
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`the lower energy output of the ethanol (i.e., lower cetane value) makes the resulting fuel less
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`than optimal.
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`Unlike regular diesel fuel, marine diesel oil contains some heavy fuel oil, and
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`sometimes contains waste products such as used motor oil. While marine diesel engines are
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`reliable and fuel efficient, they also produce relatively high levels of particulate emissions, up
`
`to fifiy times more than gasoline engines. These emissions add to the visible pollution
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`attributable to shipping, and adversely affect air quality. The particulate emissions associated
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`with marine diesel are so significant that efforts are underway to find ways to minimize these
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`emissions. It would be advantageous to provide alternative marine diesel oil compositions
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`that provide less particulate emissions.
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`Jet fuel is a mixture of a variety of compounds, including hydrocarbons such as
`
`cycloparaffins, n-paraflins, isoparai‘fins, and aromatics, typically in the range of €5.20, such as
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`naphthalenes and alkylbenzenes, and, occasionally, oxygenates such as ethylene glycol
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`monobutyl ether and ethylene glycol monoethyl ether, which are used as icing inhibitors.
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`The range of hydrocarbons in jet fuel typically ranges fiom €5-15, although hydrocarbons
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`above C15 can also be used. Significant efforts have been undertaken to provide renewable
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`compositions that can replace all or part ofjet fuel.
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`It is known that LIP—8, atype ofjet fuel commonly used by the US. military, induces
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`dermal immunotoxicity. JP-S is produced from commercial Jet-A fuel by blending in an
`additive package containing diethylene glycol monomethyl ether, (DiEGME) as an anti—icing
`compound. It has been suggested that DiEGME is a dermal immunotoxin, and may be
`involved in JP-8-induced immune suppression. It would be advantageous to provide
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`alternative de—icing compositions, particularly those which are renewable and which are not
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`associated with immune suppression.
`
`Fuel additives are marketed directly to retail consumers, usually in single or dual-
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`use sized containers of approximately 12 fl oz for between $1.75 to $5 (a price equivalent to
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`$18.66 to $53 per gallon). They are advertised as improving fuel efficiency and increasing
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`gas mileage. They are sold at large—scale retail outlets such as Wal-Mart, gas station-affiliated
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`convenience stores, and elsewhere. One well-known example of such products is the STP ®
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`line, owned by Clorox Corp. Fuel additives produced by STP include “Gas Treatment”,
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`“Super Concentrated Gas Treatment”, “Complete Fuel System Cleaner”, “Super
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`Concentrated Fuel Injection Cleaner”, “Fuel Injector and Carburetor”, “Octane Performance
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`Booster”, “All Season Water Remover”, “Diesel Fuel Treatment & Injector Cleaner”, and
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`“Lead Substitute”. Other well-known lines of fuel additive products include Prestone,
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`Marvel Mystery Oil, and Valvoline (Pyroil). Such products are marketed to help restore lost
`
`fuel efficiency, keep fuel intake systems clean, and restore lost horsepower.
`
`These products contain primarily petroleum-based components. For example, STP’s
`
`Octane Performance Booster contains, in addition to a trade-secret additive, naphthalene;
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`1,2,4-Trimethylbenzene; Mesitylene; Xylene; Petroleum Distillates (JPS jet fuel); Stoddard
`
`Solvent; Kerosene, petroleum, hydrodesulfurized; Solvent Naptha, petroleum, medium
`
`aliphatic; and, Solvent Naphtha, petroleum, light aromatic.
`
`These products tend to function by improving engine performance, rather than by
`
`improving the effectiveness ofthe fuel itself. For example, STP’s “Super Concentrated Gas
`Treatment” dissolves deposits that may accumulate in the fuel system (including fuel
`
`injectors, intake valves, and carburetor). All engines develop combustion chamber deposits
`that can lead to the engine needing higher-octane gasoline than recommended by the
`
`manufacturer to operate efficiently. STP’s “Octane Performance Booster” helps remove
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`combustion chamber deposits to reduce an engine’s appetite for higher-octane gasoline,
`reducing knocking and‘pinging, andreston‘ng lost performance.
`
`In some cases, these retail additives are intended for consumers affected by changes in
`
`the national gasoline market. For example, lead began to be phased out of gasoline sold in the
`‘ U.S. beginning in the 1970’s. A product such as STP’s “Lead Substitute” can be mixed with
`
`unleaded gasoline to allow such gasoline’s use in older cars that would otherwise have
`
`required leaded gasoline. Such products allow older cars to operate properly in an
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`environment where the optimal fuel is not readily available.
`
`According to the Federal Trade Commission (http://www.i’tcgov/bcp/conline/
`
`pubs/autos/gasave.htm), “no government agency endorses gas-saving products for cars. The
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`most that can be claimed in advertising is that the EPA has reached certain conclusions about
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`possible gas savings by testing the product or by evaluating the manufacturer's own test
`data”
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`It would be advantageous to provide alternative fuels and fuel additive compositions,
`
`for use in gasoline, diesel, marine diesel, and jet engines. It would further be advantageous to
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`provide alternative fuels which overcome the limitations of current gasoline/ethanol and
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`diesel/ethanol blends. The present invention provides such alternative fuel and firel additive
`
`compositions, and methods for producing same.
`
`SUMMARY OF THE INVENTION
`
`Alternative fuel compositions and methods for their preparation and use are
`
`disclosed. The alternative fuel compositions include one or more conventional fuels, in
`
`combination with one or more renewable components.
`
`In one embodiment, the renewable component is a glycerol ether or blend of
`
`glycerol ethers. The glycerol ethers include one, two, or three €1-19 alkyl groups, preferably
`
`one or two C3.5 groups, more preferably one or two t—butyl groups. When present in
`
`alternative fuel compositions, the glycerol ethers are typically present in an amount of
`
`between about 0.5 and 15 percent by volume, in one aspect, between about 1 and about 10
`
`percent by volume, in another aspect, between about 2 and about 8 percent by volume, and in
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`another aspect, around 5 percent by volume.
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`Gasoline/ethanol blends suffer from relatively low energy content per unit volume.
`
`For example, E85, a mixture of about 85% ethanol and about 15% gasoline by volume tends
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`to provide roughly 20% fewer miles per gallon than gasoline. Blends ofglycerol ethers with
`gasoline/ethanol blends can improve their gasoline mileage. The glycerol ethers are present
`in a range of between about 1 to about 15% by volume, preferably between about 2 and about
`12 percent by volume, more preferably, between about 4 and about 8 percent by volume. The
`gasoline/ethanol blends can include between about 5 and about 85% ethanol by volume, in
`one embodiment, between about 15 and about 85% by volume (i.e., E85).
`In one aspect, the fuel is E85, in a second aspect, the fuel is E10. In a third aspect,
`the amount of alcohol is between about 1 and 20 percent by volume, and more ideally, about
`10 to 20 percent by volume of the fuel composition, with gasoline being present in about 75
`to about 85 percent by volume ofthe fuel composition In a fourth aspect, the amount of
`alcohol is between about 75 and 85 percent by volume ofthe fiiel composition. In any of
`these aspects, although any amount ofglycerol ethers can be present, the composition
`typically comprises between about I to about 15 percent glycerol ethers, by volume, based on
`the total volume of the fuel composition plus glycerol ethers.
`
`In another aspect, the fuel includes only gasoline (i.e., gasoline itself is combined
`with glycerol ethers, but no alcohol is present). In this embodiment, the glycerol ethers are
`present in a fuel additive, alone or in combination with various conventional fuel additives,
`such as hydrocarbons. Fatty acids can also be present, as can fatty acid alkyl esters.
`Glycerol ethers can be also combined with ethanol and/or butanol to form an
`alternative fuel composition, with or without the addition ofgasoline. The high oxygenate
`concentration results in a clean burning fuel or fuel additive.
`
`Diesel fuel is combined with up to 10% ethanol, but this composition has less
`
`energy per unit volume than diesel fiiel. A further embodiment of the present invention is a
`fuel composition including diesel fuel including between about 5 and about 15% by volume
`ethanol and between about 1 and about 15% glycerol ether(s)_ The diesel fuel can be
`
`conventional diesel fuel, or can include any amount of biodiesel fuel (i.e., alkyl esters offatty
`acids) or syntroleum (hydrocarbons in the diesel fuel range derived from Fischer—Tropsch
`synthesis).
`In one aspect, the diesel fuel/alcohol blends including between about 75 and 95%
`diesel/5 and 25% alcohol, ideally, about 90% diesel and about 10% alcohol, are combined
`with glycerol ethers, for example, in a range of between about 1 and about 10% by volume,
`ideally from about 2 to about 8 percent by volume, and more ideally, around 5 percent by
`volume.
`
`A further embodiment ofthe present invention relates to blends of glycerol ethers
`and marine diesel. These blends can significantly reduce the particulate emissions of marine
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`diesel fuel, relative to marine diesel alone. The glycerol ether is present in a range of from
`about 1 to about 15% by volume, preferably between about 2 and about 10 % by volume,
`more preferably, between about 4 and about 8 % by volume.
`Still a further embodiment relates to jet fuel incorporating glycerol ethers as deicing
`additives. Glycerol ethers can improve the safety of the jet fuel compositions, relative to
`
`compositions including diethylene glycol monomethyl ether, which is known to cause dermal
`
`immunotoxicity. The glycerol others can be incorporated in substantially the same
`
`percentages as the conventional deicing additives, which typically range from about 0.1 to
`
`about 4 percent by volume. As an added benefit, the addition of glycerol ethers can reduce
`
`the particulate emissions, which can lower the appearance of contrails, thus providing an
`environmental benefit. In one embodiment, butanol, in place ofor in addition to glycerol
`others, is used as an oxygenate additive injet fuel. In another embodiment, the alternative jet
`fuel composition includes those hydrocarbons typically found in JP-8, but glycerol others are
`present in addition to or in lieu of ethylene glycol ethers.
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`The alternative fuel can also be a gasoline/alcohol blend, where the alcohol includes
`
`a combination of a) methanol and/or ethanol and b) n-butanol, sec—butanol, or t-butanol,
`where the alcohols are present in amounts up to about 90 percent by volume of the
`
`gasoline/alcohol blend. In one aspect of this embodiment, gasoline is blended with between
`about 5 and about 85 percent by volume 'of ethanol, between about 5 and about 85 percent by
`volume of butanol (n-butanol, sec-butanol, and/or t-butanol), and between about 5 and 85
`
`percent by volume of gasoline. Butanol provides roughly the same energy content per unit
`volume as gasoline, whereas ethanol provides relatively lower energy content than gasoline.
`Ethanol and butanol can both be formed by fermenting sugars such as glucose and xylose,
`which can be formed by depolymerizing cellulose and hemicellulose, respectively. Glucose
`is relatively easy to ferment to ethanol using yeasts, and xylose is relatively easy to ferment
`to butanol using certain bacteria, such as Clostridium acetobutylicum. However, it is
`relatively inefficient to ferment xylose to ethanol, due to the formation ofxylose as a major
`by—product. Since these two sugars (glucose and xylose) are more easily fermented by
`different biological agents to form different products (i.e., ethanol and butanol), combinations
`of both ethanol and butanol in gasoline will take advantage of the entire cellulosic sugar
`composition, and provide the fuel with better properties than either alcohol alone. That is,
`ethanol has relatively low energy content per unit volume, and butanol can increase the
`
`relative energy content ofthe alternative fuel. Butanol has a strong odor, which can be
`mitigated by using both ethanol and gasoline to dilute the odor.
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`The glycerol ethers can have from one to three ofthe hydroxyl group on glycerol
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`etherified with a CHo alkyl group, and can exist as purified compounds, or as mixtures Of a
`
`variety of glycerol ethers. It is preferred that at least a portion of the glycerol ethers include
`
`one or two hydroxyl groups, so that the product has the ability to hydrogen bond with
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`ethanol, and thus help lower the vapor pressure of the ethanol.
`
`The glycerol ethers lower the vapor pressure of the ethanol in gasoline/ethanol
`
`blends, thus improving their performance. The glycerol ethers also increase the cetane value
`
`of diesel/ethanol blends, which improves their performance as well.
`
`The glycerol ethers, when combined with conventional diesel file], biodiesel fuel, or
`
`conventional gasoline products, provide advantageous properties similar to those provided by
`
`methyl t-butyl ether (MTBE). The glyceryl ethers lower the viscosity of the fuel, and
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`hydroxy groups on partially etherified glycerol may help to incorporate a small amount of
`
`water into the fuel, which can lower NOx emissions.
`
`The glycerol ethers can be prepared by reacting an olefin or alcohol with glycerol,
`
`using an acid catalyst. The acid catalyst can be a proton source, such as hydrochloric acid,
`
`sulfuric acid, and hydrobrornic acid, or can be a Lewis acid, for example, aluminum chloride,
`
`ferrous chloride, and zeolites.
`
`The olefins are typically (32.6 olefins, ideally C34 olefins, and preferably, are either
`
`isobutylene or propylene. The mole ratio of olefin to glycerol ranges between 1/1 and 3/1,
`
`but is ideally in the range of about 2/1.. That is, it is believed that di-ethers are preferable to
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`mono-ethers and tri-ethers, although mixtures of mono-, di- and/or tri-ethers are within the
`
`scope of the invention
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`The olefins can be derived, in whole or in part, by Fischer-Tropsch synthesis on
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`syngas formed using, for example, coal, glycerol, ethanol, methanol, methane, or lignin as a
`starting material. The etherification, when performed using an olefin, can be run at room
`
`temperature, to avoid excessive polymerization ofthe olefin, although higher temperatures
`may be required when flie olefins are not highly substituted (i.e., will not generate a
`
`secondary or tertiary carbocation as a reactive intermediate). Use of ferrous chloride can be
`
`preferred, since this catalyst is known to minimize the polymerization of olefins. If the
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`etherification and esterification are run at temperatures in excess of 70°C, a some amount of
`
`olefin dimerization, trimerization, and polymerization might be observed.
`
`The resulting alternative fuel is derived, at least in part, from renewable resources,
`
`in that the glycerol and/or other components such as alcohols, can be derived from renewable
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`resources. In those embodiments where the fuel comprises diesel fuel, the presence of
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`biodiesel and/or syntroleumtwhich can be blended in any desired ratio), in the fuel can help
`reduce U.S. dependence on foreign crude oil.
`
`Fuel additive compositions, for use in gasoline, diesel, marine diesel, jet, and
`flexible fuel engines, and methods for their preparation and use, are also disclosed. The
`diesel fuel can be conventional diesel fuel, or can include any amount ofbiodiesel fuel (i.e., '
`alkyl esters of fatty acids) or syntroleum (hydrocarbons in the diesel firel range derived fiom
`Fischer-Tropsch synthesis).
`
`The additives include glycerol ethers, in an amount up to about 100 percent by
`volume, and hydrocarbons such as kerosene and/or jet fiiel, in an amount up to about 95
`percent by volume. Ideally, the amount of glycerol ethers and hydrocarbons is, individually,
`between about 1 and 90 percent by volume, and more ideally, about 15 to 80 percent by
`volume.
`»
`,
`The glycerol ethers, when combined with conventional diesel fuel, biodiesel fuel,
`marine diesel fuel, gasoline, gasolindalcohol blends, or jet fire], provide advantageous
`
`properties similar to those provided by methyl t-butyl ether (MTBE). MTBE was an
`
`attractive additive from an emissions perspective because it has no sulfur, aromatics, or
`olefins, which contribute to air emissions. In addition, MTBE had some important indirect
`
`benefits. When MTBE was added, it diluted those chemical properties in the blend that
`
`increase air emissions, reducing their average concentration. Furthermore, MTBE’s
`
`distillation profile and vapor pressure required little if any adjustment to the base gasoline to
`which it was added. MTBE’s high octane allowed refiners to reduce the severity at which
`they ran their reformers, which in turn reduced the aromatic content of the reformulated
`
`gasoline. Glycerol ethers will accomplish the same. The glycerol ethers lower the viscosity of
`the fuel, and hydroxy groups on partially etherified glycerol may help to incorporate a small
`amount of water into the fuel, which can lower NOx emissions.
`
`DETAILED DESCRIPTION OF THE INVENTION
`
`Fuels such as marine diesel orjet fuel, or fuel blends such as gasoline/ethanol or
`
`diesel/ethanol fuel compositions, that also include glycerol ethers or butanol, as well as
`
`methods for preparing the fuel compositions, are disclosed. Depending on the nature ofthe
`
`starting fuel or fuel blend, the resulting fuel compositions can be used to fuel gasoline, jet,
`diesel, and/or marine diesel fuel engines to provide an alternative to similar fuels produced
`entirely from crude oil.
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`As used herein, the term “renewable components” refers to components that can be,
`but need not be, produced from renewable resources. That is, while ethanol and butanol can
`be produced by fermentation, they can also be produced from petrochemical sources. Some ‘
`renewable components are produced by reacting a renewable material, such as glycerol, with
`a petrochemical component, such as isobutylene.
`
`In some embodiments, the processes described herein are integrated processes. As ,
`used herein, the term "integrated process" refers to a process which involves a sequence of
`steps, some of which may be parallel to other steps in the process, but which are interrelated
`
`or somehow dependent upon either earlier or later steps in the total process.
`
`The following definitions will further define the invention:
`
`The term "alkyl", as used herein, unless otherwise specified, refers to a
`
`saturated straight, branched, or cyclic hydrocarbon of (31.5, and specifically includes
`methyl,
`ethyl, propyl,
`isopropyl, butyl,
`isobutyl,
`t-butyl, pentyl, cyclopentyl,
`isopentyl, neopentyl, hexyl, isohexyl, cyclohexyl, 3—methylpentyl, 2,2-dimethylbutyl, .
`and 2,3-dimethylbutyl.
`
`The term "olefin" refers to an unsaturated straight, branched or cyclic
`hydrocarbon of €2.10,
`and specifically includes ethylene, propylene, butylene,
`isobutylene,
`pentene,
`cyclopentene,
`isopentene,
`hexane,
`cyclohexene,
`3—
`methylpentene, 2,2-dimethylbutene, 2,3-dimethylbutene,
`l-heptene, 2-heptene, 3-
`heptene, 1-octene, 2-octene, 3-octene, 4-octene,
`l-nonene, 2-nonene, 3-nonene, 4-
`
`nonene, 1-decene, 2-decene, 3-decene, 4-decene, and 5-decene. Ethylene, propylene
`and isobutylene can be preferred due to their relatively low cost, and C24; olefms can
`
`be preferred as they are produced as the major products in Fischer-Tropsch synthesis ,
`when an iron catalyst is used.
`
`Highly substituted olefins are preferred because they can stabilize a
`
`carbocation intermediate more readily than unsubstituted olefins.
`
`1. Fuel Compositions
`
`A variety offuel compositions include hydrocarbons in the (25.20 range, including
`diesel, gasoline, and jet fuel. Marine diesel also falls largely in this range, but often includes
`used motor oil and other components that may include hydrocarbons outside this range. Most
`hydrocarbons used for fiiel, be it gasoline, diesel, jet, or marine diesel, have boiling points in
`the range of between about 68 450° F. Specifications for the most commonly used diesel
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`fuel (No. 2) are disclosed in ASTM D 975. The minimum flash point for diesel fuel is 52° C
`
`(125° F).
`
`'
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`A. Jet Fuel
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`Jet fuels are well known to those of skill in the alt. Specifications for jet fiiel are
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`disclosed in ASTM D 1655, standard Specification for Aviation Turbine Fuels. The minimum
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`flash point for jet fuel is typically 38° C. Among the various well known formulations for jet
`fuel are civil and military jet fuels.
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`mm
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`There are currently two grades of turbine fuel used in civil commercial aviation.
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`These include Jet A-1 and Jet A, both of which are kerosene-type fuels. Jet Bis another jet
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`fuel, which is a wide cut kerosene (a blend of gasoline and kerosene). Jet B is rarely used,
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`except in very cold climates.
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`Jet A-l
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`Jet A~l is a kerosene grade of fuel, and can be used for most turbine engine aircraft.
`There is a stringent internationally agreed standard for Jet A-l, which is well known to those
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`of skill in the art. Jet A—l has a flash point above 38°C (100°F) and a freeze point maximum
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`of -47°C. Among the standards for Jet A-l are British specification DEF STAN 91—91 (Jet
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`A-l), (formerly DERD 2494 (AVTUR)), ASTM specification D1655 (Jet A—1) and IATA
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`Guidance Material (Kerosene Type), and NATO Code F-35 .
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`Jet A
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`Jet A is a similar kerosene type of fuel, but is normally only available in the USA.
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`It has the same flash point as Jet A—l, but a higher freeze point maximum (40°C). Jet A is
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`well known to those of skill in the art, and falls under the ASTM D1655 (Jet A) specification.
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`Jet B
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`Jet B is a distillate covering the naphtha and kerosene fractions. It tends to be more
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`highly flammable than Jet A—1, and is typically used in very cold climates where its better
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`cold weather performance is important. Jet B is also well known to those of skill in the art,
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`and falls under Canadian Specification CAN/CGSB 3.23.
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`Milim Jet Fuels
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`JP—4
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`JP-4 is similar to Jet B, but adds corrosion inhibitors and anti-icing additives. JP-4
`is well known to those of skill in the art, and falls under US. Military Specification MIL-
`PRF-5624S Grade JP-4, British Specification DEF STAN 91-88 AVTAG/FSII (formerly
`DERD 2454),where F811 stands for Fuel Systems Icing Inhibitor, and NATO Code F40.
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`JPeS
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`JP-S is a high flash point kerosene, and falls under US. Military Specification MIL-
`PRF-5624S Grade JP-5, British Specification DEF STAN 91-86 AVCAT/FSII (formerly
`DERD 2452), and NATO Code F-44.
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`JP-S
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`SIP-8 is similar to Jet A-l, but adds corrosion inhibitors and anti—icing additives. It is
`a Widely used and well known jet fuel, falling under US. Military Specification MIL-T—
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`83188D, British Specification DEF STAN 91-87 AVTUR/FSII (formerly DERD 2453), and
`NATO Code F-34.
`'
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`Aviation Fuel Additives
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`Aviation fuel additives are typically added to jet fuel in very small quantities, oflen
`measurable only in parts per million. These additives provide special or improved qualities
`to the jet fiiel. The desired amount of these additives is well known to those of skill in the art,
`and often controlled by appropriate specifications. A few of the more common additives are
`discussed below:
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`Anti-knock additives such as tetra-ethyl lead (TEL) reduce the tendency of gasoline
`to detonate.
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`Anti~oxidants prevent the formation of gum deposits on fuel system components
`caused by oxidation of the fuel in storage and also inhibit the formation ofperoxide
`compounds in certain jet fuels.
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`Static dissipator additives reduce the hazardous efi‘ects of static electricity generated
`by movement of fuel through modern high flow—rate fuel transfer systems.
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`Corrosion inhibitors protect ferrous metals in fuel handling systems, such as
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`pipelines and fuel storage tanks, from corrosion, and may improve the lubricity of certain jet
`fuels.
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`Anti-icing additives reduce the freezing point of water precipitated fi'om jet fuels
`due to cooling at high altitudes. These additives can prevent ice crystal formation, which
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`would otherwise restrict the flow of fuel to the engine, but do not affect the freezing point of
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`the fuel itself. Anti-icing additives can also provide some antimicrobial effects to the jet fuel
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`3
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`although other biocides can be added. Diethylene glycol mono—alkyl ethers are often used,
`but are known to cause skin toxicity and other dermatological problems. Replacement of
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`some or all of these anti-icing additives with glycerol ethers can reduce the dermal toxicity.
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`Further, as glycerol ethers can lower the particulate emissions of fuels, they can reduce the
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`presence of contrails when added to jet fuel.
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`Metal de-activators suppress the catalytic efl‘ect which some metals, particularly
`copper, have on fuel oxidation.
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`Thermal Stability Irnprover additives are sometimes added to JP-8 to produce JP~
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`8+100. These additives inhibit deposit formation in high temperature areas of the aircraft
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`fiiel system.
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`In one embodiment, the alternative jet fuel composition includes those
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`hydrocarbons typically found in JP-S, but glycerol ethers are present in addition to or in lieu
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`of ethylene glycol ethers or other such conventional deicing additives.
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`In addition to petroleum-based fuels, fuels derived from other sources can also be
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`used. Examples include biodiesel and syntroleum (fuels derived from the Fischer-Tropsch
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`synthesis using syngas).
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`&._Bio_dies_el
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`The alternative fuel compositions described herein can include bicdiesel. Biodiesel
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`is a fatty acid alkyl ester, where the ester is not 3 glycerol ester, but rather, an ester formed
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`with a monohydroxy alcohol. Examples of alcohols used to prepare biodiesel fuel include
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`methanol, ethanol, and mixtures thereof, although virtually any C1-10 alcohol can be used.
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`The biodiesel is typically formed by transesterification of a triglyceride with an alcohol,
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`although it can also be formed by esterification of a free fatty acid.
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`Any source of triglycerides can be used to prepare the biodiesel fuel that provides
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`the fuel with acceptable properties (that is, which functions as a diesel fuel). Preferred
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`sources of triglycerides for use inpracticing the present invention include, but are not limited
`to, vegetable oils and fats, as well as animal oils and fats. Examples of suitable vegetable oils
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`include, but are not limited to, crude or refined soybean, corn, coconut (including copra),
`palm, rapeseed, cotton and oils. Examples of suitable animal fats include, but are not limited
`to, fallow, lard, butter, bacon grease and yellow grease. Naturally-occurring fats and oils are
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`the preferred source of triglycerides because oftheir abundance and renewability. Oils with a
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`higher boiling point ar