WO2017214493A1 - Mélanges de combustibles hygroscopiques et leurs procédés de production - Google Patents

Mélanges de combustibles hygroscopiques et leurs procédés de production Download PDF

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WO2017214493A1
WO2017214493A1 PCT/US2017/036731 US2017036731W WO2017214493A1 WO 2017214493 A1 WO2017214493 A1 WO 2017214493A1 US 2017036731 W US2017036731 W US 2017036731W WO 2017214493 A1 WO2017214493 A1 WO 2017214493A1
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fuel
agent
compound
energy
water
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Ronald Mills
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FUELTEK Inc
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FUELTEK Inc
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    • C10L1/00—Liquid carbonaceous fuels
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Definitions

  • the present disclosure is directed to hygroscopic fuel blends and processes for producing same.
  • the fuel blends disclosed herein can absorb water and provide an enhanced energy output for use with internal combustion engines.
  • the present invention is in the field of fuel compositions, for example, those used with internal combustion engines.
  • Such engines may be used in various vehicles and other applications, including automobiles, trucks, locomotives, airplanes, and electric generators.
  • Such engines may comprise four cycle or two cycle engines.
  • Gasoline the average American's idea of a "fuel” is not a homogenous substance. Rather, it is a mixture of hundreds of different molecules and additives to impart specific characteristics, such as corrosion resistance.
  • Petroleum based internal combustion engine fuels are typically produced by being separated from crude oil by distillation and isolating predominately a distribution of alkane compounds centered around 8 carbons (octane) for gasoline and 12 carbons (cetane) for diesel.
  • Nicolas Carnot was a French physicist and military engineer who, in his 1824 "Reflections on the Motive Power of Fire", gave the first successful theoretical account of heat engines, now known as the Carnot cycle, thereby laying the foundation for the second law of thermodynamics. He is often described as the "father of thermodynamics", being responsible for such concepts as Carnot efficiency, Carnot theorem, the Camot heat engine, and others.
  • the maximum efficiency is defined as the change in temperature between the combustion temperature and the exhaust temperature divided by the combustion temperature.
  • the European Fuel Quality Directive allows up to 3% methanol with an equal amount of co-solvent to be blending in gasoline sold in Europe.
  • China uses more than one billion gallons of methanol per year as a transportation fuel in both low level blends used in existing vehicles, and as high level blends in vehicles designed to accommodate the use of methanol fuels, an M-85 gasoline substitute and M-15 gasohol made from coal.
  • Gasoline and diesel each including hundreds of components, as well as methanol and ethanol, which are largely single chemical component fuels, use additives to achieve desired lubricity, anti- corrosive, anti foam, and other characteristics to make them suitable as fuels in a particular use.
  • MTBE was added to gasoline to provide oxygen to reduce emissions.
  • Ethanol has replaced MTBE, and is also used to provide oxygen.
  • the consumer may pay less per gallon for E-85, but this price reduction is often less than the decrease in energy per gallon that is reflected in a reduction in the miles per gallon (MPG) provided by such fuels.
  • MPG miles per gallon
  • the chief advantage of a methanol fuel is that it could be adapted to present internal combustion engines with a minimum of modification in both engines and infrastructure to store and deliver liquid fuel.
  • the world first used carbon based fuels in the form of wood, peat, and coal. Over time, the world began using petroleum derived hydrocarbons to bum hydrogen with carbon. Such petroleum based hydrocarbons (such as gasoline and diesel) provide a hydrogen to carbon ratio between about 2 and 3 to t Now alcohols (particularly methanol) offer even greater hydrogen content in the fuel. Each hydrogen contains twice the energy on combustion of a carbon with l/12th the weight, and produces water and not carbon dioxide. These are very desirable conditions associated with hydrogen as a fuel in terms of its impact on the environment. The hydrogen to carbon ratio of hydrocarbons is typically between 2 and 3 to 1, with ethanol providing 3: 1 and methanol providing 4: 1.
  • Fuels particularly petroleum-based fuels, have been generally viewed to be both (a) combustive agents and (b) compositions designed to foster, or average-out, heterogeneous chemical reactions. Fuels are often designed to be fungible in their particular compositional mix. For a given volume of fuel added to the active "combustion" chamber of an engine, the induced chemical transformation is considered to be a single-valued, average "bum”. For a gasoline or Otto cycle four-stroke engine, the effect is ideally defined to be: adiabatic compression, heat addition at constant volume, adiabatic expansion, and rejection of heat at constant volume.
  • the effect is ideally defined to be: isentropic compression, reversible constant pressure heating, isentropic expansion, and reversible constant volume cooling.
  • the effect is summarized as: Work out (Wout) is done by the working fluid expanding against the piston, which produces usable torque.
  • Fuels delivered into tanks will be acclimatized with water pooling at the bottom of the fuel tank in 72 hours or less. Water in fuel tanks, lines, injectors, filters, etc. will freeze more readily than the fuel. Most fuels freeze at lower than -20°F (-7°C); water freezes at 32°F (0°C). Water allowed to remain in hydrocarbon fuel (aviation and diesel) cultures a microorganism or bacteria that feed on the hydrocarbons in the fuel. These microorganisms will produce offspring (spores) which become active and produce colonies and mats of growth. The colonies of microorganisms produce slime, which clog filters by covering the media. Water in suspension in burning fuel reduces the amount of energy available (BTUs/KCals), and will result in less horsepower output.
  • BTUs/KCals energy available
  • Acetone when added to gasoline, improves the mileage up to a dosage of about 3 fluid ounces per 10 gallons of gasoline and beyond that dosage, a further increase in acetone dosage decreases the mileage from the 3 oz /10 gal peak. At a dosage of approximately 6 ounces per 10 gallons of gasoline the mileage is approximately the same as with no acetone; 3. 3.30% by volume of nitromethane in methanol is the minimum dosage of nitro-methane that can be used as a fuel.
  • a class of detonative sub-fuel unit components can be determined through analysis of the parameters of the stabilized fuel's component's dipole density (which is the molecular weight divided by the dipole moment at 20 degrees centigrade measured in Debye) and then constraining the composition's mixture to those solutions which will exist in dynamic equilibrium within the stabilized combustive fuel.
  • Temporary transformations between the molecular compounds found in the resulting solution form a distributing dynamic 'cage' solution, as the core of material of the detonative sub-fuel component is distributed in a unique molar ratio of component organic compounds through, as the principal force, the stabilized combustive fuel sub-unit's dipole moments.
  • a fuel additive includes a compound for adding to a base fuel to provide the base fuel with (1) hygroscopic properties and (2) detonative potential energy.
  • the compound includes a polar protic agent in an amount from about 2% to about 10 % by volume of the compound.
  • the compound also includes a polar aprotic agent in an amount ranging from about 10% to about 32 % by volume of the compound.
  • the compound also includes an explosive agent in an amount ranging from about 15% to about 32% by volume of the compound.
  • the compound also includes a nonpolar agent in an amount ranging from about 2% to about 10 % by volume of the compound.
  • the polar protic agent includes one of methanol, ethanol, butanol, n-propanol, or combinations thereof.
  • the polar aprotic agent includes one of acetone, nitromethane, ethyl acetate, dichloromethane, or combinations thereof.
  • the explosive agent includes one of nitroalkanes such as, for example, 2-ethylhexyl nitrate, dinitromethane, or trinitromethane, IsoOctane, acetone, acetone peroxide, or combinations thereof.
  • the detonative agent is 2- ethyhexyl nitrate.
  • the nonpolar agent includes one of petroleum distillates such as, for example, liquefied petroleum gas, naphtha, kerosene, jet fuel, diesel, heavy fuel oils, or lubricating oils, benzene derivatives such as, for example, phenol, toluene, aniline, or biphenyls, or combinations thereof.
  • the fuel additive includes at least one additional polar aprotic agent.
  • a synthetic fuel in another embodiment, includes a base fuel having a first energy density.
  • the synthetic fuel also includes a compound.
  • the compound includes a water absorbing agent for absorbing water from the base fuel to prevent poor combustion.
  • the compound also includes an explosive agent having a detonative energy value that is sufficient so as to provide the compound with a second energy density equal to or greater than the first energy density.
  • the synthetic fuel includes about 15% to about 85% by volume of the base fuel and about 15% to about 85% by volume of the compound.
  • the water absorbing agent has a lower energy density than the first energy density.
  • the water absorbing agent includes one of methanol, ethanol, acetone, or combinations thereof.
  • the explosive agent includes one of nitroalkanes such as, for example, 2-ethylhexyl nitrate, dinitromethane, or trinitromethane, IsoOctane, acetone, acetone peroxide, or combinations thereof.
  • the base fuel includes one of gasoline, diesel, biodiesel, jet fuel such as, for example, JP1, JP2, JP3, JP4, JP5, JP6, JP7, JP8, JP9, JP10, Jet A, Jet A-l, or Jet B, avgas, ethanol, methanol, butanol, naphtha, or combinations thereof.
  • the compound also includes a polar protic agent.
  • the compound also includes a polar aprotic agent.
  • the polar protic agent and the polar aprotic agent form a molecular cage for encapsulating the explosive agent within the compound.
  • a method for using a synthetic fuel includes providing a synthetic fuel.
  • the synthetic fuel includes a base fuel.
  • the synthetic fuel also includes a compound including a water absorbing agent and an explosive agent.
  • the method also includes combusting the base fuel to produce mechanical and thermal energy.
  • the method also includes releasing, by an endothermic solvenation reaction initiated by the mechanical and thermal energy, the explosive agent from the compound.
  • the method also includes detonating, in the presence of the mechanical and thermal energy, the released explosive agent.
  • the method also includes injecting the synthetic fuel into a combustion chamber of an engine.
  • the step of combusting also includes producing a spark from a spark plug of the engine.
  • the step of combusting also includes pressurizing air in the combustion chamber.
  • the method also includes absorbing, by the water absorbing ingredient, water in the synthetic fuel.
  • FIG. 1 shows a general representation of a water molecule outside a possible schematic structure in which the detonative fuel component is 'caged' or surrounded by the stabilizing fuel component.
  • the cage may be a buckyball (Buckminster fullerene) including 5 or 6 other polygonal sided faces as shown;
  • FIG. 2 shows a general representation of a possible schematic structure in which the water molecule has been absorbed into the ⁇ caged' structure together with the detonative fuel component surrounded by the stabilizing fuel component.
  • This 'cage' is any molecule composed entirely of carbon, in the form of a hollow sphere, ellipsoid, or tube.
  • Spherical fullerenes are also called buckyball, and they resemble the balls used in association football. Cylindrical ones are called carbon nanotubes or bucky tubes.
  • Fullerenes are similar in structure to graphite, which is composed of stacked graphene sheets of linked hexagonal rings; but they may also contain pentagonal (or sometimes heptagonal) rings.
  • the "mortar” which holds the fullerene structure together is small molecules with relatively high dipole moment densities (e.g., greater than about 1.5 D, preferably greater than about 2 D) and the "bricks" are larger nitrated molecules. Furthermore, such a combination produces an unexpected previously unknown benefit in that the energy density of this "cage", when used in an engine, is greater than the sum of the energy of the components of the cage when measured by a calorimeter using conventional teachings (i.e., thereby producing a synergistic interaction).
  • the cage molecule performs best when mixed with 1/10 the concentration of nitromethane and 500 times the amount of acetone believed optimal for intemal- combustion engine fuels, and allows the cetane-improving nitro compound to positively impact the performance of a gasoline engine.
  • Gasoline storage tanks may contain varying amounts of separate phase water depending upon the tank volume. Water is the most common fuel contaminant. A process for creating a fuel that can effectively remove water from the storage containers by
  • Combustion waves come in subsonic (deflagration) and supersonic (detonation) values within their respective limits of fiammability or detonation.
  • the present invention is directed to fuels, fuel additives; and methods of producing such materials that result in enhanced mechanical energy output while absorbing water from the gasoline component of the mixture. It is believed that this enhanced mechanical energy output may result from an ability to safely commingle and harness different combustion waves in order to make for a more thermally efficient internal combustion engine.
  • Combining deflagrative combustion with a detonative or explosive combustion wave within an engine can create a far higher effective torque and consequent efficiency by joining the immediate kinetic "kick" of the detonative or explosive wave and the sustained pressure of the deflagrative wave on the piston head during the power stroke.
  • Devising a fuel blend that will, for a given range of combustive fuels e.g., gasoline, diesel, ethanol, methanol, butanol, or mixtures thereof
  • intermix to form a composition with the stabilizing and non-detonative combustible material while absorbing water may be accomplished by devising a dynamically stable solution of the two parts.
  • Methanol has about half the thermal energy density of gasoline, so that two gallons of methanol are required to provide the same thermal energy as one gallon of gasoline.
  • Butanol has about an equal thermal energy density as compared to gasoline.
  • One and one half times the volume of ethanol is required to have the same thermal energy as one gallon of gasoline.
  • the added materials depart from the conventional Carnot heat engine principles. These materials do not add to the thermal energy density of the fuel, but result in a secondary reaction under the conditions existing in the internal combustion engine creating additional mechanical energy while absorbing water and cooling the engine from the inside.
  • the fuel may be blended to provide the same combustive energy density as measured by calorimetry, (e.g., 128,700 BTU/gal as for diesel), but in which, because one or more of the components produces a detonative or explosive wave and another absorbs water in the mixture, the apparent energy density is higher.
  • calorimetry e.g., 128,700 BTU/gal as for diesel
  • the physical chemistry of the Camot cycle is supplemented by the physical chemistry of the present invention.
  • the engine provides something of a chemical processing plant with temperatures and pressures available to make the secondary reactions occur.
  • This composition is one where the molecular pressures of the stabilizing combustive fuel continually "cage" a core detonative material together with water molecules whose dipole nature maintains the cage assembly in place until heat is available to overcome the bonding forces from relatively weak dipole attractions.
  • the heat provided by combustion of the base combustive fuel provides the energy necessary to drive a solvation reaction, which breaks down the "cage", which is followed by detonation or explosion of the detonative material. The detonation accelerates the large mass of combustion products into the piston.
  • the cage allows the explosive material to survive combustion and persist to detonate even with the water molecule present. If the explosive material were simply combusted, it would only add a small increment to the heat density of the fuel, providing only a small (if any) increase in Camot efficiency. Instead, the explosive in the secondary reaction is characterized by detonation with associated supersonic velocities to dramatically increase the apparent thermal efficiency of the engine. When the cage breaks down, the water molecules are released as water vapor together with the outgases of the engine.
  • Water is known as the universal solvent, having the highest dipole moment density, with a high dipole moment and a relatively small molecular weight. Methanol has a lower dipole moment density, but approaches the usefulness of water as a solvent.
  • the solvation or solution reaction by which sugar or another material dissolves in water, is an endothermic reaction requiring the input of heat.
  • Detonation of an explosive is similar, as it requires an input of energy (or activation energy) to achieve detonation.
  • the detonative fuel component material may be used to raise the energy density of gasohol, ethanol, or methanol to the energy density of gasoline.
  • a "Hygroscopic Fuel” product may be an ⁇ - ⁇ 85 product similar to E-85 in that it contains 85% methanol in summer and 70% in winter but with the detonative fuel component at a dose of as little as one part to 1 ,000 parts and providing an apparent energy density about equal to that of gasoline.
  • a "Hygroscopic Diesel” product may be blended with diesel fuel at one part to about one hundred parts of diesel, increasing the MPG of the vehicle by as much as two times.
  • a gallon of "Hygroscopic Diesel” may contain about 0.1% detonative fuel component, about 0.1% of a stabilizing, water absorbing and enhancing combustive mixture, and about 99.8% biodiesel, which can be made from a constant feed stock such as soy beans.
  • the present invention is directed to a process for producing an internal combustion engine fuel.
  • the process comprises: (1) selecting a petroleum based fuel to be replaced which contains up to 20% water by volume; (2) identifying its combustive, performance, and energy values; (3) selecting a polar, small-molecule hydrocarbon (e.g., having 4 or less carbon atoms, for example, acetone and/or an alcohol) having a known deflagrative combustion value as a fuel stabilizing component; (4) comparing the known deflagrative combustion value of the fuel stabilizing component to the energy value of the petroleum-based fuel to be replaced; (5) calculating the relative energy deficiency of the fuel stabilizing component against the petroleum-based fuel to be replaced; and (6) forming a fuel mixture by combining with the fuel stabilizing component that amount of a detonative fuel component which will provide an energy density sufficient to substantially equal the combustive, performance, and energy values of the petroleum-based fuel to be replaced.
  • a polar, small-molecule hydrocarbon e.g.,
  • a class of detonative fuel components can be determined through analysis of the dipole density of the other fuel components.
  • the dipole density is the dipole moment at 20° C. measured in Debye of the particular component divided by the molecular weight of the component.
  • the fuel composition is then constrained to those mixtures which will exist in dynamic equilibrium between the molecular compounds found in the resulting solution of the stabilized combustive fuel.
  • a mixture is then formed by mixing a selected detonative fuel component (e.g., a nitro-alkane such as 2-ethylhexyl nitrate) with the stabilizing combustive fuel component so as to form a distributed dynamic "cage" solution in which the detonative fuel component is dispersed within the stabilizing combustive fuel component as a result of the dipole moment of the stabilized combustive fuel component.
  • the fuel unit may comprise a concentrated mixture that may be diluted by adding to another base fuel material.
  • the present disclosure is directed to a fuel blend including the stabilizing fuel component and the detonative fuel component (interchangeably referred to herein as a core polar component or material) blended together with a base combustive fuel (e.g., diesel fuel, gasoline, methanol, ethanol, or other combustible liquid fuel) that contains separate phase water.
  • a base combustive fuel e.g., diesel fuel, gasoline, methanol, ethanol, or other combustible liquid fuel
  • a process for devising a stable and usable hygroscopic liquid fuel that combines deflagrative and detonative combustion waves suitable for use in internal combustion engines would enable the partial or complete replacement of petroleum-based fuels with fuels that include a higher hydrogen to carbon ratio. As a general rule, the greater this ratio, the cleaner the emissions.
  • the ability to substitute a "Hygroscopic Fuel” or “Hygroscopic Diesel” for gasoline or diesel substantially lowers the emissions of vehicles, reduces the carbon footprint and solves the vexing problem of water in fuel containers. For example, for each 100 gallons of diesel saved by use of "Hygroscopic Diesel", one carbon credit is earned, shrinking the carbon footprint of diesel fuel use.
  • a single "treatment" of the proposed fuel blend can potentially eliminate up to 20% of the separate phase water from any fuel storage container returning it to the environment as water vapor and the corresponding fuel mixture would retain its enhanced energy output.
  • To retain the actual effective energy provided within each "bum unit" of the new fuel something would need to be added to the lower energy density substitutes that would remain stable until burned, yet provide sufficient extra energy to balance out the greater stability of the base fuel.
  • the process is self-limiting so that over-dosing is not a danger.
  • For the reaction to occur it is necessary to have the core polar material at a given concentration in the bulk fuel. However, this is necessary, but not sufficient to have the desired detonation reaction occur.
  • the combined, dynamically-stable fuel unit comprises a mixture of components providing deflagrative and detonative combustion waves, wherein the different components are held together in a particular molar ratio principally through the dipole moment(s) of the small molecule stabilizing fuel component.
  • the detonative fuel component (sometimes herein referred to as the core polar material or component) is homogeneous in composition when measured at the general level of the entire fuel unit, yet it may exist in dynamic equilibrium where it forms and reforms differentiated molecular combinations as the liquid responds to gross motions.
  • the detonative fuel component belongs to a class of combustible or explosive materials that are defined by reference to the dipole density of the stabilizing fuel component. 1 1 will be understood that each of the stabilizing fuel component(s) and the detonative fuel component(s) may each comprise two or more subcomponents (i.e., each may be a mixture as well).
  • the fuel formulation had an energy density as measured by a calorimeter that is greater than the energy density of methanol and less that the energy density of gasoline.
  • Methanol has an energy density that is approximately one half of the energy density of gasoline.
  • the formulation including the core material performs similar to gasoline as measured by a calorimeter. This difference between the caloric measured value and the apparent energy density may be termed the virtual energy density (VED).
  • VED virtual energy density
  • the actual energy density in the ICE is the sum of the caloric measured specific energy and the VED.
  • Cetane number or CN is a measure of a fuel's ignition delay, the time period between the start of injection and the first identifiable pressure increase during combustion of the fuel. In a particular diesel engine, higher cetane fuels will have shorter ignition delay periods than lower cetane fuels. Cetane numbers are only used for the relatively light distillate diesel oils. For heavy (residual) fuel oil two other scales are used, Calculated Carbon Aromaticity Index (CCAI) and Calculated Ignition Index (CII).
  • CCAI Carbon Aromaticity Index
  • CII Calculated Ignition Index
  • compression setting such as a diesel engine.
  • the characteristic diesel "knock" occurs when the first portion of fuel that has been injected into the cylinder suddenly ignites after an initial delay. Minimizing this delay results in less unburned fuel in the cylinder at the beginning and less intense knock. Therefore higher-cetane fuel usually causes an engine to run more smoothly and quietly. This does not necessarily translate into greater efficiency, although it may in certain engines.
  • diesel engines operate well with a CN from 40 to 55. Fuels with higher cetane number have shorter ignition delays, providing more time for the fuel combustion process to be completed. Hence, higher speed diesel engines operate more effectively with higher cetane number fuels.
  • diesel cetane numbers were set at a minimum of 38 in 1994 and 40 in 2000.
  • the current standard for diesel sold in European Union, Iceland, Norway and
  • Switzerland is set in EN 590 with a minimum cetane index of 46 and a minimum cetane number of 51.
  • Premium diesel fuel can have a cetane number as high as 60.
  • the fuel mixture in the present invention maintains octane/cetane ratings above standard limits.
  • the present invention teaches that a process exists for a given basic stabilizing fuel component which comprises the vast majority of the fuel mixture; and whose energy densities, molar, and solvent characteristics are known; and which is preferably one of the simpler hydrocarbons having 8 or less carbons, more preferably 4 or less carbons, and in one embodiment having 1 or 2 carbons.
  • a suitable balancing fuel additive i.e., the detonative fuel component
  • water absorbing components can be determined that will produce the requisite VED when they are combined for use within an internal combustion engine.
  • the value of the deflagrative and detonative effect within any given ICE may depend in part on the fuel mix which the ICE was designed for, one may assume that most engines were designed to use standard octanes of gasoline or standard cetanes of diesel. Knowing what the effect of the VED must be, and also knowing the values for the basic stabilizing fuel component, one can determine a set of possible fuel additives which will provide the combined hygroscopic, deflagrative and detonative effect. This may be done by determining a specific molar ratio of a given compound in the core that needs to be maintained based on the selection of the compound(s) that serve as the explosive and the one or more cage-forming compounds.
  • the cage materials preferably have a dipole energy density (DED) in the range of twice the DED of the solvent portion of the core material and in the range of 25% or more of the DED of the explosive material of the core material (e.g., a nitrogen containing explosive such as a nitro-alkane).
  • DED dipole energy density
  • FIGS. 1 and 2 One theoretical structure for the fuel mixture is shown in FIGS. 1 and 2.
  • the structure may be likened to a soccer ball with panels of the ball-like structure in polygons with the explosive molecules and the water molecules positioned inside the structure.
  • the explosive molecule is thought to be part of the outer Fullerene-like buckyball structures, with polygonal faces forming a cage and the inner explosive molecule may be another Fullerene- like structure of nitromethane molecules arranged in four molecule sub groups, forming an inner cage.
  • the core structure is subject to detonation by the spark initiated in the confined space during the downward power stroke.
  • the core structure may be fully compressed with the expanding gases traveling at about Mach 1.8 (1.8 times the speed of sound) to impart momentum onto the cylinder.
  • This action sufficiently compresses other core caged structures (CCS) to cause a chain reaction of detonation within the combustion chamber.
  • the speed of a combustion wave is subsonic and is approximated to less than Mach 0.1.
  • An explosion wave travels at about Mach 6 to 10.
  • the detonation results in at least 18 times the momentum imparted onto the piston as compared to combustion that occurs in an ICE fueled by gasoline if we assume the same mass of combustion products.
  • the VED is greater than the DED of the products in the detonation of the CCS. In one embodiment, the DED is approximately one half the DED of gasoline.
  • An engine designed for gasoline travel at about 60 miles per hour getting about 30 miles per gallon burns about 4.3 ounces (0.205 pounds) per minute and 3.02 pounds of air at 14.7: 1 stoichiometric ratio.
  • the reduced air flow allows for a reduced number of cylinders to two from four, six or eight and reduced running RPM. So an automobile engine would be replaced by a motorcycle or lawn mower sized engine matched with the fuel feed system of a smaller engine.
  • the fuel could be used with two cycle engines as well as four cycle engines.
  • the core material may be blended with thesolvent (e.g., methanol) to produce a shock stable product at about 28.5% or more methanol.
  • concentrations of methanol may be up to about 95% V/V to make a fuel substitute or a replacement for the ethanol that is blended in US gasoline.
  • one typical blended ethanol gasoline includes up to 10% V/V ethanol, while other formulas may include higher fractions of ethanol (e.g., a winter formula biofuel may typically contain about 85% ethanol and about 15% gasoline to provide sufficient volatile concentration to initiate combustion at colder ambient conditions, another formulation use 70% ethanol and 30% gasoline).
  • methanol vs. ethanol as a fuel is that methanol may be readily manufactured from methane gas present in biogases from refuse, compost, and natural gas, not from food products such as com, typically required to make ethanol.
  • methane also produces lower levels of common pollution emissions.
  • the lower levels of emissions do not require any more stringent or efficient clean up by exhaust devices or e.g., addition of urea to diesel exhaust.
  • methane has a greater ratio of hydrogen to carbon, which produces less carbon dioxide emissions per unit of energy production and less residual materials that must be absorbed by the environment.
  • the world's history of energy supply has moved from carbon based fuels with little or no hydrogen (e.g., wood, peat and coal) to hydrocarbon fuels (e.g., gasoline, diesel and natural gas).
  • Each hydrogen atom has 1/2 the weight of an atom of carbon but delivers twice the energy on combustion to water as compared to an atom of carbon on combustion to carbon dioxide.
  • Coal has an infinite carbon to hydrogen ratio and thus is the poorest choice for a fuel in terms of carbon dioxide production, which is the foundation of global warming concerns.
  • Gasoline and diesel have a 2.0 to 2.5 to 1.0 hydrogen to carbon ratio, depending on the particular components of the mixture.
  • the present invention in one preferred mode employs a methanol fuel component that supports a 4 to 1 hydrogen to carbon ratio and is well suited to minimize global warming effects from combustion of fuels.
  • An engine designed specifically to be fueled by caged core material that has 28.5% V/V methanol solvent requires a significantly lower fuel flow than if it were fueled by gasoline, because the VED of the present inventive fuel exceeds the DED of gasoline.
  • the oxygen content of the present inventive fuel supplements oxygen from air so that a lower air to fuel ratio is required than the air to fuel ratio for gasoline.
  • the cooling effect of the high heat of vaporization associated with the methanol and core material components allows more air to be added. Because a portion of the VED is associated with the structure of the caged core, there is less waste heat, and air cooling rather than water cooling of the engine may be possible.
  • An engine specifically designed to be fueled by the present inventive fuel at a maximum core material concentration would have approximately 10 times the energy density, about 150 ml of displacement, two cylinders, and a 1 gallon gas tank.
  • Such an engine and vehicle would have a similar range to a gasoline engine auto mobile, but much improved cost per mile, 400 miles per gallon, $25 a gallon for fuel, and a torque/horsepower profile more like a diesel engine than a gasoline ICE.
  • a production package may incorporate a portion of the base stabilizing fuel component (e.g., methanol) to serve as a "containing" or stabilizing shipping adjunct to the detonative fuel component.
  • the base stabilizing fuel component e.g., methanol
  • the product may comprise in its shipping stabilized form the following percentages by volume, which include a corrosion inhibitor, an ignition enhancer, a power enhancer and a water absorbing component sufficient for a final product:
  • the composition can include the nitromethane in a range from about 10% to about 32% by volume.
  • the composition can include the water absorbing component in a range from about 2% to about 10% by volume.
  • the composition can include ethanol in a range from about .002% to about 10% by volume.
  • the composition can include the power enhancing component in a range from about 10% to about 49% by volume.
  • the composition can include the 2-ethylhexyl nitrate in a range from about 15% to about 32% by volume.
  • the composition can include acetone in a range from about 3% to about 15% by volume.
  • Another exemplary composition has the following components:
  • the composition can include the methanol in a range from about 5% to about 93% by volume. In some embodiments, the composition can include ethanol in a range from about .002% to about 30% by volume. In some embodiments, additional methanol, additional ethanol, or another component can be included as the water absorbing component. In some embodiments, the composition can include the conventional gasoline blending components (CBOB) in a range from about 7% to about 51% by volume.
  • Corrosion inhibitors can include, for example, zinc dithiophosphates, DCI-4A, DCI-6A, DCI-1 1, DCI-28, DCI-30, DMA-4, other suitable corrosion inhibitors, and combinations thereof.
  • the particular amount of methanol or other polar small molecule hydrocarbon necessary to stabilize the detonative fuel component may be determined by adding sufficient methanol (or other) to the detonative fuel component until there is no longer a possibility of reaction occurring for the 2- ethylhexyl nitrate (e.g., upon agitation or impact).
  • the high MPG engine briefly described above may optionally use the above with a small amount (e.g., 20 ml of the additive package for a 20 gallon volume).
  • methanol comprises between about 85% and about 93% of the final blend, the nitromethane about 0.05%, the 2-ethylhexyl nitrate about 0.03 %, the acetone about 0.02% and the base stabilizing fuel component (gasoline) about 7% to 15%.
  • the amount of methanol is adjusted primarily due to the amount of water dissolved in the gasoline and the amount of water that has separated out from the gasoline at the bottom of the tank.
  • Other formulations of the blend that contain small amounts of other components are derived based upon the analysis of the gasoline with respect to its water content and other impurities that would inhibit the gasoline from being absorbed into the final blend.
  • Nitromethane is used as a fuel in motor racing, particularly drag racing, as well as for rockets and radio-controlled models (such as cars, planes and helicopters) and is commonly referred to in this context as "nitro.”
  • the oxygen content of nitromethane enables it to bum with much less atmospheric oxygen.
  • Alkyl nitrates (principally 2-ethylhexyl nitrate) are partially utilized to raise the cetane number and can be used as an ignition-enhancing additive and are known to reduce emissions from gas engines; however, the mechanisms by which the emissions reduction occur are not understood.
  • the proportion of the detonative fuel component can be modified to provide less or more of the total "bang" to make the combined dynamically stable fuel's performance match that of whatever fuel that an engine is designed for.
  • the base stabilizing fuel component is methanol and comprises about 60% of the solution
  • the base stabilizing fuel component provides about one-half of the combustive energy in deflagrative form
  • the "cage" detonative fuel component provides the other half of the combustive energy in detonative form. Matching the solution desired thus requires calculating the relative energy which is being replaced by the detonative fuel component, until the new combination equals the energy performance of the target fuel to be replaced.
  • the combined, stabilized, hygroscopic fuel mixture can be envisioned as a dynamically-stable liquid in which each of the detonative component molecules exists in a cage whose bars are made of the molecules of a homogenous solvent with a relatively high dipole moment.
  • acetone has a dipole moment of about 2.88 D.
  • Methanol, ethanol, and other low alcohols have a dipole moment of about 1.65-1.7 D.
  • This dynamically-stable fuel unit because of its structure and mixture of deflagrative and detonative reactions when combusted, has more energy than the calorimetric measurements in Kcal or BTU of the individual components because at least a portion of the fuel is detonated in the confined space of an engine. If ignited in the open, the detonative effect rapidly dissipates as the dispersive limit of the supersonic wave disperses the deflagrative aspect beyond the sustainable detonative limit. In other words, the chain reaction can be maintained within the confines of the engine, but would be unlikely to continue in the open.
  • This cage is formed by the dynamically-moving molecules of a single-component, high-dipole-energy, dense solvent such as methanol (or a mixture of alcohols to adjust the vapor pressure or other parameters for the engine intended).
  • a synthetic, non crude-oil based fuel including two defined components, a solute (the cage) and a solvent (e.g., methanol, ethanol, butanol, propanol, their isomers, or a combination thereof), and the detonative fuel component.
  • the fuel mixture may be quite unlike a mixture such as gasoline or diesel, made from thermal distillation of crude oil that principally contains unknown proportions of hydrocarbons with chains and other structures (e.g., aromatics) of 4 to 80 carbons each.
  • one embodiment of the present disclosure comprises a fuel unit to be used in an internal combustion engine that establishes and maintains a stable operating threshold temperature and pressure.
  • This fuel unit comprises a base combustive fuel which contains separate phase water such as, for example, gasoline, diesel, biodiesel, jet fuel such as, for example, JP1, JP2, JP3, JP4, JP5, JP6, JP7, JP8, JP9, JP 10, Jet A, Jet A-l, or Jet B, avgas, ethanol, methanol, butanol, naphtha, any other suitable combustive base fuel, or combinations thereof, to which is added a fuel additive including a mixture of both a core polar material and a stabilizing and enhancing combustive mixture.
  • the core polar material includes a detonative component such as, for example, nitroalkanes such as, for example, 2-ethylhexyl nitrate, dinitromethane, or trinitromethane, IsoOctane, acetone, acetone peroxide, any other suitable detonative component, or combinations thereof, and may have a similar composition as the detonative fuel components described above
  • a detonative component such as, for example, nitroalkanes such as, for example, 2-ethylhexyl nitrate, dinitromethane, or trinitromethane, IsoOctane, acetone, acetone peroxide, any other suitable detonative component, or combinations thereof, and may have a similar composition as the detonative fuel components described above
  • Polar protic components serve to encapsulate or cage the explosive and unstable nitro-alkane component as well as the water molecules which arise from the base combustive fuel.
  • Polar protic components in accordance with various embodiments, can include, for example, methanol, ethanol, butanol, n-propanol, any other suitable polar protic compound, or combinations thereof.
  • Polar aprotic components in accordance with various embodiments, can include, for example, acetone, nitromethane, ethyl acetate, dichloromethane, any other suitable polar aprotic compound, or combinations thereof.
  • the stabilizing and enhancing combustive mixture may contain some proportion of a stabilizing yet combustive compound, at least one nonpolar molecule such as, for example, petroleum distillates such as, for example, liquefied petroleum gas, naphtha, kerosene, jet fuel, diesel, heavy fuel oils, or lubricating oils, benzene derivatives such as, for example, phenol, toluene, aniline, or biphenyls, any other suitable nonpolar molecule, or combinations thereof and an explosion-enhancing compound such as, for example, IsoOctane, a nitro alkane such as, for example, nitromethane or nitroethane, any other suitable explosion- enhancing compound, or combinations thereof).
  • a stabilizing yet combustive compound such as, for example, petroleum distillates such as, for example, liquefied petroleum gas, naphtha, kerosene, jet fuel, diesel, heavy fuel oils, or lubricating oils, benzene derivatives such as,
  • the stabilizing combustive compound enables separate storage and shipment without hazard of explosion
  • the nonpolar compound enables the core polar material to be maintained and dispersed in the fuel blend resulting after mixture with the base combustive fuel.
  • the nonpolar component is believed to overcome the base combustive fuel's miscibility limitations to increase the explosive potential when the synthetic fuel is used in an ICE.
  • the fuel blend may be referred hereinafter to as a hygroscopic synthetic fuel, although it will be understood that the base combustive fuel does not necessarily have to come from a synthetic source (e.g., it may be diesel, gasoline, or any other petroleum fuel derived from crude oil processing).
  • the ICE initiates deflagrative combustion of the base combustive fuel (which in the preferred embodiment is a petroleum-based fuel that contains separate phase water). This deflagration is believed to immediately initiate and sustain a solvation reaction between compounds from the stabilizing and enhancing combustive mixture and the core polar material. Together, the deflagrative combustion and solvation reaction enable a detonative or explosive reaction of the nitro-alkane compound, and thus release the explosion potential energy contained within the nitro-alkane compound.
  • the base combustive fuel which in the preferred embodiment is a petroleum-based fuel that contains separate phase water.
  • This endothermic solvenation may occur via a concerted mechanism (e.g., a mechanism that takes place in one step, with bonds breaking and forming at substantially the same time) at the balanced ratio of heat and pressure within the ICE's optimal operating temperature and power-stroke compression ratio and timing (more heat, less pressure; lower heat, more pressure).
  • This endothermic solvenation then synergistically facilitates detonation of the nitro-alkane compound which responds at that same heat/pressure combinations that a detonation or explosion occurs, thereby releasing the explosive potential energy of the nitro- alkane compound. It is this released explosion potential energy which, because it is significantly greater than the thermal combustive energy available should the nitro-alkane compound just be burned, supplements the mechanical energy created from the thermal processes.
  • combustion of the base fuel and stabilizing compound can be ignited by increasing temperature in the combustion chamber of the ICE to at least, for example, 43 °C or higher to reach a flash point of the fuel. Combustion of the base fuel and stabilizing compound then provides sufficient thermal energy to maintain a temperature of 43°C or higher to initiate and sustain the endothermic solvenation reaction, thereby releasing the nitro-alkane, which, in some embodiments, can detonate at a temperature as low as 38°C.
  • the dipole moment of the polar protic compound (e.g., methanol) holds together the "cage” that stabilizes the nitro-alkane compound and the water molecule until the moment of combustion.
  • the polar protic compound is present in stoichiometric ratios with other subordinate components of the synthetic fuel such that they will react with each other (e.g., in pairs) and the core polar material to synergistically engage in solvenation of positively charged spe ⁇ cies via the negative dipole of the aprotic compounds (e.g., acetone and nitromethane), thereupon enabling a detonative or explosive release of the nitro-alkane from the dynamic molecular cage, creating a pressure wave that progresses at a detonation velocity estimated to be about 18 times that of the combustion wave, or an explosive wave that is about 100 times or more that of the combustion wave.
  • aprotic compounds e.g., acetone and nitromethane
  • the momentum is transferred to the combustive and explosive reaction products and to the cylinder and piston head, driving the resultant power stroke with some combination of the thermal and explosive energies.
  • Precise timing and interim molecular recombination and responses of explosive products are generally not of concern so long as there is a predictable and measurable energy release as there is with the synthetic fuels.
  • the energy yield per gram of TNT when exploded is 4, 184 joules, which is far greater than the 2,724 joules generated by combustion of TNT.
  • a first process e.g. combustion
  • a second process e.g. explosion
  • the power stroke of the ICE provides two buffers for the resulting explosion.
  • the combustion products of the primary fuel are present at several orders of magnitude greater mass than the products of the explosion. So the kinetic energy of the explosion of the nitro- alkane compound is "cushioned” even as it contributes to an increase in velocity and thus kinetic energy of the combustion products.
  • the second buffering arises from the movement of the piston which in the power down stroke creates a larger volume in the cylinder, thus allowing the detonation or explosion to occur without creating a "knock", as the direction of the movement of the piston allows the desired expansion of volume.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Output Control And Ontrol Of Special Type Engine (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

L'invention concerne un combustible synthétique. Le combustible synthétique comprend un combustible de base présentant une première densité d'énergie et un composé, le composé comprenant un agent d'absorption d'eau permettant d'absorber l'eau du combustible de base pour empêcher une combustion pauvre, et un agent explosif présentant une valeur d'énergie de détonation qui est suffisante de façon à produire le composé avec une seconde densité d'énergie égale ou supérieure à la première densité d'énergie.
PCT/US2017/036731 2016-06-09 2017-06-09 Mélanges de combustibles hygroscopiques et leurs procédés de production Ceased WO2017214493A1 (fr)

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US15/618,347 US20170355917A1 (en) 2016-06-09 2017-06-09 Hygroscopic fuel blends and processes for producing same

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