Patent Application
20140311020
The present disclosure relates to fuel compositions, and particularly, diesel fuel compositions, as well as blendstocks for combining with fuel to form fuel compositions.
The invention provides fuel compositions for use in internal-combustion engines, and methods of forming and using such compositions.
The fuel compositions generally comprise (1) a hydrocarbon fuel, such as diesel, (2) a polar fluid, such as alcohol, water, and/or other oxygen rich fluids, (3) an emulsifier present in an amount effective for the hydrocarbon fuel, polar fluid, and emulsifier to form an emulsion; and (4) a cetane enhancer, such as 2-ethylhexyl nitrate. The emulsifier may be selected from a group consisting of noncyclic polyol fatty acid esters and noncyclic polyol fatty alcohol ethers. In some embodiments, at least about half of the emulsifier is selected from this group. In other embodiments, at least about half of this group is mono-substituted. The emulsifier also may consist essentially of a single molecular species having both polar and nonpolar portions.
The methods generally comprise methods of forming and using the fuel compositions, including components thereof. For example, the invention provides methods of forming the emulsifier, by synthesizing and/or purifying components of the emulsifier. These components may include noncyclic polyol fatty acid esters and noncyclic polyol fatty alcohol ethers.
These and other aspects of the invention are described in the following four sections: (1) synthesis of noncyclic polyol fatty acid esters and noncyclic polyol fatty alcohol ethers, (2) purification of noncyclic polyol fatty acid esters and noncyclic polyol fatty alcohol ethers, (3) fuel compositions, and (4) examples.
Monoglycerides of fatty acids have been used for years as surfactants in a variety of food, cosmetic, and other formulated products. In most applications, industrial-grade monoglyceride compositions having 40-55% monoglyceride content have proven suitable. However, the present application in fuel formulations requires high-purity monoglycerides to yield optimal performance, and inexpensive monoglycerides to be economically practical.
Monoglycerides have been synthesized by a variety of methods. Unfortunately, these methods generally yield products that must be further distilled or extracted to obtain high-purity monoglycerides. Moreover, these methods generally are unsuitable for forming monoglycerides of unsaturated fatty acids, such as oleic acid, because of oxidative decomposition at the point of unsaturation. U.S. Pat. No. 2,022,493 to Christensen et al. discloses the conventional method for synthesizing monoglycerides, which involves the transesterification of triglycerides with glycerol and sodium hydroxide to form the monoglycerides. However, the product of this method is a mixture of 40-55% monoglyceride, 20-30% diglyceride, and a remainder of unreacted triglyceride. U.S. Pat. No. 2,132,437 to Richardson et al. and U.S. Pat. No. 2,073,797 to Hilditch et al. disclose two methods of increasing monoglyceride selectivity by converting the triglyceride to free fatty acid before esterification. However, the products of these methods are still contaminated with at least 20% di- and triglyceride, and the methods are considerably more complex than the conventional method. U.S. Pat. No. 5,153,126 to Schroder et al. discloses a method for making additional gains in selectivity by using a lipase enzyme as the transesterification catalyst. However, this method is very costly and difficult to scale up.
These steps may be performed under conditions that would tend not to substantially reduce an unsaturated fatty acid or fatty chloride. Such conditions may include performing one or more of the steps in an inert atmosphere, such as a nitrogen atmosphere, or performing one or more of the steps in the absence of light.
The preferred acid catalyst is p-toluenesulfonic acid, but any concentrated mineral acid will suffice. Suitable solvents include any solvent that (1) does not react with the reactants, (2) is easily separated from acetone in a fractionating column, and (3) will carry water over by vapor condensation. Such solvents include benzene and solvents having 1-2 parts of chlorocarbons, such as chloroform. In a second step 152, the 1,2-iso-propylidene glycerol is reacted with oleic acid to form the corresponding 1,2-iso-propylidene glyceryl ester. In a third step 154, the 1,2-iso-propylidene glyceryl ester is reacted with aqueous acetic acid to remove the protecting group and give the corresponding α-monoglyceride. Acetic acid acts as both solvent and acid catalyst. Water is added at a rate that sustains hydrolysis without rendering reactants insoluble. Hydrolysis also can be effected by formation of intermediate borate esters, which are then hydrolyzed with water.
The methods in
The apparatus is a simple and efficient means of driving the reaction to completion. During reflux, chloroform and water vapors are separated from reactants by the use of fractionating column 206, which is packed with glass beads 220. The chloroform/water vapors are then condensed by means of condenser 210, such as a Friedrichs condenser, with the condensate flowing down into light oil-type separation trap 208, where the water and chloroform phases separate. The denser chloroform phase continuously returns to the reaction vessel via a sidearm 222, while water accumulates in a receiver trap 224. Water can be periodically removed from the receiver trap via a stopcock 226 if the production scale exceeds the volume capacity of the trap. Upon completion of step 1, the desired organic acid can be added and step 2 then carried out without interruption of reflux. The system works smoothly with little operator attention up to semi-pilot (22-liter reaction volume) scale. Although reaction times for steps 1 and 2 were fairly long (24-26 h) with the equipment used, reaction times can be shortened greatly by increasing the capacity of the fractionating column and condenser. Chloroform solvent can be replaced with other less harmful solvents, as long as the substitute has a density greater than water and an appropriate boiling point.
The final acid hydrolysis step using glacial acetic acid represents an improvement over other acetonide hydrolysis reagents previously employed, such as mineral acids or boric acid/2-methoxyethanol. The process takes advantage of the product's limited solubility in aqueous acetic acid. By adding water only gradually during hydrolysis, all reactants are kept in solution throughout the step. Once hydrolysis is complete, the addition of a small amount of water to the cooled product solution causes the product to precipitate. The acetic acid/water mixture, containing less than 20% water, is then decanted and can be purified and recycled. The combined attributes of selectivity, simplicity, and recyclability of materials all make the process amenable for use at an industrial scale. In contrast, in the past, the acetonide protecting group was removed using a two-step process. The acetonide was first converted into the borate ester using boric acid and 2-methoxyethanol, and the borate ester was then extracted into ether and washed with water to hydrolyze the ether back to the original diol functionality. This procedure is cumbersome, and some of the reagents are too costly to use on an industrial scale.
There are many attributes of the present process that render it a practical means for monoglyceride production. All three steps of the reaction sequence are accomplished in the same reaction vessel. By using a co-solvent such as chloroform in combination with a separation trap, water is continuously removed from the reaction mixture, thereby driving both the acetonide and ester formation steps to completion. In the past, acetonide formation steps were driven to completion by mechanisms only suitable at very small scales, such as using water carrier solvents such as chloroform or benzene, and either a collection tube or Soxhlet extractor filled with drying agent to remove water from the reaction mixture as it is formed. The solvent mixture obtained by distillation of the iso-propylidene glyceryl ester product mixture can be recycled for use in the next batch. The final acetonide hydrolysis step is mild and fast, and the acetic acid recovered can be purified and recycled.
The product yield from each step is virtually quantitative, and the overall yields range from 94-98%. Thin layer chromatography (TLC) reveals only traces of residual reactants and no di- or triglyceride contaminants. The product work-up is easy; involving neutralization of residual acid with sodium bicarbonate, followed by three water washes. This crude product can be used in microemulsion formulations without further purification. However, partitioning of the crude product between aqueous ethanol and hexane removes residual reactants; concentration of the aqueous ethanol phase affords a pure α-monoglyceride product that readily crystallizes. In microemulsion formulations using glyceryl-α-monooleate (α-GMO) as the surfactant, only one-sixth the amount of this α-monoglyceride is needed versus the amount of industrial grade glyceryl monooleate (GMOI) needed otherwise to emulsify an equivalent amount of aqueous ethanol in diesel fuel.
The method also may be used to synthesize glyceryl fatty alcohol ethers from the corresponding fatty alcohol chloride. For example, the method may be used to synthesize 1,2-iso-propylidene glyceryl R, where R is a hydrocarbon chain, from RCI and 1,2-iso-propylidene glycerol.
The monoglyceride product may be purified by a variety of methods. U.S. Pat. No. 3,826,720 to Lowrey discloses a monoglyceride purification method based on the partitioning of crude glyceride mixtures between aqueous methanol and hexane. Monoglycerides preferentially migrate to the aqueous methanol phase. However evaporation of the aqueous methanol proves difficult because of excessive foaming. Since the present application uses the monoglyceride in combination with aqueous ethanol, it would be advantageous if aqueous ethanol could be substituted for aqueous methanol in an analogous procedure. Working with product solutions would reduce the materials handling problems associated with such products, which are typically very tacky and viscous in the liquid state. Such a method might also be useful for upgrading industrial grade monoglycerides.
The solvent partitioning purification method for removing residual contaminants from the crude product is also effective for upgrading the purity of industrial grade GMOI. It is based on a commonly employed method using a counter-current separatory column with aqueous methanol as the descending phase and hexane as the ascending phase to separate monoglycerides from di- and triglyceride contaminants. The monoglycerides migrate to the aqueous methanol phase, while the di- and triglycerides migrate to the hexane phase. In the present application, 5% aqueous ethanol was substituted for the aqueous methanol. The crude GMO sample is dissolved in 10 parts of hexane and 15 parts of 5% ethanol to afford a homogeneous solution. Upon addition of 1 part of water, the solution separates into two phases. Concentration of the aqueous ethanol phase affords a viscous oil that crystallizes on standing and contains very little residual di- and triglyceride by TLC. Concentration of the hexane phase affords an oil that is primarily di- and triglyceride by TLC.
In formulation experiments with diesel fuel, the GMO thus purified performs as well as crude α-GMO. If either this product or crude α-GMO is again partitioned by the same procedure, the requirement for either surfactant is further reduced by 50%, which represents an overall six fold reduction in GMO requirement compared to industrial GMOI. Further partitioning does not afford significant additional performance improvements. This method therefore appears to be effective in removing both residual reactants and di- and triglycerides from monoglyceride products.
One purpose of the synthesis and purification research is to provide options for the low cost manufacture of purified GMO. The ability to accomplish this has proven critical to the feasibility of using GMO and other polyol fatty acid esters as surfactants for stabilizing water/ethanol/diesel microemulsions. Previous investigations have demonstrated that such microemulsions can be made using industrial grade GMOI but have serious drawbacks. Nearly three parts of GMOI are needed to create a 10% microemulsion of 5% aqueous ethanol with diesel fuel that is stable at room temperature. At current prices, the cost of a 30 wt % GMOI: 10 wt % aqueous ethanol: 60 wt % diesel is more than $2.50/gallon which is more than twice the current price of diesel. Such emulsions also are temperature sensitive, and prolonged storage at temperatures below the freezing point of water results in the precipitation of solids and/or phase separation depending upon the particular source of GMOI. The composition of GMOI varies considerably from supplier to supplier, making it difficult to predict the behavior of a particular source of GMOI.
These microemulsions are considered to be extremely fine colloidal dispersions consisting of micelles, or “bubbles,” of water and alcohol coated with a layer of surfactant. As depicted in
However, the industrial grade product, GMOI, is only 40-55% monooleate with the balance being di- and trioleate. Neither the di- or trioleate fits well into the model; the dioleate has little hydrophilic character and the trioleate none. Their presence only serves to interfere with the action of the monooleate. The need for higher purity material drove the investigations into synthesis and purification options. It was subsequently discovered that a higher purity grade of GMO, which analyzed as 90% monooleate, is commercially available for specialized uses in cosmetics. Formulation tests using either the α-GMO obtained by direct synthesis or the 90% GMO available commercially demonstrated a six-fold reduction in the amount of GMO needed. The 30:10:60 GMOI:aqueous ethanol:diesel fuel formulation possible with the industrial grade product could be achieved using a 5:10:85 α-GMO (or 90% GMO): aqueous ethanol: diesel fuel formulation with high purity GMO (α-GMO and 90% GMO). The fact that a six-fold increase in effect was achieved with only a two-fold increase in purity has important implications. The disproportionate increase suggests that the relationship between the constituents is, indeed, quite specific. The dilution effects of the contaminants are compounded by another effect, which is most likely their interference in the efficient ordering of the monooleate molecules. Microemulsions made with high purity GMO exhibit the positive Tyndall effect expected of colloidal dispersions. All indications support a well-ordered micelle with an ethanol/water core and a monomolecular layer of monooleate molecules.
It also was found that the formulations using high purity GMO had much more thermal stability. In addition to the known antifreeze action of the ethanol, it is reasonable that the hydrophilic ends of the monooleate molecule duplicate the antifreeze ethylene glycol and thereby cause an analogous effect. The addition of a small amount of high purity GMO considerably enhances the microemulsion's thermal stability. Whereas microemulsions using industrial GMOI were only stable for a period of hours at −10° C., microemulsions using high purity GMO could be stored at −10° C. for months without phase separation or the formation of any precipitate. The additional stabilizing benefits of adding small portions of ethylene glycol, iso-propanol, or a 6:1 mixture of cyclohexanol and cyclohexanone also were noted, with small portions of either (less than 0.5%) further stabilizing the emulsions down to −20° C. For practical purposes, the high purity GMO enables use of the fuel without concern in most of the coastal and southern United States. Fuel system heaters that might be needed in cold climates are already in use for diesel trucks operating in these regions.
It is possible that there may be some cold starting difficulties, because formulations with diesel incorporating high levels of alcohol have exhibited such problems in the past. Also, engine timing in diesel engines varies with engine type and model year, and this can affect the emissions reductions achieved. Although water has a beneficial effect by lowering combustion temperature, it also can retard ignition, which can have a counter-productive effect depending upon engine timing. If either of these problems arises with particular formulations, the addition of cetane enhancing organic nitrates such as 2-ethyl hexyl nitrate or organic peroxides such as ditertiary butyl peroxide should alleviate either problem. Although the presence of nitrogenous components in emulsion formulations may contribute to NOx formation, there is strong evidence that the nitro groups in alkyl nitrate cetane enhancers are converted to harmless nitrogen gas in the combustion process. However, the surfactant has a good cetane value itself, so the levels of cetane enhancer that may be required would not be high (0.5-3.0 wt %) in any event. 2-Ethylhexyl nitrate also was found to have a modest stabilizing effect in emulsion formulations.
The microemulsions using high purity GMO also tolerate the presence of more water than that present in just the 5% aqueous ethanol phase, as long as the ethanol content is relatively high. Formulations using a 5:10:85 ratio can tolerate up to two percent added water. Stable formulations with water contents exceeding 5% have been made using only 2 parts high purity GMO per part of water. Thermal stability is compromised as the water content is increased, but this, too, can be compensated for by increasing the ethanol or GMO content or by using the stabilizing additives previously noted. The presence of water accounts for NOx-reducing effects of microemulsions by reducing combustion temperature and results in smoother running by broadening the temperature-time profile. The particulate reduction effects also are accounted for by the “steam explosion” of the microbubbles upon combustion, which better atomizes the fuel and thereby results in more complete combustion. The ability to control the level of water is important in efforts to find the maximum emissions-reducing effects. Ethanol also burns very cleanly in diesel engines, producing no smoke, so its presence can dramatically reduce particulate emissions. Ethanol also contributes to the moderation of combustion temperature and can, thereby, reduce NOx emissions by 10% or more even in the absence of any water.
Another constituent, ammonia, shows a dramatic NOx-reducing effect. Stable emulsions also can be made using GMO in combination with the ammonium salt of oleic acid or other suitable carboxylic acids. Ammonia is used to reduce NOx in exhaust gas in both high-temperature and catalytic low-temperature systems. It reacts with NOx to produce harmless nitrogen gas and water. It was reasoned that introducing ammonia in the form of ammonium oleate might neutralize NOx formed during the combustion process, and the emissions data presented at the end of the example section show a large NO reduction when ammonia is present in this form. Ammonia reduces NO emissions in formulations both with and without cetane enhancer. In formulations with cetane enhancer, ammonia also appears to reduce particulate emissions. Calculations show that 12-59% of the ammonia present is consumed in neutralizing NOx. Ammonia and oleic acid also are inexpensive and reduce the requirement for the more expensive GMO.
It is possible to combine almost any proportions of ingredients by using the appropriate amount of high-purity GMO surfactant. However, significant emissions reductions have been noted at a level of only 10% aqueous ethanol (overall water content of 0.5 wt %). Since the GMO costs more than diesel fuel, the quantity used should be kept to the minimum needed to obtain the desired effect. The estimated cost of a microemulsion containing 10 wt % aqueous ethanol is about 20% greater than diesel fuel alone at current diesel, ethanol, and high-purity GMO prices. Reasonable reductions in manufacturing costs could reduce the price differential to as little as 10% at the current, very low price for diesel. Only a modest increase in diesel price is needed to offset this disadvantage.
All constituents in the subject formulations come from renewable resources, the aqueous ethanol being produced by fermentation and the GMO being derived from corn oil. The microemulsion formulations that are the object of the present invention are fully renewable fuels, the 5:10:85 formulation having a renewable content of 15%. Users not only qualify for consideration as a renewable fuel but also may qualify for CO2 reduction credits should programs to curb global warming be put into effect.
Although the GMO:aqueous ethanol:diesel fuel formulations have been identified as one preferred embodiment, the method has considerable generality. Stable emulsions can be formed with any of the C1-C4 alcohols. The level of monoglyceride required can be reduced through the use of the ammonium salts of fatty acids, preferably unsaturated fatty acids such as oleic acid. Monoglycerides incorporating other unsaturated fatty acids such as elaidic, erucic, or linoleic acid also are effective in amounts comparable to those of GMO and exhibit reasonable thermal stability. Monoglycerides incorporating saturated fatty acids such as lauric, myristic, or stearic acid also form microemulsions, but most are thermally unstable. To those skilled in the art, it is evident that both the synthesis and the application can be generalized to a wide range of polyol fatty acid esters and polyol fatty alcohol ethers. The corresponding glyceryl fatty alcohol ethers exercise effects comparable to their ester analogues. This is to be expected from the model because the position of the oxygen absent in the ethers has no bearing on the key structural features of the monoglycerides as surfactants.
It also should be noted that the use of these emissions-reducing microemulsions will enable the use of additional control methods such as catalytic conversion and exhaust gas recycle that are currently impractical because of the high level of particulate soot in diesel exhaust.
The present disclosure provides for the dilution of fuel to meet certain (or predetermined) pre-combustion specifications, for example, by reducing a concentration of aromatics, sulfur, phosphorus, and other fuel-refinery contaminants.
The present disclosure provides for incorporating hydrous or other polar components into fuel to form a fuel composition. The hydrous or other polar components may cool combustion of the fuel composition, which may reduce emissions of NOx and other undesirable contaminates, such as particulate matter or criteria pollutants.
One or more components of the fuel composition may be described as petroleum-displacer material. For example, the fuel of the fuel composition may include a petroleum-based component, and the petroleum-displacer material may increase a content of “renewables” (e.g., hydrous ethanol and/or low grade ethanol) in the fuel composition.
Low grade ethanol may be hydrous ethanol having a water content of 1-30%, more preferably 5-20%. Low grade ethanol may include a greater percentage of contaminants (other than water) as compared to higher grade ethanol.
The one or more components of the fuel composition may also displace required amounts of additives (e.g., lubricants, etc.).
In combustion, carbon, oxygen, and hydrogen combust, while other fuel components (e.g., aromatics, sulfur, phosphorus, among others) are contaminants. In some embodiments, the fuel composition may reduce carbon intensity by replacing these contaminants with oxygenates that bring oxygen into the fuel.
The one or more polar fluids may include a water component and/or an alcohol component, or any other suitable polar fluid component. For example, the polar fluid may include ethanol of a relatively low grade, such as ethanol having a water content of 5-20%, assuming water is the main contaminant.
Providing one or more polar fluids may involve selecting the alcohol component from a group comprising (a) n-propyl alcohol, (b) iso-propyl alcohol, (c) n-butyl alcohol, a mixed alcohol formulation (e.g., ENVIROLENE®), methanol, and ethanol, and blending the alcohol component and water component to form the one or more polar fluids. Blending the alcohol and water may involve formulating the amount of water so that the amount of water comprises about 1-30% of the one or more polar fluids. Preferably, the amount of water comprises about 5-20% of the one or more polar fluids. Preferably, the alcohol component includes ethanol.
ENVIROLENE® is a mixed alcohol formulation made by Standard Alcohol Company of America. Examples of suitable mixed alcohol formulations are described in U.S. Pat. No. 8,277,522 and U.S. Patent Application No. 2013/0019519, which are hereby incorporated by reference.
Providing one or more polar fluids may include adding a cetane enhancer and/or other additives to the one or more polar fluids.
Selecting the microblender may involve selecting a fatty acid component, such as a fatty acid component chosen from a group comprising saturated and/or unsaturated carboxylic acids and/or esters containing 14 to 24 carbons, such as oleic acid, elaidic acid, erucic acid, linoleic acid, lauric acid, myristic acid, and stearic acid. Selecting the microblender may involve selecting the fatty acid component chosen from a group comprising suitable unsaturated fatty acids. Selecting the microblender may involve selecting the fatty acid component chosen from a group comprising suitable saturated fatty acids. Preferably, the fatty acid component includes oleic acid.
Selecting the neutralizer may involve selecting a component or composition that is capable of neutralizing the microblender. For example, selecting the neutralizer may involve selecting a component of a lower pH than the microblender. For example, if the microblender includes an acidic component, then selecting the neutralizer may involve selecting a basic component. Preferably, the neutralizer includes an ammonia component, such as ammonium hydroxide.
Method 300 may include a step 308 of forming a blendstock or microblend. Step 308 may involve adding (or blending, or introducing) the neutralizer and the microblender to the one or more polar fluids. Amounts of the neutralizer, the microblender, and the one or more polar fluids which are added together in step 308 may be formulated to allow the neutralizer to substantially neutralize the microblender, and/or allow the microblender to substantially spontaneously blend with the one or more polar fluids. For example, the neutralizer may include ammonium hydroxide and the microblender may include oleic acid, as described. The ammonium hydroxide may be present in an amount effective to neutralize an amount of the added oleic acid, in order to form ammonium oleate. The ammonium oleate may then blend substantially spontaneously with the one or more polar fluids, for example, at standard temperature and pressure and without being otherwise heated or stirred.
Typically, the direct formation of ammonium oleate by mixing oleic acid and ammonium hydroxide (NH4OH) requires an extended period of time and a considerable about of labor, as does the addition of ammonium oleate to another component (e.g., ammonium oleate being a very viscous partially solidified oil that is difficult to work with). However, Applicants discovered that by further diluting the ammonium hydroxide (e.g., in the one or more polar fluids), and placing the oleic acid in solution with the one or more polar fluids (e.g., ethanol, ethanol and 2-EHN), the ammonium hydroxide and the oleic acid may substantially spontaneous blend to form the ammonium oleate. In other embodiments, the alcohol component (e.g., ethanol) may be part of an aqueous mixture (e.g., a combination of NH4OH and water). The aqueous mixture including the alcohol, may then be added to the oleic acid and 2-EHN, which may allow for substantially spontaneous blending (e.g., for the NH4OH and the oleic acid to substantially spontaneously form the ammonium oleate).
In some embodiments, the neutralizer, the microblender, and the one or more polar fluids may substantially spontaneously blend together at or below 20 degrees Celsius, such as at 15 degrees Celsius, or at or slightly above 13-14 degrees Celsius (e.g., a melting point of oleic acid being around 13-14 degrees Celcius).
The blendstock or a combination of components of the blendstock may include a surfactant. For example, the microblender and the neutralizer may combine to form the surfactant.
In step 308, the one or more polar fluids, the neutralizer, and the microblender may be introduced (or added) to one another in any suitable order. For example, one or more components of the microblender may be introduced to the one or more polar fluids before the neutralizer. In some embodiments, the neutralizer and the microblender may be added to the one or more polar fluids substantially simultaneously. Preferably, the neutralizer is added to the one or more polar fluids before the microblender is added to the one or more polar fluids.
Method 300 may include a step 310 of providing a fuel. The fuel provided may include any fuel component suitable for use in internal-combustion engines, such as a hydrocarbon component, a diesel fuel component, a bio-diesel component (e.g., B100), an ultra-low-sulfur diesel (ULSD) component, a synthetic or renewable diesel fuel component, or any other suitable fuel component or combination thereof.
Method 300 may include a step 312 of forming the fuel composition. Step 312 may involve introducing (or adding) the blendstock to the fuel. When introduced, the blendstock may be combined with (or dispersed throughout, or blend with) the fuel to form the fuel composition. The fuel composition may be formulated to be 0.25-50% blendstock and 50%-99.75% fuel.
In some embodiments, step 312 may include blending the fuel composition with a second provided fuel to form a second fuel composition. For example, the microblend may be mixed with a biodiesel component (e.g., B100) to form a biodiesel fuel composition with a microblend concentration of 0.25-20% (e.g., the microblend being 0.25-20% of the fuel composition). The biodiesel fuel composition may then be blended with a diesel fuel (e.g., ULSD) to form a biodiesel-diesel fuel composition having a non-petroleum concentration of 5-20%, which may correlate to the biodiesel-diesel fuel composition having a microblend concentration of 0.25-2% (e.g., the microblend being 0.25-2.0% of the biodiesel-diesel fuel composition).
In some embodiments, the fuel composition may include a cetane enhancer component. The cetane enhancer may be added to any component or combination thereof in either of steps 302, 304, 306, 308, 310, and/or 312.
Method 300 may be described as a two-stage process of forming a fuel, wherein the process includes a first-stage of forming the blendstock, and a subsequent second-stage of forming the fuel composition.
The blendstock may be described as a micro-blend and/or a pre-combustion fuel treatment, which may be combined with a post-combustion fuel treatment, such as a catalytic converter, or other suitable oxidation catalysts.
For example, a Diesel Oxidation Catalyst or DOC is an exhaust post-combustion fuel treatment device for diesel engines. In general, DOCs contain palladium and platinum which serve as catalysts to oxidize hydrocarbons and carbon monoxide into carbon dioxide and water in the following reactions:
2CO+O2→2CO2
[HC]+O2→CO2+H2O
The fuel composition may have complementary if not synergistic results when combined with such a DOC. For example, oxygen provided by the neutralizer, such as from the ammonium hydroxide component, may increase the amount of hydrocarbons and/or carbon monoxide oxidized by the DOC.
The blendstock may be combined with the larger volume of fuel sometime after the fuel is refined at a refinery. For example, the fuel additive may be combined with the fuel at the refinery after the fuel has been refined, or at another location downstream from the refinery (e.g., any suitable location where the refined fuel has been received).
In some embodiments, the blendstock may be provided in a blendstock tank (e.g., a large underground or above ground tank) at a filling station. The blendstock from the blendstock tank may be combined with the fuel from (or in) a second tank (e.g., another large underground or above ground tank) to form the fuel composition. The filling station may then offer the fuel composition as a filling choice, and may pump the fuel composition directly into a vehicle fuel tank of a customer's vehicle. Alternatively, the blendstock may be blended with the fuel by a fuel blender at a terminal (e.g., a location between a refinery and a distributor), and the distributor may then distribute the fuel composition to filing stations.
In other embodiments, the filling station may provide the blendstock and the fuel as separate filling options. The customer's vehicle may include a first tank for the fuel, a second tank for the blendstock. The first tank may be at least partially filled with the fuel at the filling station. The second tank may be at least partially filled with the blendstock at the filling station. Suitable apparatus in the vehicle, as is well-known in the art (e.g., see http://en.wikipedia.org/wiki/Bi-fuel_vehicle, which is hereby incorporated by reference), may then combine the blendstock and the fuel (e.g., in a third tank of the vehicle, or any other suitable location within the vehicle) to form the fuel composition for subsequent combustion in an internal combustion engine of the vehicle.
In other embodiments, the blendstock may be provided as an after-market product, which the customer may purchase and add to the vehicle fuel tank subsequent to the vehicle fuel tank being filled with the fuel at the filling station.
The blendstock may exhibit enhanced lubricity, and adding the blendstock to fuel to form the fuel composition may have the effect of increasing the lubricity of the fuel. In addition, the blendstock may be useful for lubricating and/or cooling a drill in drilling applications.
The following examples illustrate without limitation these and other aspects of the invention.
50.0 g (0.543 moles) of glycerol, technical grade was added to a 500 mL round bottom flask fitted with a magnetic stir bar, heating mantle, and 400 mm fractionation column packed two-thirds full with glass beads connected to a light oil separation trap and Liebig condenser, as shown in
The crude ester product was placed in a 500 mL Erlenmeyer flask, and 200 mL 2-ethoxyethanol and 60.0 g (0.97 moles) of ground powdered boric acid, technical grade were added. The mixture was heated on a hot plate at 100° C. for 45 minutes then allowed to cool. The boric acid gradually dissolved upon heating but white solids, presumably unreacted boric acid, precipitated on cooling. The mixture was transferred to a 1 L separatory funnel and extracted with 500 mL of diethyl ether. The ethereal solution was washed 4 times with 500 mL portions of distilled water. The third and fourth water washes formed strong emulsions that took 45 minutes to break and partition. The ethereal solution was dried over anhydrous sodium sulfate, technical grade, filtered into a 1 L beaker, and gently warmed until all the ether was evaporated. The oil was placed in a vacuum desiccator and subjected to high vacuum overnight to give 44.6 g (0.125 moles, 72.3% yield) of light amber viscous oil that crystallized on standing. The product melting point was 32-37° C. Chromatographic analysis by comparison with known standards using silica gel plates in 10% methanol in benzene confirmed that the product was glyceryl-1-monooleate uncontaminated with any di- or trioleate with trace amounts of intermediate 1,2-iso-propylidene glycerol and 1,2-iso-propylidene glyceryl oleate impurities.
To a 22 L 3-neck flask fitted with mechanical stirrer, heating mantle, 900 mm fractionating column two-thirds full of glass beads and fitted with a light oil-type liquid-liquid separator and Friedricks condenser and nitrogen inlet and outlet were added: 3,000 g (2,372 mL, 32.6 moles) glycerol, technical grade, 4,500 mL (3,546 g, 61.1 moles) acetone, reagent grade, 4,800 mL chloroform, Unisolv methanol-free grade, and 12.0 g (0.07 moles) p-toluenesulfonic acid, reagent grade. The reaction mixture was carefully heated to a state of reflux, producing an appropriate rate of condensation into the separator. Reflux was continued until no more water accumulated in the separator (approximately 24 h at a collection rate of 25 mL/h with 580 mL of water collected). The separator was designed with sufficient capacity (1 l) to eliminate any need to remove reaction water during reflux. Nitrogen gas flow was initiated, and the reaction vessel was protected from light. 3,070 g (3,431 mL, 10.87 moles) of oleic acid, technical grade were added to the still hot reaction mixture via a dropping funnel, and reflux was continued until no more water accumulated in the separator (approximately 20 h at a collection rate of 10 mL/h with 195 mL collected). Heat was discontinued, and 26.4 g (0.32 moles) of anhydrous sodium acetate, technical grade was added with vigorous stirring. After cooling, 4 L of distilled water was added and thoroughly mixed. Mixing was stopped, the phases were allowed to separate, and the aqueous phase was removed by siphon. This step was repeated twice with 8 L portions of distilled water.
The dense organic phase was separated from residual water in a separatory funnel and charged into a clean 22 L flask for distillation and hydrolysis. The flask was fitted with a distilling head and 900 mm Liebig condenser, heating mantle, and mechanical stirrer. Chloroform and residual acetone were distilled off. The distillation temperature went from 57° C. to 72° C., at which point 4,500 mL of distillate had been collected. The distillation system was put under mild vacuum, and another 300 mL of distillate were collected. In subsequent runs, the chloroform/acetone solvents were distilled entirely under mild vacuum, such that the head temperature was kept between 40-45° C. This reduced the distillation time to 2 h. 4,083 mL of glacial acetic acid, technical grade was added, and the reaction mixture was warmed to 60° C. 600 mL of distilled water was added until the reaction mixture just became cloudy. An additional 1,800 mL of distilled water were added in 100 mL portions via a dropping funnel whenever the reaction mixture completely cleared, and the temperature was maintained between 60-70° C. After 5 h, the reaction mixture was allowed to cool overnight. In subsequent runs, the distilled water was added as fast as the cloudiness dissipated, which reduced the reaction time to 2 h. The reaction mixture was poured into 12 L of rapidly stirring distilled water. Subsequent trials showed that the added water volume could be reduced to as little as 2 L without significantly affecting product purity or handling as long as the crude product mass was washed well. After the precipitated product mass had time to set on standing (going from a viscous liquid to a semi-solid state), the aqueous acetic acid was decanted off. The mass was washed 3 times with 6 L of distilled water with maceration to penetrate the product mass. The mass was transferred to a glass reactor and treated with 5 L of saturated aqueous sodium bicarbonate with warming and maceration. When effervescence subsided, the bicarbonate solution was decanted, and the mass was washed twice with 4 L of distilled water and then heated just to the boiling point in 6 L of fresh distilled water and allowed to cool gradually to give an amber gel which formed at the surface as the α-GMO melted and then re-solidified. This process effectively expresses most of the water from the mass. The gel was dried overnight under a strong vacuum with gentle warming at 45-50° C. to give 3,717 g (10.42 moles, 96% yield) of viscous amber oil that crystallized on cooling. The product melting point was 33-36° C. TLC analysis showed a single spot corresponding to glyceryl-1-monooleate (α-GMO) with no di- or trioleate contamination and only faint traces of acetonide intermediates.
5.0 g of GMOI (Canamex Glicepol 182 Lot G-20Z7) was weighed into a flask. 75 mL (50 g) hexane, technical grade and 94 mL (75 g) 5% aqueous ethanol, technical grade were added and the contents mixed until a uniform solution was obtained. An additional 7.0 g of distilled water was added to the flask and mixed and decanted into a 250 mL separatory funnel. The funnel was capped, thoroughly shaken, then allowed to stand so the phases could separate. The phases were separated into two 125 mL Erlenmeyer flasks, and the solvent was removed by gentle heating. The hexane fraction weighing 45.6 g with solvent afforded 2.96 g of light tan oil. The ethanolic phase weighing 86.39 g with solvent was evaporated, then 100 mL anhydrous ethanol was added and evaporated to remove any residual water to give 1.92 g of light tan oil that spontaneously crystallized on cooling. TLC analysis using silica gel plates in 10% methanol in benzene showed the hexane-derived oil to be primarily di- and trioleate with some residual monooleate and the ethanol-derived solid to be primarily monooleate with only traces of di- and trioleate evident.
In formulation experiments using either unrefined or refined GMOI, 10 parts diesel fuel were mixed with 1 part hydrous ethanol in a flask, and then the GMOI sample was added in portions until a clear homogeneous mixture was obtained. The final proportions are compared in the following:
The formulation using the refined GMOI also appeared particularly stable to temperature, remaining completely clear on prolonged storage at −9° C. Refining reduced the amount of GMOI needed by 50%. This method when applied to crude α-GMO obtained by direct synthesis also afforded substantial performance improvements, which indicated that it also is effective in removing intermediate acetonide contaminants as well.
40.0 g of industrial grade glyceryl monooleate (GMOI) of 40%+ monooleate content (PPG Industries) was blended with 60 g of diesel fuel until a homogeneous mixture was achieved. Hydrous ethanol (190 proof) was then added in portions and mixed until homogeneous. The mixture remained homogeneous over the following range of proportions:
The mixtures with the above ranges were clear and stable at room temperature. The phases did not separate after refrigeration for 24 h at −12° C. until the ethanol concentration exceeded 25%. At room temperature up to 2.0 wt % water could be added before phase separation was noted.
To determine the minimum amount of GMOI needed to effect a stable emulsion of hydrous ethanol (190 proof) with diesel fuel, GMOI (PPG Industries), hydrous ethanol, and diesel fuel were mixed in the following proportions with the indicated results:
The mixture containing 30 g GMOI became cloudy upon cooling below 7° C., but the mixture containing 35 g GMOI remained clear to 0° C. The 60:30:10 diesel:GMOI:hydrous ethanol mixture, which contained 0.5 wt % of added water was subjected to water analysis by Karl-Fischer titration (Coffey Laboratories, Inc.) to determine the exact total amount of water present, and a mean result of 1.0 wt %±0.2 wt % was obtained. This indicates that another 0.5 wt % of water was inadvertently introduced by way of water contamination of the GMOI and, to a much lesser extent, of the diesel. This means that the maximum water holding capacity of the 60:30:10 mixture at room temperature is 3.0 wt %. This means that there is considerable flexibility to add water to formulations to enhance NOx reduction effects. Further experiments using high purity GMO (90%+) demonstrate that as much as 4% water can be formulated while retaining diesel as the main component.
Experiments to test the sensitivity of emulsions to chemical contaminants were conducted by adding a small amount (10 drops) of concentrated base (50% sodium hydroxide) or concentrated acid (37% hydrochloric acid) to a 60:30:10 emulsion and observing the effects with time. Results showed that the emulsion was quite stable to base, being unchanged after 30 days, but rapidly darkened and separated into two phases after only 4 days upon exposure to acid.
It was found that GMOI samples from different suppliers varied in terms of the minimum amount needed. The cold stability of the emulsions appeared more variable from supplier to supplier. Specifications varied in terms of monooleate content from 40-55%, residual glycerol from 1-3%, and residual triglyceride from 2-5%, but no particular variable clearly correlated with cold stability. In another experiment, a 60:30:10 emulsion with GMOI was stored for 4 days at −15° C., at which point a substantial amount of white flocculent solid had precipitated out. This solid was isolated by vacuum filtration in the cold to give a white waxy solid upon vacuum drying that appeared to be a mixture of trioleate and dioleate by chromatographic analysis. The filtrate obtained, which was now devoid of these solids, remained clear and homogeneous upon prolonged storage at −15° C. It, therefore, appears that the di- and triglyceride contaminants present in formulations using GMOI are a leading cause of solids precipitation in the cold and contribute nothing to the stability of the emulsion because their removal stabilizes rather than destabilizes the emulsion. This evidence provided a strong impetus to seek a means of synthesizing glyceryl monooleate free of di- and trioleate contaminants.
The foregoing formulations are advantageous because they employ only a single surfactant compared to the use of a minimum of two surfactants in prior art examples. The absence of any nitrogen containing substances should help to minimize NOx emissions. However, there is considerable product variability depending upon supplier, and the fairly large amounts of GMOI needed rendered the formulation cost about twice that of diesel alone.
30.0 g of Glyceryl monostearate flake was placed in a 250 mL Erlenmeyer flask. 10.0 g of hydrous ethanol (190 proof) was added and stirred. At room temperature, the two did not form a homogeneous solution. Upon gentle warming until the glyceryl monostearate melted (56° C.), the two components mixed to give a homogeneous solution that remained clear upon addition of 60.0 g of diesel fuel while warm. The still warm clear homogeneous emulsion formed a dense white solid precipitate of glyceryl monostearate upon standing at room temperature. Additional experiments using purified GMO having a significant concentration of saturated fats such as stearic acid showed a similar tendency to precipitate solids upon cooling.
30.0 g of Industrial GMOI (PPG Industries) was mixed with 10.0 g of anhydrous methanol. 60.0 g of diesel fuel was then added, and the mixture was stirred until clear and homogeneous. 0.5 g of distilled water was added dropwise and stirred until fully dispersed to give a clear homogeneous emulsion of the following final proportions:
The mixture was clear and stable at room temperature. The phases did not separate after refrigeration for 24 h at 0° C. At room temperature, up to 1 wt % water could be added before phase separation was noted.
Methanol is currently the least expensive of the C1-C4 alcohols. Although it is currently manufactured by the reforming of natural gas, it can be produced from synthesic gas obtained by biomass gasification so it has future potential as a renewable energy source.
30.0 g of GMOI (Kemester 2000, 50-60% monoester content) was weighed into each of three flasks. 10.0 g was then added of one of (a) n-propyl alcohol, (b) iso-propyl alcohol, or (c) n-butyl alcohol, and each flask was stirred until a homogeneous mixture was obtained. 60.0 g diesel fuel was then added and thoroughly mixed. In all three cases, homogeneous mixtures were obtained. 0.5 wt % distilled water was then added dropwise to each and mixed until fully dispersed. Again, all three cases gave clear homogeneous mixtures, although it appeared to take longer for the water to disperse in case (c) using n-butyl alcohol. All of the emulsions were stable down to a temperature of 10° C., but a gel-like solid formed upon prolonged storage of samples (a) and (c) at 7° C. The sample using iso-propyl alcohol was stable down to 0° C.
10.0 g of crude α-GMO was placed in a flask. 10.0 g of hydrous ethanol (190 proof) was then added and mixed until homogeneous. 80.0 g of diesel fuel was then added and mixed to give a cloudy suspension. Additional warm liquid α-GMO was added dropwise with stirring until a clear homogeneous mixture was obtained, requiring the addition of 2.7 g. The emulsion was then chilled to 1° C., which resulted in a cloudy emulsion. Addition of a further 0.5 g of α-GMO while still cold rendered a clear emulsion. Further chilling to −13° C. resulted in solids formation and a small amount of a dense liquid phase. Further addition of 1.5 g of α-GMO while in the cold afforded a clear emulsion that was stable to prolonged storage at −13° C. The final proportions needed to achieve stable emulsions over the temperature range are:
The α-GMO used represents a crude synthesis product that was not subjected to any purification. Although the α-GMO was devoid of di- and triglyceride contaminants, there were trace amounts of residual reactants present. Some variability was observed from batch to batch, with the wt % of α-GMO needed to effect a stable emulsion of 10 wt % hydrous 2 23° C.:
The emulsion having the maximum ethanol concentration was stable at room temperature, but phase separation occurred upon cooling to 12° C. Upon addition of another 1.7 wt % α-GMO, the emulsion was stable to 0° C. Emulsions having a hydrous ethanol concentration of 10 wt % and 10 wt % crude α-GMO were thermally stable to prolonged storage at −12° C. Note that the α-GMO lot used in this test proved more thermally stable than the lot used in Example 9. There are a number of subtle factors that affect thermal stability. This variability underscores the importance of cleaning up crude α-GMO by solvent partitioning before use.
5.0 g of hydrous ethanol and 50.0 g of diesel fuel were added to a flask and mixed. Portions of GMO (Germany, 90% monooleate, M.P. 33-38° C.) were added and mixed until a clear homogeneous mixture was obtained at room temperature. The sample was then chilled to −9° C., at which point a fine white solid and dense liquid phase had formed. Portions of GMO were again added until a mixture was achieved that remained clear and homogeneous at −9° C. The final proportions were:
This result shows that higher purity GMO grades available commercially are quite suitable as is for producing stable emulsions and can reduce the amount of GMO required by four to six fold over emulsions using industrial GMOI. Although the price for the 90% purity grade is $1.50/lb in bulk versus $0.83/lb for GMOI in bulk, the cost of the emulsion fuel (at a 10% hydrous ethanol level) is $1.66/gallon using high purity GMO versus $2.45/gallon using GMOI. This is quite favorable when compared to the current diesel price of $1.19/gallon. The synthesis and purification methods that are the object of the present invention should enable a reduction in high purity GMO prices by 25-30%, which would render emulsion formulations competitive with diesel.
50.00 g of certified diesel (Phillips, Lot D-538) was weighed into a flask, and 5.00 g of hydrous ethanol (190 proof) was added and mixed. GMO (German, 90%) was added in portions and mixed until a clear, homogeneous emulsion was obtained. Another portion of ethanol was added and then more GMO was added to render the mixture clear. These sequential additions were continued until the ethanol concentration exceeded 36 wt %. In a separate experiment, 50.00 g of hydrous ethanol and 5.00 g of certified diesel were weighed into a flask, and GMO was added until clear and homogeneous. This cycle of diesel and GMO additions was continued until the diesel concentration exceeded 36 wt %. Thus, the GMO requirement for blending hydrous ethanol and diesel was determined over the entire range of possible concentrations. These results are tabulated on the following page.
40.00 g of certified diesel (Phillips, Lot D-538) and 24.00 g of anhydrous ethanol were weighed into a flask. A portion of water was then added, followed by portions of GMO (German, 90%) until a clear, homogeneous emulsion was obtained. This cycle of water and GMO additions was continued until the water concentration exceeded 5 wt % with the following results:
25.00 g of No. 2 diesel fuel and 0.51 g of distilled water were measured into a flask, and portions of GMO (German, 90%) were added and mixed until dispersed. After addition of 1.72 g GMO, it was evident that the water and GMO were not going to mix to give a clear emulsion, although the water was well-dispersed. Upon addition of 1.00 g of anhydrous ethanol, the mixture formed a clear emulsion, which became cloudy upon further addition of 0.72 g of anhydrous ethanol. Addition of a 0.28 g portion of GMO again afforded a clear emulsion. Portions of water were then added followed by portions of GMO until clear emulsions were obtained. The proportions affording clear, stable emulsions at room temperature are summarized in the following table:
5.0 g of oleic acid was first mixed with 6.0 g of hydrous ethanol (190 proof) in a flask. 0.55 g of 28% aqueous ammonium hydroxide was then added and mixed until a clear homogeneous solution was obtained. 22.5 g of diesel fuel was then added in portions and mixed to the following final proportions:
The resulting emulsion was clear and homogeneous at 23° C.
Upon addition of 27.5 g more diesel fuel, phase separation occurred. Crude α-GMO obtained by direct synthesis was then added in portions until a clear homogeneous emulsion was obtained with the following final proportions:
The emulsion was stable at 23° C. Upon cooling to 12° C., phase separation occurred. Upon addition of 0.5 wt % α-GMO, the emulsion cleared and remained stable to 0° C. Results of emissions tests shown in the table following Example 16 show a dramatic drop in NO emissions using the formulation with ammonia even though cetane enhancer is absent. The same formulation without ammonia showed no reduction in emissions. This is strong evidence that ammonia is exerting a “neutralizing” effect on NOx, presumably by reacting with NO to give nitrogen and water.
Two emulsions were formulated by successive mixing of ingredients in a flask to the following final compositions:
The cetane enhancer, 2-ethylhexyl nitrate, was added in proportions of 1.5 and 3 wt % to compositions 1 and 2, respectively. The properties of the resulting emulsions were compared to the original emulsions lacking cetane enhancer. All compositions remained stable to temperatures down to −8° C., although those having cetane enhancer appeared to be somewhat more stable to colder temperatures. The cetane number of composition 1 was raised from 37.8 to 51.1 by the addition of 1.5 wt % of 2-ethylhexyl nitrate.
Selected formulations were tested for cetane number, exhaust emissions, and mileage at California Environmental Engineering using a 1995 Dodge Ram and certified testing procedures. The results are presented in the following table:
The test vehicle employed represents a late model vehicle that produces inherently lower emissions than earlier model or heavy-duty engines. Although a number of formulations afforded emissions reductions when tested in an earlier model engine (1989 Cummins), the same formulations afforded little or no emissions reductions when re-tested in the 1995 vehicle. Both compositions referenced in Example 16 afforded dramatic reductions in NOx and particulate, while fuel economy was maintained. Examination of particulate filters used in these tests shows very low soot levels. The cetane enhancer proved important in realizing emissions reduction by reducing the ignition time of the fuel which would otherwise be retarded by the presence of water and ethanol. As noted, Example 15 containing ammonia also showed a dramatic reduction in NOx emissions, even though one would predict no emissions reduction because cetane enhancer was absent. Indeed, there was no reduction in particulate emissions as expected. This powerful NOx reducing effect of ammonia is in addition to the emissions reducing effects of water and ethanol in the presence of cetane enhancer. Thus, formulations having both water, ethanol, ammonia, and cetane enhancer are predicted to give twice the NOx emissions reduction shown for either separately.
10.0 g of certified diesel and 1.0 g of ethylene glycol were added to a flask and mixed. GMO (German, 90%) was added in portions and mixed until a clear, homogeneous emulsion was obtained with the following final composition:
Although stable at room temperature, chilling quickly induced the precipitation of white solids.
71.35 g of certified diesel fuel (lot D-538) was weighed into a flask. 12.63 g of hydrous ethanol (190 proof, USP grade) was added and mixed to give two immiscible phases. 10.62 g of oleic acid (USP grade) was added and mixed to give a very hazy unstable suspension. 190 g of 28% ammonium hydroxide solution (technical grade) was added and mixed to give a clear homogeneous emulsion. 1.50 g of 2-ethyl hexyl nitrate was added and mixed. The emulsion was stable at room temperature but became very cloudy upon cooling to 0° C. Portions of high purity GMO (German) were added and mixed until the resulting emulsion was stable overnight at −14° C. 2.00 g of GMO was required. The final proportions required to produce stable emulsions at various temperatures are shown in the following table:
Results of emissions tests shown in the table following Example 16 show a dramatic drop in NOx emissions using the formulation with ammonia. The same formulation without ammonia showed a smaller reduction in NOx and particulate emissions. This provides additional confirmation that ammonia is exerting a “neutralizing” effect on NOx.
A low-water microemulsion containing approximately 2 wt % water rather than relatively high-water microemulsions containing approximately 10 wt % water have also been found to be effective to reduce undesired emissions and to provide desirable mileage and performance. By contrast, a relatively high-water microemulsion shows increased emissions reductions but also exhibits a 15% loss in mileage and peak horsepower (see table):
The low water formulation shown below was produced to examine its cold temperature stability. The formulation had the following proportions:
The above formulation was stable at room temperature and above but immediately separated into two phases below 60° F.
It is also desirable to reduce the ethanol content to raise the flashpoint of the formulation to within the diesel range. The following formulation was prepared with 8% ethanol rather than 12% ethanol. This formulation had the following composition:
The above microemulsion was extremely stable to the cold remaining clear down to 6.4° F. and slightly viscous but unbroken down to 1.1° F.
The following describes a formulation of 110 gallons of blendstock. To a 250 gallon tote was added: 1 drum (55 gallons) of oleic acid, 35 gallons of 190-proof ethanol, and 13 liters of 2-ethyl hexanitrate (2-EHN). Contents were added at ambient temperature and pressure (e.g., 25 degrees Celcius and 0.986 atm) without further purification or treatment. The ethanol and oleic acid was transferred by electric pump, which functioned as splash blending, and the 2-EHN was poured manually. In a separate container, 9.5 gal of ammonium hydroxide (28%) was added to 5.5 gal of water. This aqueous mixture was then manually added to the tote containing the organic components. Heat and bubbles are generated during the addition of the aqueous components as the ammonium hydroxide neutralizes the oleic fatty acid to form an ammonium salt. After 5 min of manual stirring or swirling, a single phase is formed. Bubbles and heat subside within 30 minutes of addition.
The blendstock exhibited the following physical properties:
Blendstock is manually poured or transferred by electric pump to a container or vehicle fuel tank containing diesel up to a volume concentration of 43% (e.g., 43% blendstock, 57% diesel or other components) to form a fuel composition. Or, 2-20 gallons of blendstock is added to a fuel tank containing at least 25 gallons of diesel to form at least 27-45 gallons of the fuel composition. No additional mixing, agitation, or treatment takes place.
The fuel composition exhibited the following physical properties. The flashpoint of the fuel composition stays below 38 degrees Celsius for blendstock concentrations greater than 1% (e.g., more than 1% of the fuel composition being blendstock), but increases for concentrations below 1% (e.g., less than 1% of the fuel composition being blendstock).
In the preceding description, various aspects of claimed subject matter have been described. For purposes of explanation, specific numbers, systems and/or configurations were set forth to provide a thorough understanding of the claimed subject matter. However, it should be apparent to one skilled in the art having the benefit of this disclosure that claimed subject matter may be practiced without the specific details. In other instances, features that would be understood by one of ordinary skill were omitted and/or simplified so as not to obscure claimed subject matter. While certain features have been illustrated and/or described herein, many modifications, substitutions, changes and/or equivalents will now occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and/or changes as fall within the true spirit of claimed subject matter.
The invention can also be described in the following paragraphs:
A/0. A blendstock for forming a fuel composition for use in internal-combustion engines, the blendstock comprising:
a polar fluid component;
a microblender component; and
a neutralizer component being present in an amount effective to substantially neutralize the microblender component to allow for the microblender component to substantially spontaneously blend with the polar fluid component.
A/1. The blendstock of paragraph A/0, wherein the neutralizer component includes an ammonia component.
A/2. The blendstock of paragraph A/0, wherein the blendstock is added to a hydrocarbon fuel to form the fuel composition.
A/3. The blendstock of paragraph A/2, where the hydrocarbon fuel includes a diesel fuel component.
A/4. The blendstock of paragraph A/0, wherein the polar fluid component includes a water component and an alcohol component.
A/5. The blendstock of paragraph A/4, wherein the alcohol component is selected from a group consisting of methanol, ethanol, (a) n-propyl alcohol, (b) iso-propyl alcohol, (c) n-butyl alcohol, and a mixed alcohol formulation.
A/6. The blendstock of paragraph A/0, wherein the polar fluid component is hydrous ethanol having a water content of 5-20%.
A/7. The blendstock of paragraph A/0, wherein the microblender component includes a fatty acid component.
A/8 The blendstock of paragraph A/7, wherein the fatty acid component includes oleic acid.
A/9. The blendstock of paragraph A/1, wherein the ammonia component includes ammonium hydroxide.
B/0. A fuel composition for use in internal-combustion engines, the fuel composition comprising:
a fuel component including an amount of a hydrocarbon fuel; and
a blendstock component including a micro-blend of a polar fluid, a microblender, and a neutralizer, the blendstock component being present in an amount effective for the micro-blend to disperse throughout the first amount of fuel.
B/1. The fuel composition of paragraph B/0, wherein the fuel component includes a biodiesel fuel component.
B/2. The fuel composition of paragraph B/1, where the hydrocarbon component includes a diesel fuel component.
B/4. The fuel composition of paragraph B/0, wherein the polar fluid includes a water component and an alcohol component.
B/5. The fuel composition of paragraph B/4, wherein the alcohol component is selected from a group consisting of methanol, ethanol, (a) n-propyl alcohol, (b) iso-propyl alcohol, (c) n-butyl alcohol, and a mixed alcohol formulation.
B/6. The fuel composition of paragraph B/0, wherein the polar fluid is hydrous ethanol having a water content of 5-20%.
B/7. The fuel composition of paragraph B/0, wherein the neutralizer includes an ammonia component present in an amount effective to substantially neutralize the microblender.
B/8. The fuel composition of paragraph B/7, wherein the microblender includes a fatty acid component.
B/9 The fuel composition of paragraph B/8, wherein the fatty acid component includes oleic acid.
B/10. The fuel composition of paragraph B/8, wherein substantially neutralizing the fatty acid component with the ammonia component produces an ammonium salt component.
C/0. A lubricating micro-blend comprising:
a polar fluid component;
a neutralizer component; and
a microblender component being present in an amount effective for the polar fluid component, the neutralizer component, and the microblender component to substantially spontaneously form the lubricating micro-blend.
C/1. The lubricating micro-blend of paragraph C/0, wherein the lubricating micro-blend is added to a hydrocarbon fuel component to form a fuel composition.
C/2. The lubricating micro-blend of paragraph C/1, where the hydrocarbon fuel component includes a diesel fuel component.
C/3. The lubricating micro-blend of paragraph C/0, wherein the polar fluid component includes a water component and an alcohol component.
C/4. The lubricating micro-blend of paragraph C/4, wherein the alcohol component is selected from a group consisting of methanol, ethanol, (a) n-propyl alcohol, (b) iso-propyl alcohol, (c) n-butyl alcohol, and a mixed alcohol formulation.
C/5. The lubricating micro-blend of paragraph C/0, wherein the polar fluid component includes hydrous ethanol having a water content of 5-20%.
C/6. The lubricating micro-blend of paragraph C/0, wherein the microblender component includes a fatty acid component.
C/7 The lubricating micro-blend of paragraph C/7, wherein the fatty acid component includes oleic acid.
C/8. The lubricating micro-blend of paragraph C/8, wherein the neutralizer component includes an ammonia component.
A/0. A method of formulating a fuel composition for use in internal-combustion engines, the method comprising:
providing one or more polar fluids;
selecting a microblender;
selecting a neutralizer;
forming a blendstock by adding the neutralizer and the microblender to the one or more polar fluids;
providing an amount of fuel; and
forming the fuel composition by adding the blendstock to the amount of fuel.
A/1. The method of paragraph F/0, wherein the amount of fuel includes a diesel fuel component.
A/2. The method of paragraph F/0, wherein the blendstock includes a cetane enhancer component.
A/3. The method of paragraph F/0, wherein the one or more polar fluids include an alcohol component.
A/4. The method of paragraph F/3, wherein selecting the polar fluid involves choosing the alcohol component from a group consisting of methanol, ethanol, (a) n-propyl alcohol, (b) iso-propyl alcohol, (c) n-butyl alcohol, and a mixed alcohol formulation.
A/5. The method of paragraph F/0, wherein selecting the one or more polar fluids involves blending an alcohol component and a water component.
A/6. The method of paragraph F/0, wherein the selecting the one or more polar fluids involves choosing hydrous ethanol having a water content of 5-20%.
A/7. The method of paragraph F/0, wherein selecting the microblender involves choosing a fatty acid component.
A/8 The method of paragraph F/7, wherein the fatty acid component includes oleic acid.
A/9. The method of paragraph F/7, wherein selecting the neutralizer involves choosing an ammonia component.
A/10. The method of paragraph F/9, wherein adding the neutralizer and the microblender to the one or more polar fluids forms a micro-blend of the ammonia component, fatty acid component, and the one or more polar fluids without application of a heat source or stirring.
B/0. A method of forming a fuel composition, the method essentially consisting of:
forming a blendstock by introducing a microblender and a neutralizer to a polar fluid; and
forming the fuel composition by introducing the blendstock to an amount of fuel.
B/1. The method of paragraph B/0, wherein the amount of fuel includes a diesel fuel component.
B/2. The method of paragraph B/0, wherein the amount of fuel includes a biodiesel component.
B/3. The method of paragraph B/0, wherein the polar fluid includes an alcohol component.
B/4. The method of paragraph B/3, wherein the alcohol component is chosen from a group consisting of methanol, ethanol, (a) n-propyl alcohol, (b) iso-propyl alcohol, (c) n-butyl alcohol, and a mixed alcohol formulation.
B/5. The method of paragraph B/0, wherein the polar fluid includes a blend of an alcohol component and a water component.
B/6. The method of paragraph B/0, wherein the polar fluid includes hydrous ethanol having a water content of 5-20%.
B/7. The method of paragraph B/0, wherein the microblender includes a fatty acid component.
B/8 The method of paragraph B/7, wherein the fatty acid component includes oleic acid.
B/9. The method of paragraph B/7, wherein the neutralizer includes an ammonia component.
B/10. The method of paragraph B/0, wherein introducing the neutralizer and the microblender to the polar fluid forms a stable micro-blend at standard temperature and pressure.
C/0. A method of forming a micro-blend fuel treatment, the method comprising:
providing a polar fluid;
selecting a microblender;
selecting a neutralizer; and
adding the neutralizer and the microblender to the polar fluid to form the micro-blend fuel treatment;
wherein the step of adding the neutralizer and the microblender to the polar fluid results in the polar fluid, the microblender, and the neutralizer substantially spontaneously blending together.
C/1. The method of C/0, further comprising providing an amount of fuel, and adding the micro-blend fuel treatment to the amount of fuel to form a fuel composition.
C/2. The method of paragraph C/1, wherein the amount of fuel includes a diesel fuel component.
C/3. The method of paragraph C/1, wherein the amount of fuel includes a biodiesel fuel component.
C/4. The method of paragraph C/0, wherein the polar fluid includes an alcohol component.
C/5. The method of paragraph C/4, wherein the alcohol component is chosen from a group consisting of methanol, ethanol, (a) n-propyl alcohol, (b) iso-propyl alcohol, (c) n-butyl alcohol, and a mixed alcohol formulation.
C/6. The method of paragraph C/0, wherein providing the polar fluid involves blending an alcohol component and a water component.
C/7. The method of paragraph C/0, wherein the polar fluid component includes hydrous ethanol having a water content of 5-20%.
C/8. The method of paragraph C/0, wherein selecting the microblender involves choosing a fatty acid component.
C/9. The method of paragraph C/8, wherein choosing the fatty acid component involves choosing oleic acid.
C/10. The method of paragraph C/8, wherein the selecting the neutralizer involves choosing an ammonia component.
C/11. The method of paragraph C/0, wherein adding the neutralizer and the microblender to the polar fluid forms a micro-blend without application of a heat source or stirring.
D/0. A method of forming a pre-combustion fuel treatment, the method comprising:
providing a polar fluid;
selecting a microblender;
selecting a neutralizer; and
adding the microblender and the neutralizer to the polar fluid to form the pre-combustion fuel treatment;
wherein the step of adding the microblender and the neutralizer to the polar fluid results in a substantially spontaneous reaction which blends together the polar fluid, the microblender, and the neutralizer.
D/1. The method of paragraph D/0, further comprising providing an amount of fuel, and adding the pre-combustion fuel treatment to the amount of fuel to form a fuel composition.
D/2. The method of paragraph D/0, further comprising combining the pre-combustion fuel treatment with a post-combustion fuel treatment.
D/3. The method of paragraph D/2, wherein the post-combustion fuel treatment includes a diesel oxidation catalyst.
D/4. The method of paragraph D/3, wherein the amount of fuel includes a diesel fuel component.
D/5. The method of paragraph D/1, wherein the amount of fuel includes a biodiesel component.
D/6. The method of paragraph D/0, wherein the polar fluid includes an alcohol component.
D/7. The method of paragraph D/6, wherein providing the polar fluid involves choosing the alcohol component from a group consisting of (a) n-propyl alcohol, (b) iso-propyl alcohol, (c) n-butyl alcohol, and a mixed alcohol formulation.
D/8. The method of paragraph D/0, wherein providing the polar fluid involves blending an alcohol component and a water component.
D/9. The method of paragraph D/0, wherein the polar fluid component includes hydrous ethanol having a water content of 5-20%.
D/10. The method of paragraph D/0, wherein selecting the microblender involves choosing a fatty acid component.
D/11 The method of paragraph D/10, wherein choosing the fatty acid component involves choosing oleic acid.
D/12. The method of paragraph D/10, wherein selecting the neutralizer involves choosing an ammonia component.
D/13. The method of paragraph D/0, wherein adding the neutralizer and the microblender to the polar fluid forms a micro-blend at ambient temperature and pressure.
E/0. A method of forming a lubricating micro-blend, the method comprising:
providing a polar fluid;
selecting a microblender;
selecting a neutralizer; and
forming the lubricating micro-blend by adding the neutralizer and the microblender to the polar fluid, wherein the neutralizer substantially neutralizes the microblender allowing for substantially neutralized microblender to substantially spontaneously blend with the polar fluid.
E/1. The method of paragraph E/0, wherein the lubricating micro-blend is applied to a drill in a drilling application.
E/2. The method of paragraph E/0, wherein the polar fluid includes an alcohol component.
E/3. The method of paragraph E/0, wherein providing the polar fluid involves choosing an alcohol component from a group consisting of ethanol, methanol, (a) n-propyl alcohol, (b) iso-propyl alcohol, (c) n-butyl alcohol, and a mixed alcohol formulation.
E/4. The method of paragraph E/0, wherein providing the polar fluid involves blending an alcohol component and a water component.
E/5. The method of paragraph E/0, wherein the polar fluid includes hydrous ethanol having a water content of 5-20%.
E/6. The method of paragraph E/0, wherein selecting the microblender component involves choosing a fatty acid component.
E/7 The method of paragraph E/6, wherein choosing the fatty acid component involves choosing oleic acid.
E/8. The method of paragraph E/6, wherein selecting the neutralizer involves choosing an ammonia component.
E/9. The method of paragraph E/8, wherein adding the neutralizer and the microblender to the polar fluid forms a micro-blend at standard temperature and pressure.
F/0. A method of supplying a fuel composition to a customer, the method comprising:
providing a filling station;
providing a blendstock in a first tank at the filling station;
providing a fuel in a second tank at the filling station;
and pumping the blendstock and the fuel into a vehicle belonging to a customer.
F/1. The method of paragraph F/0, wherein the blendstock is mixed with a first amount of the fuel at the filling station to produce the fuel composition, and the fuel composition is pumped into a fuel tank of the vehicle belonging to the customer.
F/2. The method of paragraph F/0, wherein the blendstock is pumped into a first tank in the vehicle, the fuel is pumped into a second tank in the vehicle, and apparatus in the vehicle combines the blendstock with the fuel to produce the fuel composition.
F/3. The method of paragraph F/1, wherein the blendstock is mixed with the fuel prior to the pumping step.
F/4. The method of paragraph F/0, wherein the fuel includes a diesel fuel component.
F/5. The method of paragraph F/0, wherein the blendstock includes a polar fluid, a microblender, and a neutralizer in an amount effective to substantially neutralize the microblender.
F/6. The method of paragraph F/5, wherein the polar fluid includes an alcohol component.
F/7. The method of paragraph F/6, wherein the alcohol component is chosen from a group consisting of ethanol, methanol, (a) n-propyl alcohol, (b) iso-propyl alcohol, (c) n-butyl alcohol, and a mixed alcohol formulation.
F/8. The method of paragraph F/5, wherein the polar fluid includes a blend of an alcohol component and a water component.
F/9. The method of paragraph F/5, wherein the polar fluid includes hydrous ethanol having a water content of 5-20%.
F/10. The method of paragraph F/5, wherein the microblender includes a fatty acid component.
F/11. The method of paragraph F/10, wherein the fatty acid component includes oleic acid.
F/12. The method of paragraph F/10, wherein the neutralizer includes an ammonia component.
F/13. The method of paragraph F/5, wherein the polar fluid, the microblender, and the neutralizer form a micro-blend without application of a heat source or stirring.
This application is a continuation-in-part of U.S. patent application Ser. No. 13/966,207, filed Aug. 13, 2013 and entitled METHOD OF FORMULATING A FUEL COMPOSITION FOR USE IN INTERNAL-COMBUSTION ENGINES, which application is a continuation-in-part of U.S. patent application Ser. No. 13/217,171, filed Aug. 24, 2011 and entitled METHOD OF FORMULATING A FUEL COMPOSITION FOR USE IN INTERNAL-COMBUSTION ENGINES, which application is a continuation of U.S. patent application Ser. No. 12/105,164, filed Apr. 17, 2008 and entitled METHOD OF FORMULATING A FUEL COMPOSITION FOR USE IN INTERNAL-COMBUSTION ENGINES, which application claims priority to U.S. Provisional Patent Application Ser. No. 60/974,779, filed Sep. 24, 2007 and entitled MICROEMULSION FUEL COMPOSITIONS AND METHODS FOR PRODUCING THE SAME and also claims priority to U.S. Provisional Patent Application Ser. No. 61/036,007, filed Mar. 12, 2008 and entitled FUEL COMPOSITIONS FOR USE IN INTERNAL-COMBUSTION ENGINES AND METHODS OF FORMING USING SUCH COMPOSITIONS, each of which is incorporated herein by reference in its entirety for all purposes.
| Number | Date | Country | |
|---|---|---|---|
| 60974779 | Sep 2007 | US | |
| 61036007 | Mar 2008 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12105164 | Apr 2008 | US |
| Child | 13217171 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13966207 | Aug 2013 | US |
| Child | 14318365 | US | |
| Parent | 13217171 | Aug 2011 | US |
| Child | 13966207 | US |
