Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
  • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
  • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
  • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/12—Inorganic compounds
  • C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
  • C10L1/125—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof water
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
  • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

• Diesel engines continue to find wide use in trucks, ships, trains, and the like. Commercially acceptable diesel fuel must be capable of performing over a range of climatic conditions and, accordingly, must be able to be used at temperatures down to 0 0 C and preferably as low as at least -10 0 C.
• Diesel engine exhaust often includes particulates, CO, and various nitrogen oxide (NO x ) species.
• lower alcohols such as methanol and ethanol.
• a blend of 15% (by vol.) ethanol and 85% (by vol.) diesel oil has been found to improve the combustion byproducts emitted in the engine exhaust (generally believed to be due to the increased oxygen content of the fuel) without requiring modifications to existing diesel engines; in recent years, the amount of ethanol has been increased at times to 20% (by vol.).
• lower alcohols typically are immiscible with diesel oil and tend to separate over time, so the components often are stored separately and mixed just prior to use.
• E-diesel Fuel blends of the type just described often are referred to as "E-diesel” (or some similar variant).
• E-diesel typically generate fewer objectionable combustion byproducts than neat diesel oil, it produces less energy when combusted and still employs petroleum-derived diesel oil for at least 80% of its volume.
• Sustainability and sourcing concerns regarding fossil fuels have grown significantly over the past decade. In turn, this has increased interest in fuels prepared from sources other than petroleum has grown significantly over the past decade or so.
• bio fuels which are the transesterifi- cation products of any of a variety of animal fats and vegetable oils.
• the major components of oils and fats are fatty acid triglycerides, molecules in which three long chain fatty acids are ester linked to a glycerol radical.
• an alcohol typically methanol
• the fatty acids can cleave from the glycerol radical and react with the alcohol to form fatty acid esters.
• the transesterif ⁇ cation reaction significantly reduces the viscosity of the oil.
• Biofuels can be used neat but, more commonly, small proportions are blended into petroleum-derived diesel (hereinafter "petrodiesel”). Blends of biofuel and petrodiesel often are referred to as B-diesel or, more commonly, with a number following the B to indicate the percentage of petrodiesel replaced with biodiesel (e.g., B20 diesel indicating of blend of 80% petrodiesel and 20% biodiesel).
• B-diesel e.g., B20 diesel indicating of blend of 80% petrodiesel and 20% biodiesel.
• a fuel composition that includes ethanol and a C 2 -C 6 ester of one or more long chain fatty acids.
• the composition generally includes at least about 2.5% (by vol.), typically from about 5 to about 10% (by vol.), of a lower alkyl monool such as ethanol and a complementary amount of long chain fatty acid ester(s); all other components typically are present in no more than trace amounts.
• at least 99.99% (by wt.) or even 99.999% (by wt.) of the composition can constitute just C, H and O atoms; in these and other embodiments, the composition can be essentially free of at least one of, and preferably both of, sulfur and nitrogen atoms.
• the composition typically includes at least about 0.2% (by vol.), commonly at least about 0.25% (by vol.), and occasionally at least about 0.3% (by vol.) water.
• the fuel composition can include at least about 0.5% (by vol.) water. Water in a fuel composition typically is considered something to be avoided if at all possible, yet the presence of up to about 1% (by vol.) has not proven to be particularly deleterious to the efficacy of the present fuel composition.
• the fuel composition can have an acidic pH, at times as low as, e.g., 4.5, but more commonly from about 6.0 to about 6.8.
• the composition typically has a kinematic viscosity of from about 3.5 to about 4.0 IM 2 Zs (i.e., cSt), commonly about 3.7 ⁇ 0.2 mm 2 /s. Even in the absence of flow improving additives, the composition can have a cloud point of at least as low as about -5°C and a pour point of at least as low as about -15°C.
• a method for synthesizing and refining a fuel composition includes providing a liquid that contains at least one C 2 -C 6 ester of one or more long chain fatty acids and adjusting the pH of the liquid to less than 7.0.
• the C 2 -C 6 ester(s) can be provided by transesterification of a triglyceride-containing composition using a C 2 -C 6 monool and, in such cases, the pH adjustment results in separation of a salt and glycerine- related byproducts (e.g., glycerol) from the liquid phase, thereby resulting in a raw fuel composition.
• the raw fuel composition then is treated so as to remove particulates having an average diameter greater than ⁇ 1 ⁇ m and to ensure that the concentration of Group I metal ions is less than about 50 parts per million (ppm), preferably even 5-10 times lower than this number.
• the transesterification process typically is performed in the presence of a stoichiometric excess of one or more C 2 -C 6 alcohols.
• the alcohol(s) typically are present in from -25 to -200% excess (by vol.), preferably from -50 to -150% excess, more preferably from -70 to -130% excess, and most preferably from -80 to -120% excess.
• the pH adjustments is accomplished by adding a strong acid to the liquid.
• the acid is halogenated (e.g., HCl)
• the salt removed from the liquid is KX where X is a halogen atom (e.g., Cl).
• the raw fuel treatment can be accomplished by passing the raw fuel composition through a series of filters, optionally of progressively smaller pore sizes.
• the process can provide a fuel composition that has a kinematic viscosity of from about 3.5 to about 4.0 mm 2 /s, most commonly of no more than about 3.8 mm 2 /s.
• the process also can provide a fuel composition that remains fluid even in the absence of flow improving additives. Specifically, the composition can have a cloud point at least as low as -5°C and a pour point at least as low as -15°C.
• the cetane number of a refined fuel composition typically is greater than about 45 and can be significantly (e.g., 5-15%) higher.
• all steps of this process can be performed without utilizing external sources of heat, i.e., at or near ambient temperatures. Additionally, the process can be performed without the addition of significant amounts of water, thereby eliminating the need to collect and treat (typically very caustic) waste water.
• a method of powering a vehicle involves introducing a fuel that includes the aforesaid fuel composition into a diesel engine and allowing the engine to combust the fuel.
• the aforesaid fuel composition can result in simultaneous reductions in opacity, CO, SO 2 , and NO x in the exhaust compared to the exhaust of the same engine combusting petrodiesel. Simultaneously, the amount of O 2 in the same exhaust increases relative to that seen when petrodiesel is combusted.
• the aforesaid composition also greatly reduces the amount of and, in some instances, removes carbonaceous deposits (often referred to as "coking") on metal parts of the engine.
• carbonaceous deposits often referred to as "coking”
• the other characteristics might be more evident in a two-cycle diesel engine than in a four-stroke diesel engine.
• the synthesis portion of the process involves a transesterification reaction.
• certain aspects of the reaction differ from that which has become conventional in the manufacture of bio fuels.
• any triglyceride can be transesterified with an alcohol.
• some are using the filtered waste oil from fast food restaurants as a low-cost reactant.
• the present process gives preference to highly pure vegetable oils, more preferably to food-grade materials, examples of which include corn, linseed, peanut and soybean oils.
• Table Ia Weight percentages of fatty acids in fats and oils
• Table Ib Weight percentages of fatty acids in fats and oils
• a preferred starting material is a food-grade vegetable oil selected from the foregoing list. Particularly preferred are those that are refined, bleached, and deodorized (RBD); such materials are available from a variety of commercial sources including, for example, ConAgra, Bunge Ltd., ADM and the like. The remainder of this description is based on an RBD soybean oil although, in view of the advantages found with this material and its composition relative to that of other oils, the ordinarily skilled artisan should be able to identify other sources of long chain fatty acids that can provide similar advantages and/or advantages in different end-use conditions.
• RBD refined, bleached, and deodorized
• the fatty acid source(s) can be provided in or to a reaction vessel. While the art teaches that most any type of vessel can be used, preparation of a high quality biodiesel-type fuel composition is facilitated by use of a vessel made from a clean, essentially non-reactive material. Preference here is given to materials such as steel, stainless steel, glass-lined metals, and the like.
• the other reagent in transesterif ⁇ cation reactions is an alcohol.
• the vast majority of biofuels being made employ methanol as a reagent. In fact, the European Biodiesel Board mandates the use of methanol where a producer wishes to have its product certified as a biodiesel fuel; see, e.g., EN14214.
• Each alcohol employed preferably is aliphatic, and more preferably has the general formula C n H 2n+ i0H where 2 ⁇ n ⁇ 6. As indicated by the formula, the use of monools is preferred so as to avoid the formation of longer chain diesters.
• Preferred alcohols include ethanol, 1- propanol, 2-propanol, and 1-butanol, with absolute ethanol (denatured by means of, e.g., gasoline) being particularly preferred.
• the alcohol preferably is free of heteroatoms that can be involved in the formation of undesirable species; non- limiting examples of such heteroatoms include N, S, and P.
• the catalyst can be delivered in some or all of the alcohol(s). This can be done by dissolving a strong base, e.g., KOH, in the alcohol(s) prior to delivery of the alcohol(s) to the reaction vessel. Conveniently, this can be done in a relatively short amount of time (less than an hour) through simple mixing at ambient or slightly elevated temperatures. If desired, the catalyst solution can be added stepwise, i.e., through the addition of sequential aliquots followed by mixing or agitation.
• a strong base e.g., KOH
• An excess of alcohol preferably is introduced to the reaction vessel.
• the fuel composition contains both C 2 -C 6 esters of long chain fatty acid(s) and C 2 -C 6 alcohol(s).
• certain processing and performance advantages might be obtained by introducing the alcohol components) during the transesterification step.
• a significant excess of alcohol can be added to the reaction vessel; the amount typically ranges from -25 to -200%, preferably from -50 to -150%, more preferably from ⁇ 70 to -130%, even more preferably from -80 to -120%, and most preferably at least -100% excess (all by volume).
• the stoichiometric excess of alcohol can be varied somewhat so as to create fuel compositions with slightly different properties. In this manner, one can create seasonal blends of fuel. For example, during cold weather seasons, the excess of alcohol can be increased so as to provide a fuel composition having a lower viscosity than a similar composition intended for summertime use.
• the second product of the transesterif ⁇ cation reaction is glycerol and other glycerine byproducts.
• the glycerol in the reaction vessel can separate on its own, can partially separate, or separate only minimally.
• glycerol (and derivatives) typically separates from the alkyl ester/ethanol phase in a few hours (e.g., 4-12 hours) after agitation is ceased.
• addition of more alcohol e.g., up to -20% additional alcohol
• additional time can be needed to achieve the desired level of separation.
• the alcohol added for separation purposes need not be the same as that used in the reaction and, in fact, methanol can be used for this purpose, if desired.
• the glycerol phase is heavier than the alkyl ester/ alcohol phase and thus separates to the bottom of the reaction vessel. Where the reaction vessel includes an egress at or near its bottom, the glycerol layer can be drained from the reaction vessel. Typically, the glycerol phase constitutes from -10-20% of the triglyceride reactant. Based on the excess amount of alcohol used during the transesterif ⁇ cation reaction, the glycerol layer is presumed to contain a not insignificant amount of alcohol. Processing and/or disposal techniques for glycerol are known.
• the material used as the basic catalyst contains a Group I or II metal atom (e.g., KOH or Ca(OH) 2 )
• the majority of the Group I or II metal ions partition into the glycerol phase. Removing the glycerol phase thereby conveniently removes the majority of Group I or II metal ions present in the reaction vessel.
• the remaining alkyl ester/ alcohol phase typically contains on the order of 500 to 1000 ppm of such ions, more commonly on the order of 600 to 800 ppm.
• the alkyl ester/ alcohol blend can be further treated in the reaction vessel or, more commonly, transferred to one or more additional vessels for further refining. At this point, the blend typically has a kinematic viscosity of -6.2 to -6.8 mm 2 /s.
• the raw fuel which, assuming stoichiometric amounts of triglyceride and methanol, will be extremely caustic
• NPB National Biodiesel Board
• the raw fuel composition can be passed by or through a cationic exchange resin which replaces Group I or II metal ions with H atoms.
• a cationic exchange resin which replaces Group I or II metal ions with H atoms.
• Such resins are widely known and available from a variety of commercial sources including, e.g., Rohm and Haas Co. (Philadelphia, Pennsylvania).
• a strong acid can be used to neutralize the alkyl ester/alcohol blend.
• Halogen-containing strong acids e.g., concentrated HCl
• other strong acids that contain the types of heteroatoms mentioned previously, e.g., H 2 SO 4 , HNO3, etc.
• each liter of concentrated HCl can treat over 500 L of raw fuel composition.
• Such refining techniques result in removal of Group I or II metal ions.
• the ions are removed as salt along with a very significant portion of any glycerol-type byproduct that did not phase separate previously. The latter is evidenced by a fairly significant reduction in kinematic viscosity.
• a raw fuel composition typically has a kinematic viscosity at 40 0 C of ⁇ 6.5 mm 2 /s; conversely, the same composition having undergone the type of acidulation refining just described typically has a kinematic viscosity at 40 0 C of from ⁇ 4.0 to ⁇ 5.5 mm 2 /s.
• the various ethyl ester biofuels had kinematic viscosities of from 4.5 mm 2 /s (soybean oil) to 6.2 mm 2 /s (rapeseed oil).
• the processed fuel composition i.e., purified alkyl ester/ alcohol blend
• the alkyl ester/alcohol blend can register a pH of as low as 4.0 to 4.5, typically between about 4.5 and about 6.9; more commonly, the pH of the blend will be in one or more of the following ranges: about 5.0 to about 6.8, about 5.5 to about 6.75, about 5.75 to about 6.7, about 5.9 to about 6.7, about 6.0 to about 6.75, about 6.0 to about 6.7, about 6.1 to about 6.6, about 6.1 to about 6.7, and about 6.4 ⁇ 0.2.
• the fuel composition includes primarily alkyl esters of long chain fatty acids and alcohol; most other materials are present in essentially just trace amounts.
• the fuel composition generally includes from about 0.2 to about 0.9% (by vol.), commonly from about 0.25 to about 0.75% (by vol.), and at times from about 0.3 to about 0.6% (by vol.) water.
• This amount of entrained or dispersed water is not significantly reduced even when the fuel composition is filtered, as discussed in more detail below; nevertheless, the presence of such water has not been found to have significant deleterious effects on combustion of the fuel composition and might even provide certain benefits (e.g., reduced combustion temperatures).
• the amount of Group I or II metal ions typically is reduced to no more than about 50 ppm, preferably no more than about 25 ppm, more preferably no more than about 10 ppm, even more preferably no more than about 5 ppm, and most preferably no more than about 4 ppm.
• the fuel composition can include up to about 50% (by vol.) alcohol relative to the overall volume.
• the fuel composition generally can include from about 2 to about 40% (by vol.) alcohol, although from about 3 to about 30% (by vol.) is more common and from about 4 to about 20% (by vol.) is most common.
• a refined fuel composition made according to this process typically includes from -5 to -15% (by vol.), commonly from -5.5 to -10% (by vol.), and most commonly from ⁇ 6 to -8% (by vol.) alcohol; preferably one or more C 2 -C 4 monools such as ethanol and/or 1-butanol.
• the refined blend can be used as is or can be used after addition and thorough mixing of one or more conditioners, stabilizers, or other additives (e.g., kerosene).
• conditioners, stabilizers, or other additives e.g., kerosene
• the fuel composition can be passed through one or more filters, optionally of progressively smaller pore size, so as to remove suspended contaminants.
• filters are available from a variety of sources including, e.g., Donaldson Co., Inc. (Minneapolis, Minnesota), Central Illinois Manufacturing Co. (Bement, Illinois), Harvard Corporation (Evansville, Wisconsin), and Wix Filtration Products (Gastonia, NC).
• Using a pump to pressurize the system to -130 to -140 kPa can provide a processing rate on the order of -550 to -700 mL/s.
• This technique is believed to be capable of providing an ethyl ester of soy oil/ethanol fuel composition with a kinematic viscosity at 40 0 C on the order of -3.6 mm 2 /s, -3.5 mm 2 /s, or even lower.
• These viscosity values are in contrast to those reported for prior art ethyl ester biofuels; see, e.g., the Peterson et al. article data mentioned above as well as the Graboski et al. article (from 4.4 to 5.9 mm 2 /s).
• the presence of free alcohol(s) in the fuel composition can explain no more than about half of the viscosity reduction seen in the present fuel composition. An explanation for the remainder of this reduction is not fully understood but might result from the acidulation step making one or more of the undesired byproducts more susceptible to removal by further refining steps such as, e.g., filtration.
• a fuel composition that has been both acidulated and filtered can have a kinematic viscosity that is on the order of 40% less than that of the raw fuel from which it has been refined.
• petrodiesel generally is expected to have a kinematic viscosity of no more than 4.1 mm 2 /s when measured at 40 0 C in accordance with ASTM D975, providing a biofuel with similar viscosity characteristics can be advantageous with respect to both commercial acceptance and in-use performance.
• the ordinarily skilled artisan understands the desirability of having a biofuel composition that has storage and performance characteristics that are as similar as possible to ubiquitous petrodiesel. For example, published reports including the aforementioned Peterson et al.
• the fuel composition can be stored without a need for significant treatments or precautions.
• the fuel composition by refining the fuel composition in a slightly acidic form, better storage and handling performance can be achieved.
• the pH of the refined fuel composition might be able to be adjusted upwardly so that fuel composition has an essentially neutral pH prior to use without negatively affecting the viscosity and storage stability of the fuel composition once the refining process is complete.
• this process can result in a fuel composition having a cloud point (as measured in accordance with ASTM D2500) of at least as low as about -2°C, -3°C, -4°C, -5°C, -6 0 C, -7°C, or even lower, and a pour point (as measured in accordance with ASTM D97) of at least as low as -10 0 C, -12.5°C, -15°C, -17.5°C, -20 0 C, or even lower.
• a cloud point as measured in accordance with ASTM D2500
• a pour point as measured in accordance with ASTM D97
• the Peterson et al. article reports that ethyl esters of fatty acids have pour points of from -10° (ethyl ester of rape- seed oil) to 12°C (ethyl ester of beef tallow).
• a fully refined fuel composition can be used as is or, depending on the end use application, diluted with an appropriate amount of petrodiesel. For example, some fueling locations have created a 50:50 blend of bio- and petrodiesel and then used this blend as a master- batch for providing further diluted blends. To date, no significant miscibility issues have been reported, even with the so-called masterbatch blends.
• a fuel composition according to the present invention generally includes a lower alkyl monool (e.g., ethanol) and a C 2 -C 6 ester of one or more long chain fatty acids.
• the composition generally includes from about 5 to about 10% C 2 -C 4 alcohol(s), preferably ethanol, and a complementary amount of long chain fatty acid ester(s); all other components typically are present in no more than trace amounts.
• at least 99.99% (by wt.) or even 99.999% (by wt.) of the composition can constitute just C, H and O atoms; in these and other embodiments, the composition can be essentially free of at least one of, and preferably both of, sulfur and nitrogen atoms.
• the composition generally includes water, typically in an amount of from about 0.2 to about 0.5 % (by vol.) and amounts of as much as 0.8% (by vol.) or more are believed possible in certain circumstances.
• the fuel composition preferably has a slightly acidic pH (at least during refining) and a kinematic viscosity at 40 0 C of about 3.7 ⁇ 0.2 mm 2 /s. Even in the absence of flow improving additives, the composition can have a cloud point of at least as low as about -5°C and a pour point of at least as low as -15°C. Each of these properties can be achieved in isolation or, in some embodiments, in combination.
• a bio fuel composition of this type can be used neat and, in some circumstances, can provide significant emission advantages over neat petrodiesel or a blend of petrodiesel and biofuel.
• a fuel composition including ethanol and an ethyl ester transesteri- fication product of RBD soybean oil was tested in a short rail line locomotive (EMD model 16- 645BC) employing a two-cycle, V- 16, roots blown, non-turbocharged engine; each cylinder had a displacement of -10.5 L (645 cubic inches), resulting in a total displacement of nearly 170 L.
• EMD model 16- 645BC a short rail line locomotive
• the locomotive was provided with -280 L (75 gallons) of neat biofuel composition and allowed to warm up, thereby flushing any remaining petrodiesel from the engine.
• Percent smoke opacity was measured continuously using a WagerTM 7500 smoke meter (Robert H. Wager Co., Inc.; Rural Hall, North Carolina) clamped on a 5 cm (2 inch) sampling elbow tube placed inside one of the exhaust stacks of the locomotive.
• Emission gases were measured using a testoTM 350XL portable gas analyzer (testo, Inc.; Flanders, New Jersey) set to measure exhaust O 2 , CO, SO 2 , total hydrocarbons, NO, NO 2 , and combined NOx levels. (Total hydrocarbon data was not collected due to a sampling issue.)
• the analyzer came equipped with a model 450 control unit and attached sampling probe. The gas analyzer probe was maintained in a constant sampling position by a bracket that held the probe approximately 5 cm (2 inch) into the center of the exhaust stack.
• Each of the emissions characteristics of the present fuel composition is highly desirable, both individually and in combination. This is particularly true in view of the fact that railroad engine emissions are coming under scrutiny from environmental agencies such as the EPA. Because two-cycle diesel engines constitute the vast majority of engines in use on railroads throughout North America and because off-road #2 petrodiesel generally is considered a relatively dirty fuel (i.e., its combustion results in large amounts of particulates, SO 2 , NO x species, etc.), the availability of alternative fuels that can assist these engines in meeting more stringent emission standards is highly desirable.
• the coolant temperature increase was determined after the engine had been warmed as close as possible to 71 0 C (160 0 F) before running it for 15 minutes with each fuel type.
• a fuel composition of the present invention appears to result in a calculated engine efficiency that is far better than that of waste vegetable oil and even better than that of a commercial B20 diesel blend. Also, use of a fuel composition according to the present invention resulted in a coolant temperature increase less than that of all other fuels tested, including two commercial fuels. With respect to fuel efficiency, a fuel composition of the present invention exhibited 10% better results than a fuel made from waste vegetable oil; additionally, assuming a linear extrapolation of efficiency decrease with an increase in percentage of biofuel in the blended product, the same fuel composition appears to yield ⁇ 5% better results than a biofuel presently considered commercially acceptable, i.e., a methyl ester derivative of soybean oil.

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• 2007
  • 2007-10-23 CA CA002607478A patent/CA2607478A1/en not_active Abandoned
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