US20100199547A1 - Cerium dioxide nanoparticle-containing fuel additive - Google Patents

Cerium dioxide nanoparticle-containing fuel additive Download PDF

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Publication number
US20100199547A1
US20100199547A1 US12/440,182 US44018207A US2010199547A1 US 20100199547 A1 US20100199547 A1 US 20100199547A1 US 44018207 A US44018207 A US 44018207A US 2010199547 A1 US2010199547 A1 US 2010199547A1
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Prior art keywords
cerium
fuel
cerium dioxide
nanoparticles
surfactant
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US12/440,182
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Kenneth Reed
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Cerion LLC
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Cerion Technology Inc
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Priority to US12/440,182 priority Critical patent/US20100199547A1/en
Assigned to CERION TECHNOLOGY, INC. reassignment CERION TECHNOLOGY, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: REED, KENNETH
Publication of US20100199547A1 publication Critical patent/US20100199547A1/en
Assigned to CERION, LLC reassignment CERION, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CERION TECHNOLOGY, INC.
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/224—Oxides or hydroxides of lanthanides
    • C01F17/235—Cerium oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01F27/812—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis the stirrers having central axial inflow and substantially radial outflow the stirrers co-operating with surrounding stators, or with intermeshing stators, e.g. comprising slits, orifices or screens
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    • Y02T50/678—Aviation using fuels of non-fossil origin

Definitions

  • the present invention relates to fuel additives and, in particular, to fuel additive reverse-micellar compositions that preferably include cerium dioxide nanoparticles.
  • Trucks, buses, tractors, locomotives, ships, power generators, etc. are examples of devices that use diesel fuel.
  • Passenger cars and sport utility vehicles are another area of potential growth for the use of diesel engines that can provide improved fuel efficiency, especially where high torque at relatively low rpm is desired.
  • Diesel fuel is principally a blend of petroleum-derived compounds called middle distillates (heavier than gasoline but lighter than lube oil). Diesel fuel is designed to operate in a diesel engine, where it is injected into the compressed, high-temperature air in the combustion chamber and ignites spontaneously. This differs from gasoline, which is pre-mixed with air and ignited in a gasoline engine by the spark plugs. D2 diesel fuel conforms to specification D 975 set by the American Society for Testing and Materials (ASTM).
  • ASTM American Society for Testing and Materials
  • diesel engines Unlike gasoline engines that operate by spark ignition, diesel engines employ compression ignition. In order to avoid long ignition delays resulting in rough engine operation, as well as to minimize misfiring and uneven or incomplete combustion which results in smoke in the exhaust gases that causes a major environmental problem, it is highly desirable to improve the burning quality of diesel fuels to minimize environmental pollutants such as hydrocarbons, carbon monoxide, particulate matter (commonly called soot), etc.
  • environmental pollutants such as hydrocarbons, carbon monoxide, particulate matter (commonly called soot), etc.
  • Cetane is an alkane molecule that ignites very easily under compression, so it is assigned a cetane number (CN) of 100.
  • the cetane number (CN) depends primarily on its hydrocarbon composition. Saturated hydrocarbons, particularly those with straight, open chains, have relatively high cetane numbers, whereas unsaturated hydrocarbons have relatively low cetane numbers. All other hydrocarbons in diesel fuel are indexed to cetane as to how well they ignite under compression. The cetane number therefore measures how quickly the fuel starts to burn (auto-ignites) under diesel engine conditions. Since there are hundreds of components in diesel fuel, with each having a different cetane quality, the overall cetane number of the diesel is the average cetane quality of all the components. Cetane improvers act to increase the effective cetane number of the fuel.
  • diesel fuels have CN numbers of at least 40.
  • the suitable diesel fuel has appropriate volatility, pour and cloud point, viscosity, gravity, flash point and contain only small but tolerable levels of sulfur. It is also important that carbon, residue formation and ash content should be kept low.
  • diesel engines During the normal course of operation, diesel engines often develop carbon deposits on the walls of their cylinders due to incomplete combustion of fuel. These deposits can increase engine wear and, because of friction induced by the deposits, decrease engine efficiency. Incomplete fuel combustion can also lead to the environmentally harmful emission of particulate materials, also referred to as soot. Thus, fuel additives that increase fuel combustion, protect the cylinder walls of diesel engines, and decrease engine friction, resulting in greater fuel efficiency, are highly desirable.
  • Peters et al. U.S. Pat. No. 6,158,397, the disclosure of which is incorporated herein by reference, describes a process for reducing soot in diesel engine exhaust gases wherein a fluid containing a peroxide compound, preferably aqueous hydrogen peroxide, is separately fed into the combustion chamber after the start of the injection and combustion of the fuel, preferably following the combustion phase.
  • a peroxide compound preferably aqueous hydrogen peroxide
  • Olsson et al. U.S. Pat. No. 5,105,772, the disclosure of which is incorporated herein by reference, describes a process for improving combustion in an engine that comprises: injecting a liquid composition that includes a peroxide or a peroxo compound into an engine combustion chamber, and passing a portion of the composition through the exhaust outlet valve as the engine goes from the exhaust phase to the intake phase, the passing occurring during the step of injecting.
  • a method of improving fuel combustion comprises: introducing a liquid composition consisting essentially of 1-10% hydrogen peroxide, 50-80% water, and 15-45% of a C 1 -C 4 aliphatic alcohol, all by volume, in the form of fine droplets into the air intake manifold of an engine, where the droplets mix with air or fuel-air mixture prior to entering the combustion chamber.
  • the liquid composition also contains up to 5% of a thin lubricating oil and up to 1% of an anticorrosive.
  • Kracklaurer U.S. Pat. No. 4,389,220, the disclosure of which is incorporated herein by reference, describes a method of conditioning diesel engines in which a diesel engine is operated on a diesel fuel containing from about 20-30 ppm of dicyclopentadienyl iron for a period of time sufficient to eliminate carbon deposits from the combustion surfaces of the engine and to deposit a layer of iron oxide on the combustion surfaces, which layer is effective to prevent further buildup of carbon deposits. Subsequently, the diesel engine is operated on a maintenance concentration of from about 10-15 ppm of dicyclopentadienyl iron or an equivalent amount of a derivative thereof on a continuous basis.
  • the maintenance concentration is effective to maintain the catalytic iron oxide layer on the combustion surfaces but insufficient to decrease timing delay in the engine.
  • the added dicyclopentadienyl iron may produce iron oxide on the engine cylinder surface (Fe 2 O 3 ), which reacts with carbon deposits (soot) to form Fe and CO 2 , thereby removing the deposits.
  • this method may accelerate the aging of the engine by formation of rust.
  • fuel additives of this type in addition to using the rare and expensive metals such as platinum, can require several months before the engine is “conditioned”.
  • conditioned is meant that all the benefits of the additive are not obtained until the engine has been operated with the catalyst for a period of time. Initial conditioning may require 45 days and optimal benefits may not be obtained until 60-90 days. Additionally, free metal may be discharged from the exhaust system into the atmosphere, where it may subsequently react with living organisms.
  • Cerium dioxide is widely used as a catalyst in converters for the elimination of toxic exhaust emission gases and the reduction in particulate emissions in diesel powered vehicles.
  • the cerium dioxide can act as a chemically active component, acting to release oxygen in the presence of reductive gases, as well as to remove oxygen by interaction with oxidizing species.
  • Cerium dioxide may store and release oxygen by the reversible process shown in equation 1.
  • Cerium dioxide may provide oxygen for the oxidation of CO or hydrocarbons in an oxygen starved environment, or conversely may absorb oxygen for the reduction of nitrogen oxides (NOx) in an oxygen rich environment. Similar catalytic activity may also occur when cerium dioxide is added as an additive to fuel, for example, diesel or gasoline.
  • the cerium dioxide must be of a particle size small enough, i.e., nanoparticulate ( ⁇ 100 nm), to remain in a stable dispersion in the fuel.
  • the small particle size renders the nanocrystalline material more effective as a catalyst.
  • the incorporation of cerium dioxide in fuel serves not only to act as a catalyst to reduce toxic exhaust gases produced by fuel combustion, for example, by the “water gas shift reaction”
  • Cerium dioxide nanoparticles are particles that have a mean diameter of less than 100 nm.
  • the diameter of a nanoparticle refers to its hydrodynamic diameter, which is the diameter determined by dynamic light scattering technique and includes molecular adsorbates and the accompanying solvation shell of the particle.
  • the geometrical particle diameter bay be estimated using transmission electron micrography.
  • cerium dioxide nanoparticles can also be added to fuel at an earlier stage to achieve improved fuel efficiency. They can, for example, be incorporated at the refinery, typically along with processing additives such as, for example, cetane improvers or added at a fuel distribution tank farm.
  • Cerium dioxide nanoparticles can also be added at a fuel distribution center, where it can be rack injected into large ( ⁇ 100,000 gal) volumes of fuel or at a smaller fuel company depot, which would allow customization according to specified individual requirements.
  • the cerium dioxide may be added at a filling station during delivery of fuel to a vehicle, which would have the potential advantage of improved stabilization of the particle dispersion.
  • Fuel additives such as PuriNOxTM manufactured by Lubrizol Corporation, have been developed that are useful for the reduction of NOx and particulate material emissions, however, the composition of these fuel additives often includes 15-20% water. This “emulsified” fuel additive is commonly mixed with fuel at a level of 5-10%. The resulting high water content can lead to a loss in engine power and lower fuel economy. Thus it would be desirable to formulate a fuel additive that afforded reduction in nitrogen oxide and particulate material emissions, while simultaneously maintaining optimum engine performance.
  • Cerium nanoparticles and the associated free radical initiators can provide a possible solution to this problem.
  • Cerium nanoparticles may form a ceramic layer on the engine cylinders and moving parts essentially turning the engine into a catalytic device. Their catalytic efficiency derives from the fact that they provide a source of oxygen atoms during combustion by undergoing reduction according to the equation (1). This results in better fuel combustion and reduced levels of particulate material emissions. Additionally, when used as a fuel additive, these nanoparticles can provide improved engine performance by reducing engine friction.
  • cerium dioxide nanoparticles can be added to the lube oil and act as a lubricity enhancing agent to reduce internal friction. This will also improve fuel efficiency.
  • cerium dioxide doped with components that result in the formation of additional oxygen vacancies being formed.
  • the dopant should be divalent or trivalent, i.e., a divalent or trivalent ion of an element that is a rare earth metal, a transition metal or a metal of Group HA, MB, VB, or VIB of the Periodic Table, and of a size that allows incorporation of the ion in a lattice position within the surface or sub-surface region of the cerium dioxide nanoparticles.
  • This substitutional ion doping is preferred to interstitial ion doping, where the dopants occupy spaces between the normal lattice positions.
  • the radicals A which are the same or different, are each an anion of an organic oxyacid AH having a pK a greater than 1, p is an integer ranging from 0 to 5, n is a number ranging from 0 to 2, and m is an integer ranging from 1 to 12.
  • the organic oxyacid is preferably a carboxylic acid, more preferably, a C 2 -C 20 monocarboxylic acid or a C 4 -C 12 dicarboxylic acid.
  • the cerium-containing compounds can be employed as catalysts for the combustion of hydrocarbon fuels.
  • Chopin et al. U.S. Pat. No. 6,210,451 discloses a petroleum-based fuel that includes a stable organic sol that comprises particles of cerium dioxide in the form of agglomerates of crystallites (preferred size 3-4 nm), an amphiphilic acid system containing at least one acid whose total number of carbons is at least 10, and an organic diluent medium.
  • the controlled particle size is no greater than 200 nm.
  • Birchem et al. U.S. Pat. No. 6,136,048, discloses an adjuvant for diesel engine fuels that includes a sol comprising particles of oxygenated compound having a d90 no greater than 20 nm, an amphiphilic acid system, and a diluent.
  • the oxygenated metal compound particles are prepared from the reaction in solution of a rare earth salt such as a cerium salt with a basic medium, followed by recovery of the formed precipitate by atomization or freeze drying.
  • Lemaire et al. U.S. Pat. No. 6,093,223, discloses a process for producing aggregates of ceric oxide crystallites by burning a hydrocarbon fuel in the presence of at least one cerium compound.
  • the soot contains at least 0.1 wt. % of ceric oxide crystallite aggregates, the largest particle size being 50-10,000 angstroms, the crystallite size being 50-250 angstroms, and the soot having an ignition temperature of less than 400° C.
  • Hazarika et al. U.S. Patent Appl. Publ. No. 2003/0154646, discloses a method of improving fuel efficiency and/or reducing fuel emissions of a fuel burning apparatus, the method comprising dispersing at least one particulate lanthanide oxide, particularly cerium dioxide, in the fuel, wherein the particulate lanthanum oxide is coated with a surfactant selected from the group consisting of alkyl carboxylic anhydrides and esters having at least one C 10 to C 30 alkyl group.
  • a surfactant selected from the group consisting of alkyl carboxylic anhydrides and esters having at least one C 10 to C 30 alkyl group.
  • Collier et al. U.S. Patent Appl. Publ. No. 2003/0182848, discloses a diesel fuel composition that improves the performance of diesel fuel particulate traps and contains a combination of 1-25 ppm of metal in the form of a metal salt additive and 100-500 ppm of an oil-soluble nitrogen-containing ashless detergent additive.
  • the metal may be an alkali metal, an alkaline earth metal, a metal of Group IVB, VIIB, VIIIB, IB, IIB, or any of the rare earth metals having atomic numbers 57-71, especially cerium, or mixtures of any of the foregoing metals.
  • Collier et al. U.S. Patent Appl. Publ. No. 2003/0221362 discloses a fuel additive composition for a diesel engine equipped with a particulate trap, the composition comprising a hydrocarbon solvent and an oil-soluble metal carboxylate or metal complex derived from a carboxylic acid containing not more than 125 carbon atoms.
  • the metal may be an alkali metal, an alkaline earth metal, a metal of Group IVB, VIIB, VIIIB, IB, IIB, or a rare earth metal, including cerium, or mixtures of any of the foregoing metals.
  • Caprotti et al. U.S. Patent Appl. Publ. No.
  • compositions for a diesel engine equipped with a particulate trap comprising an oil-soluble or oil-dispersible metal salt of an acidic organic compound and a stoichiometric excess of metal.
  • metal which is selected from the group consisting of Ca, Fe, Mg, Sr, Ti, Zr, Mn, Zn, and Ce.
  • Caprotti et al. U.S. Patent Appl. Publ. No. 2005/0060929, discloses a diesel fuel composition stabilized against phase separation that contains a colloidally dispersed or solubilized metal catalyst compound and 5-1000 ppm of a stabilizer that is an organic compound having a lipophilic hydrocarbyl chain attached to at least two polar groups, at least one of which is a carboxylic acid or carboxylate group.
  • the metal catalyst compound comprises one or more organic or inorganic compounds or complexes of Ce, Fe, Ca, Mg, Sr, Na, Mn, Pt, or mixtures thereof.
  • Wakefield U.S. Pat. No. 7,169,196 B2 discloses a fuel comprising cerium dioxide particles that have been doped with a divalent or trivalent metal or metalloid that is a rare earth metal, a transition metal, or a metal of Group Ha, IIIB, VB, or VIB of the Periodic Table.
  • Caprotti et al. U.S. Patent Appl. Publ. No. 2006/0000140, discloses a fuel additive composition that comprises at least one colloidal metal compound or species and a stabilizer component that is the condensation product of an aldehyde or ketone and a compound comprising one or more aromatic moieties containing a hydroxyl substituent and a further substituent chosen from among hydrocarbyl, —COOR, or —COR, R being hydrogen or hydrocarbyl.
  • the colloidal metal compound preferably comprises at least one metal oxide, preferred oxides being iron oxide, cerium dioxide, or cerium-doped iron oxide.
  • Cerium-containing nanoparticles can be prepared by a variety of techniques known in the art. Regardless of whether the synthesized nanoparticles are made in a hydrophilic or hydrophobic medium, the particles normally require a stabilizer to prevent undesirable agglomeration.
  • Talbot et al. U.S. Pat. No. 6,752,979 discloses a method of producing metal oxide particles having nano-sized grains that consists of: mixing a solution containing one or more metal cations with a surfactant under conditions such that surfactant micelles are formed within the solution, thereby forming a micellar liquid; and heating the micellar liquid to remove the surfactant and form metal oxide particles having a disordered pore structure.
  • the metal cations are selected from the group consisting of cations from Groups 1A, 2A, 3A, 4A, 5A, and 6A of the Periodic Table, transition metals, lanthanides, actinides, and mixtures thereof.
  • Preparations of particles of cerium dioxide and mixed oxides containing cerium and one or more other metals are included in the illustrative examples.
  • Chane-Ching et al. U.S. Pat. No. 6,271,269 discloses a process for preparing storage-stable organic sols that comprises: reacting a base reactant with an aqueous solution of the salt of an acidic metal cation to form an aqueous colloidal dispersion containing excess hydroxyl ions; contacting the aqueous colloidal dispersion with an organic phase comprising an organic liquid medium and an organic acid; and separating the resulting aqueous/organic phase mixture into an aqueous phase and a product organic phase.
  • Preferred metal cations are cerium and iron cations.
  • the colloidal particulates have hydrodynamic diameters in the range of 50-2000 angstroms.
  • Chane-Ching U.S. Pat. No. 6,649,156, discloses an organic sol containing cerium dioxide particles that are made by a thermal hydrolysis process; an organic liquid phase; and at least one amphiphilic compound chosen from polyoxyethylenated alkyl ethers of carboxylic acids, polyoxyethylenated alkyl ether phosphates, dialkyl sulfosuccinates, and quaternary ammonium compounds.
  • the water content of the sols may not be more than 1%.
  • the mean crystallite size is about 5 nm, while the particle agglomerates of these crystallites range in size from 200 to 10 nm.
  • Chane-Ching U.S. Pat. No. 7,008,965 discloses an aqueous colloidal dispersion of a compound of cerium and at least one other metal, the dispersion having a conductivity of at most 5 mS/cm and a pH between 5 and 8.
  • Chane-Ching U.S. Patent Appl. Publ. No. 2004/0029978 (abandoned Dec. 7, 2005), discloses a surfactant formed from at least one nanoparticle that has amphiphilic characteristics and is based on a metal oxide, hydroxide and/or oxyhydroxide, on the surface of which organic chains with hydrophobic characteristics are bonded.
  • the metal is preferably selected from among cerium, aluminum, titanium or silicon, and the alkyl chain comprises 6-30 carbon atoms, or polyoxyethylene monoalkyl ethers of which the alkyl chain comprises 8-30 carbon atoms and the polyoxyethylene part comprises 1-10 ethyoxyl groups.
  • the particle is an isotopic or spherical particle having an average diameter of 2-40 nm.
  • Blanchard et al. U.S. Patent Appl. Publ. No. 2006/0005465, discloses an organic colloidal dispersion comprising: particles of at least one compound based on at least one rare earth, at least one acid, and at least one diluent, wherein at least 90% of the particles are monocrystalline.
  • Example 1 describes the preparation of a cerium dioxide colloidal solution from cerium acetate and an organic phase that includes Isopar hydrocarbon mixture and isostearic acid. The resulting cerium dioxide particles had a d 50 of 2.5 nm, and the size of 80% of the particles was in the range of 1-4 nm.
  • Zhou et al. U.S. Pat. No. 7,025,943, discloses a method for producing cerium dioxide crystals that comprises: mixing a first solution of a water-soluble cerium salt with a second solution of alkali metal or ammonium hydroxide; agitating the resulting reactant solution under turbulent flow conditions while concomitantly passing gaseous oxygen through the solution; and precipitating cerium dioxide particles having a dominant particle size within the range of 3-100 nm.
  • the particle size is stated to be around 3-5 nm.
  • Noh et al. U.S. Patent Appl. Publ. No. 2004/0241070, discloses a method for preparing single crystalline cerium dioxide nanopowder comprising: preparing cerium hydroxide by precipitating a cerium salt in the presence of a solvent mixture of organic solvent and water, preferably in a ratio of about 0.1:1 to about 5:1 by weight; and hydrothermally reacting the cerium hydroxide.
  • the nanopowder has a particle size of about 30-300 nm.
  • Chan, U.S. Patent Appl. Publ. No. 2005/0031517 discloses a method for preparing cerium dioxide nanoparticles that comprises: rapidly mixing an aqueous solution of cerium nitrate with aqueous hexamethylenetetramine, the temperature being maintained at a temperature no higher than about 320° K. while nanoparticles form in the resulting mixture; and separating the foamed nanoparticles.
  • the mixing apparatus preferably comprises a mechanical stirrer and a centrifuge.
  • the prepared cerium dioxide particles are reported to have a diameter of about 12 nm.
  • Ying et al. U.S. Pat. Nos. 6,413,489 and 6,869,584, disclose the synthesis by a reverse micelle technique of nanoparticles that are free of agglomeration and have a particle size of less than 100 nm and a surface area of at least 20 m 2 /g.
  • the method comprises introducing a ceramic precursor that includes barium alkoxide and aluminum alkoxide in the presence of a reverse emulsion.
  • Illustrative example 9 of U.S. Pat. Nos. 6,413,489 and 6,869,584 describes the inclusion of cerium nitrate in the emulsion mixture to prepare cerium-doped barium hexaaluminate particles, which were collected by freeze drying and calcined under air to 500° C. and 800° C. The resulting particles had grain sizes of less than 5 nm and 7 nm at 500° C. and 800° C., respectively.
  • Illustrative example 10 describes the synthesis of cerium-coated barium hexaaluminate particles. Following calcination, the cerium-coated particles had grain sizes of less than 4 nm, 6.5 nm, and 16 nm at 500° C., 800° C., and 1100° C., respectively.
  • the nanoparticles are preferably metal oxide particles, which can be used to oxidize hydrocarbons.
  • Illustrative Examples 9 and 10 of U.S. Patent Appl. Publ. No. 2005/0152832 describe the preparation of, respectively, cerium-doped and cerium-coated barium hexaaluminate particles.
  • Example 13 describes the oxidation of methane with the cerium-coated particles.
  • a process for preparing a colloidal dispersion of the cerium (IV) compound produces particles with a hydrodynamic diameter between about 1 nm and about 60 nm, suitably between about 1 nm and about 10 nm, and desirably between about 3 nm and 8 nm.
  • Hazbun et al. U.S. Pat. No. 4,744,796, the disclosure of which is incorporated herein by reference, describes a microemulsion fuel composition that includes a hydrocarbon fuel and a cosurfactant combination of t-butyl alcohol and at least one amphoteric, anionic, cationic, or nonionic surfactant.
  • Preferred surfactants are fatty acids or fatty acid mixtures.
  • additive compositions for liquid hydrogen fuels that include one or more surfactants selected from the group consisting of amphoteric, anionic, cationic, or nonionic surfactants, and optionally one or more cosurfactants selected from the group consisting of alcohols, glycols, and ethers.
  • a typical chemical reactor that might be used to prepare cerium dioxide includes a reaction chamber that includes a mixer (see, for example, FIG. 1 in Zhou et al. U.S. Pat. No. 7,025,943).
  • a mixer typically includes a shaft, and propeller or turbine blades attached to the shaft, and a motor that turns the shaft, such that the propeller is rotated at high speed (1000 to 5000 rpm).
  • the shaft can drive a flat blade turbine for good meso mixing (micro scale) and a pitched blade turbine for macro mixing (pumping fluid through out the reactor).
  • Cerium dioxide particles prepared using this type of mixing are often too large to be useful for certain applications. It is highly desirable to have the smallest cerium dioxide particles possible as their catalytic propensity (ability to donate oxygen to a combustion system, i.e., equation 1) increases with decreasing particle size, especially for particles having a mean diameter of less than 10 nm.
  • FIG. 1 A schematic example of a batch reactor that can be used to produce cerium dioxide nanoparticles is shown in FIG. 1 .
  • the reactor ( 10 ) includes inlet ports ( 11 , and 12 ) for adding reactants, a propeller, shaft, and motor, 15 , 14 , and 13 , for mixing.
  • the reaction mixture 18 is contained in a reactor vessel 16 .
  • Addition of reactants, such as cerium nitrate, an oxidant, and hydroxide ion, can result in the formation of nanoparticles.
  • the particles initially form as very small nuclei. Mixing causes the nuclei to circulate, shown by the dashed arrows ( 17 ) in FIG. 1 .
  • nuclei As the nuclei continuously circulate through the reactive mixing regime they grow (increase in diameter) as they incorporate fresh reactants. Thus, after an initial steady state concentration of nuclei is formed, this nuclei population is subsequently grown into larger particles in a continuous manner. This nucleation and growth process is not desirable if one wishes to limit the final size of the particles while still maintaining a high particle suspension density.
  • Such a batch reactor is not useful for producing a high yield (greater than 1 molal) of cerium dioxide nanoparticles that are very small, for example, less than 10 nm in a reasonably short reaction time (for example, less than 60 minutes).
  • colloid mills In contrast to batch reactors, colloid mills typically have flat blade turbines turning at 10,000 rpm, whereby the materials are forced through a screen whose holes can vary in size from fractions of a millimeter to several millimeters. Generally, no chemical reaction is occurring, but only a change in particle size. In certain cases, particle size and stability can be controlled thermodynamically by the presence of a surfactant.
  • a surfactant For example, Langer et al., in U.S. Pat. No. 6,368,366 and U.S. Pat. No. 6,363,237, incorporated herein by reference, describe an aqueous microemulsion in a hydrocarbon fuel composition made under high shear conditions. However, the aqueous particle phase (the discontinuous phase in the fuel composition) has a large size, on the order of 1000 nm.
  • Colloid mills are not useful for reducing the particle size of large cerium dioxide particles because the particles are too hard to be sheared by the mill in a reasonable amount of time.
  • the preferred method for reducing large, agglomerated cerium dioxide particles from the micron size down into the nanometer size is milling for several days on a ball mill in the presence of a stabilizing agent. This is a time consuming, expensive process that invariably produces a wide distribution of particle sizes.
  • Aqueous precipitation may offer a convenient route to cerium nanoparticles.
  • cerium dioxide nanoparticles must exhibit stability in a nonpolar medium (for example, diesel fuel).
  • a nonpolar medium for example, diesel fuel.
  • Most stabilizers used to prevent agglomeration in an aqueous environment are ill suited to the task of stabilization in a nonpolar environment. When placed in a nonpolar solvent, such particles tend to immediately agglomerate and, consequently, lose some, if not all, of their desirable nanoparticulate properties.
  • J. Ying et al in WO 98/18884 describe a thermally and temporally stable water-in-fuel emulsion having micelle size of ⁇ 100 nm and including water in an amount of at least 8 wt. percent.
  • the claimed 85-90% reductions in particulate emissions may have been an artifact of the loss of engine power and thus been an unacceptable trade-off of power for emissions reduction.
  • Fuel additives that include cerium dioxide nanoparticles, wherein nanoparticles typically have a mean diameter of 100 nm or less, stabilized with a surfactant, such as sodium dodecyl succinate, and optionally containing copper, are known. These types of fuel additives also have a long conditioning period.
  • cerium nanoparticles to provide a high temperature oxidation resistant coating has been reported, for example, see “Synthesis Of Nano Crystalline Ceria Particles For High Temperature Oxidization Resistant Coating,” S. Seal et al., Journal of Nanoparticle Research, 4, 433-438 (2002).
  • the deposition of cerium dioxide on various surfaces has been investigated, including Ni, chromia and alumina alloys, and stainless steel and on Ni, and Ni—Cr coated alloy surfaces. It was found that a cerium dioxide particle size of 10 nm or smaller is desirable. Ceria particle incorporatiion subsequently inhibits oxidation of the metal surface.
  • CeO 2 can act as a catalytic oxygen storage material, described by equation 1, is governed in part by the CeO 2 particle size.
  • the lattice parameter increases dramatically with decreasing crystallite size (up to 0.45% at 6 nm, see for example Zhang, et al., Applied Physics Letters, 80 1, 127 (2002)).
  • the associated size-induced lattice strain is accompanied by an increase in surface oxygen vacancies that results in enhanced catalytic activity.
  • This (inverse) size dependent activity provides not only for more efficient fuel cells, but better oxidative properties when used in the combustion of petroleum fuels.
  • the present invention is directed to a fuel additive composition that comprises: a) a reverse micellar composition comprising an aqueous disperse phase that includes stabilized, non-agglomerated cerium dioxide nanoparticles in a continuous phase comprising a hydrocarbon liquid, a surfactant, and optionally a co-surfactant; and b) a reverse micellar composition comprising an aqueous disperse phase that includes a cetane improver effective for improving engine power during fuel combustion.
  • the present invention is further directed to a fuel additive composition that includes: a) a reverse micellar composition comprising an aqueous disperse phase that includes nanoparticles formed in situ and comprising a cerium (IV) oxidic compound; and b) a continuous phase comprising a hydrocarbon liquid and a surfactant/stabilizer mixture; wherein the surfactant/stabilizer mixture is effective to restrain particle size, prevent particle agglomeration, and enhance the yield of the nanoparticles.
  • the present invention is also directed to a method of making a cerium-containing fuel additive that comprises the steps of: a) providing a mixture of a nonpolar medium, a surfactant, a co-surfactant, and an aqueous-soluble cetane improver; and b) combining the mixture with an aqueous suspension of stabilized cerium dioxide nanoparticles.
  • the present invention is further directed to a reverse micellar composition for use as a fuel additive, wherein the composition comprises: a) a disperse phase comprising an aqueous composition that includes a free radical initiator providing cetane improvement; and b) a continuous phase comprising a hydrocarbon liquid and a surfactant.
  • FIG. 1 shows a schematic representation of a conventional batch reactor for forming cerium dioxide nanoparticles.
  • FIG. 2A shows a schematic exploded view of a colloid mill reactor that may be used in the invention.
  • FIG. 2B shows a partial view of a colloid mill reactor that may be used in the invention.
  • FIG. 2C shows a schematic exploded view of another type of colloid mill reactor that may be used in the invention.
  • FIG. 3 shows a schematic representation of a continuous reactor for forming very small cerium nanoparticles.
  • FIG. 4 shows the size distribution of the cerium dioxide particles prepared in Example 1.
  • FIG. 5 shows a transmission electron micrograph of a dried-down sample of the cerium dioxide particles of Example 1.
  • FIG. 6 shows an X-ray powder diffraction spectrum of cerium dioxide nanoparticles prepared in Example 1.
  • cerium dioxide nanoparticles The preparation of cerium dioxide nanoparticles is described in co-pending, commonly assigned application Ser. No. ______, METHOD OF PREPARING CERIUM DIOXIDE NANOPARTICLES, filed Sep. ______, 2007, the disclosure of which is incorporated herein by reference.
  • Cerous ion reacts, in the presence of hydroxide ion, to form cerium hydroxide.
  • the reaction vessel is then heated to convert cerium hydroxide to cerium dioxide.
  • the temperature in the reaction vessel is maintained between about 50° C. and about 100° C., more preferably about 65-75° C., most preferably about 70° C. Time and temperature can be traded off, higher temperatures typically reducing the time required for conversion of the hydroxide to the oxide.
  • the cerium hydroxide is converted to cerium dioxide and the temperature of the reaction vessel is lowered to about 15-25° C.
  • the cerium dioxide nanoparticles are concentrated, and the unreacted cerium and waste by-products such as ammonium nitrate are removed, most conveniently for example, by diafiltration.
  • a method of making cerium dioxide nanoparticles includes providing an aqueous reaction mixture comprising cerous ion, hydroxide ion, a stabilizer, and an oxidant at a temperature effective to generate small nuclei size, and achieve subsequent oxidation of cerous ion to ceric ion so that these particles can be grown into nanometric cerium dioxide.
  • the reaction mixture is subjected to mechanical shearing, preferably by causing it to pass through a perforated screen, thereby forming a suspension of cerium dioxide nanoparticles having a mean hydrodynamic diameter in the range of about 2 nm to about 15 nm.
  • the cerium dioxide nanoparticles have a mean hydrodynamic diameter of about 10 nm or less, more preferably about 8 nm or less, most preferably, about 6 nm.
  • the nanoparticles comprise one or at most two primary crystallites per particle edge, each crystallite being on average 2.5 nm (approximately 5 unit cells).
  • the resulting nanoparticle size frequency in substantially monodisperse, i.e., having a coefficient of variation (COV) less than 15%, where the COV is defined as the standard deviation divided by the mean.
  • Mechanical shearing includes the motion of fluids upon surfaces such as those of a rotor, which results in the generation of shear stress.
  • the laminar flux on a surface has a zero velocity, and shear stress occurs between the zero-velocity surface and the higher-velocity flow away from the surface.
  • the current invention employs a colloid mill, which is normally used for milling micro emulsions or colloids, as a chemical reactor to produce cerium dioxide nanoparticles.
  • a colloid mill which is normally used for milling micro emulsions or colloids, as a chemical reactor to produce cerium dioxide nanoparticles.
  • useful colloid mills include those described by Korstvedt, U.S. Pat. No. 6,745,961 and U.S. Pat. No. 6,305,626, the disclosures of which are incorporated herein by reference.
  • FIG. 2A schematically represents a colloid mill reactor, according to the present invention, that includes reactant inlet jets 34 and 35 .
  • the depicted colloid mill reactor has a rotating shaft 30 that is connected to a paddle blade rotor 31 .
  • the rotor is received in a cup-shaped screen stator 32 , which has perforations 36 and encloses the reaction chamber 37 .
  • the stator is mounted on a housing, 33 , fitted with inlet jets 34 and 35 .
  • the inlet jets 34 and 35 extend into the housing 33 to the bottom of the perforated screen stator 32 into the reaction chamber 37 .
  • a plate (not shown) forms a top to the screen stator 32 .
  • the reactants are introduced via jets 34 and 35 into the reaction chamber.
  • the colloidal mill reactor is enclosed in a reaction vessel 38 , which may be submerged in a constant temperature bath (not shown).
  • Factors include reactant ratios, the rotor speed, the “gap” of the mill, which can be defined as the space between the rotor 31 and stator 32 , and the size of the perforations 36 of the stator.
  • Typical rotor speeds are 5000 to 7500 rpm; however, at very high reagent concentrations (about 1 Molal or greater) rotor speeds of greater than 7500 rpm, such as 10,000 rpm, are preferred. It is desirable to keep the gap spacing as small as possible, typically about 1 mm to about 3 mm, consistent with a low back pressure in the colloid chamber, which allows a facile passage of the particles through the perforations of the stator.
  • the perforations of the screen have a mean diameter of preferably about 0.5 mm to about 5 mm.
  • FIG. 2B shows a partial view of the reactor, including the inlet jets 34 and 35 and the base of the reaction chamber 33 A.
  • the inlet jets 34 and 35 are substantially flush with the bottom of the reaction chamber 33 A.
  • FIG. 2C shows a schematic representation of a modification of the device described above, wherein the inlet jets, 34 and 35 , extend into the reaction chamber from the top of the mill, instead of the bottom of the mill.
  • Reactants are introduced into the reaction chamber by means of the reaction inlet(s) and the reaction mixture is stirred.
  • the reactants include an aqueous solution of cerous ion, for example cerous nitrate; an oxidant such as hydrogen peroxide or molecular oxygen; and a stabilizer, such as 2-[2-(2-methoxyethoxy)ethoxy]acetic acid.
  • a two-electron oxidant such as peroxide
  • a two-electron oxidant is present, preferably in at least one-half the molar concentration of the cerium ion.
  • the hydroxide ion concentration is preferably at least twice, more preferably three times, the molar cerium concentration.
  • the reaction chamber is maintained at a temperature sufficiently low to generate small cerous hydroxide nuclei size, which can be grown into nanometric cerium dioxide particles after a subsequent shift to higher temperatures, resulting in conversion of the cerous ion into the ceric ion state.
  • the temperature is suitably about 25° C. or less, preferably about 20° C., more preferably about 15° C. In one embodiment, the temperature is about 10-20° C.
  • a source of cerous ion, a nanoparticle stabilizer, and an oxidant is placed in the reactor and a source of hydroxide ion, such as ammonium hydroxide, is rapidly added with stirring, preferably over a time period of about 90 seconds or less, more preferably about 20 seconds or less, even more preferably about 15 seconds or less.
  • a source of hydroxide ion and an oxidant is placed in the reactor, and a source of cerous ion is added over a period of about 15 seconds.
  • the stabilizers are placed in the reaction vessel, and the cerous nitrate is simultaneously introduced into the reaction chamber with a separate jet of ammonium hydroxide at the optimum molar stoichiometric ratio of 2:1 or 3:1 OH:Ce.
  • Cerous ion reacts in the presence of hydroxide ion to form cerium hydroxide, which can be converted by heating to cerium dioxide.
  • the temperature in the reaction vessel is maintained between about 50° C. and about 100° C., preferably about 65-90° C., more preferably about 80° C. After a period of time at these elevated temperatures, preferably about 1 hour or less, more preferably about 0.5 hour, the cerium hydroxide has been substantially converted to cerium dioxide, and the temperature of the reaction vessel is lowered to about 15-25° C.
  • the time and temperature variables may be traded off, higher temperatures generally requiring shorter reaction times.
  • the suspension of cerium dioxide nanoparticles is concentrated, and the unreacted cerium and waste by-products such as ammonium nitrate are removed, which may be conveniently accomplished by diafiltration.
  • the nanoparticle stabilizer is a critical component of the reaction mixture.
  • the nanoparticle stabilizer is water soluble and forms weak bonds with cerium ion.
  • K BC represents the binding constant of the nanoparticle stabilizer to cerium ion in water.
  • Log K BC for the nitrate ion is 1 and for hydroxide ion is 14. Most desirably, log (K BC ) lies within this range, preferably towards the bottom of this range.
  • Useful nanoparticle stabilizers include alkoxysubstituted carboxylic acids, ⁇ -hydroxyl carboxylic acids, pyruvic acid and small organic polyacids such as tartaric acid and citric acid.
  • ethoxylated carboxylic acids examples include 2-(methoxy)ethoxy acetic acid and 2-[2-(2-methoxyethoxy)ethoxy]acetic acid (MEEA).
  • MEEA 2-methoxyethoxyethoxyethoxy]acetic acid
  • examples include lactic acid, gluconic acid and 2-hydroxybutanoic acid.
  • Polyacids include ethylenediaminetetraacetic acid (EDTA), tartaric acid, and citric acid.
  • EDTA ethylenediaminetetraacetic acid
  • lactic acid tartaric acid
  • citric acid citric acid.
  • Combinations of compounds with large K BC such as EDTA with weak K BC stabilizers such as lactic acid are also useful at particular ratios.
  • Large K BC stabilizers such as gluconic acid may be used at a low level or with weak K BC stabilizers such as lactic acid.
  • the nanoparticle stabilizer includes a compound of formula (Ia).
  • R represents hydrogen, or a substituted or unsubstituted alkyl group or aromatic group such as, for example, a methyl group, an ethyl group or a phenyl group. More preferably, R represents a lower alkyl group such as a methyl group.
  • R 1 represents hydrogen or a substituent group such as an alkyl group.
  • n represents an integer of 0-5, preferably 2.
  • Y represents H or a counterion, such as an alkali metal, for example Na + or K + .
  • the stabilizer binds to the nanoparticles and prevents agglomeration of the particles and the subsequent formation of large clumps of particles.
  • the nanoparticle stabilizer is represented by formula (Ib), wherein each R 2 independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic group.
  • X and Z independently represent H or a counterion such as Na + or K + and p is 1 or 2.
  • Useful nanoparticle stabilizers are also found among ⁇ -hydroxysubstituted carboxylic acids such as lactic acid or even the polyhydroxysubstituted acids such as gluconic acid.
  • the nanoparticle stabilizer does not include the element sulfur, since sulfur-containing materials may be undesirable for certain applications.
  • sulfur-containing materials may be undesirable for certain applications.
  • the use of a sulfur-containing stabilizer such as AOT may result in the undesirable emission of oxides of sulfur after combustion.
  • the size of the resulting cerium dioxide particles can be determined by dynamic light scattering, a measurement technique for the determination of a particle's hydrodynamic diameter.
  • the hydrodynamic diameter (cf. B. J. Berne and R. Pecora, “Dynamic Light Scattering: With Applications to Chemistry, Biology and Physics”, John Wiley and Sons, NY 1976 and “Interactions of Photons and Neutrons with Matter”, S. H. Chen and M. Kotlarchyk, World Scientific Publishing, Singapore, 1997), which is slightly larger than the geometric diameter of the particle, includes both the native particle size and the solvation shell surrounding the particle. When a beam of light passes through a colloidal dispersion, the particles or droplets scatter some of the light in all directions.
  • the intensity of the scattered light is uniform in all directions (Rayleigh scattering). If the light is coherent and monochromatic as, for example, from a laser, it is possible to observe time-dependent fluctuations in the scattered intensity, using a suitable detector such as a photomultiplier capable of operating in photon counting mode. These fluctuations arise from the fact that the particles are small enough to undergo random thermal (Brownian) motion, and the distance between them is therefore constantly varying. Constructive and destructive interference of light scattered by neighboring particles within the illuminated zone gives rise to the intensity fluctuation at the detector plane which, because it arises from particle motion, contains information about this motion. Analysis of the time dependence of the intensity fluctuation can therefore yield the diffusion coefficient of the particles from which, via the Stokes Einstein equation and the known viscosity of the medium, the hydrodynamic radius or diameter of the particles can be calculated.
  • a continuous process for producing small cerium dioxide nanoparticles includes combining cerous ion, an oxidant, a nanoparticle stabilizer, and hydroxide ion within a continuous reactor, into which reactants and other ingredients are continuously introduced, and from which product is continuously removed.
  • Continuous processes are described, for example, in Ozawa, et al., U.S. Pat. No. 6,897,270; Nickel, et al., U.S. Pat. No. 6,723,138; Campbell, et al., U.S. Pat. No. 6,627,720; Beck, U.S. Pat. No. 5,097,090; and Byrd, et al., U.S. Pat. No. 4,661,321; the disclosures of which are incorporated herein by reference.
  • a solvent such as water is often employed in the process.
  • the solvent dissolves the reactants, and the flow of the solvent can be adjusted to control the process.
  • mixers can be used to agitate and mix the reactants.
  • Any reactor that is capable of receiving a continuous flow of reactants and delivering a continuous flow of product can be employed. These reactors may include continuous-stirred-tank reactors, plug-flow reactors, and the like.
  • the reactants required to carry out the nanoparticle synthesis are preferably charged to the reactor in streams; i.e., they are preferably introduced as liquids or solutions.
  • the reactants can be charged in separate streams, or certain reactants can be combined before charging the reactor.
  • Reactants are introduced into the reaction chamber provided with a stirrer through one or more inlets.
  • the reactants include an aqueous solution of cerous ion, for example, cerous nitrate; an oxidant such as hydrogen peroxide or molecular oxygen, including ambient air; and a stabilizer, such as 2-[2-(2-methoxyethoxy)ethoxy]acetic acid.
  • a two-electron oxidant such as hydrogen peroxide is present, preferably in at least one-half the molar concentration of the cerium ion.
  • molecular oxygen can be bubbled through the mixture.
  • the hydroxide ion concentration is preferably at least twice the molar cerium concentration.
  • a method of forming small cerium dioxide nanoparticles includes the step of forming a first aqueous reactant stream that includes cerous ion, for example, as cerium (III) nitrate, and an oxidant.
  • Suitable oxidants capable of oxidizing Ce(III) to Ce(IV) include, for example, hydrogen peroxide or molecular oxygen.
  • the first reactant stream also includes a nanoparticle stabilizer that binds to cerium dioxide nanoparticles, thereby preventing agglomeration of the particles. Examples of useful nanoparticle stabilizers were mentioned above.
  • the method further includes a step of forming a second aqueous reactant stream that includes a hydroxide ion source, for example, ammonium hydroxide or potassium hydroxide.
  • a hydroxide ion source for example, ammonium hydroxide or potassium hydroxide.
  • the second reactant stream further includes a stabilizer, examples of which were described previously. At least one of the first or second reactant streams, however, must contain a stabilizer.
  • the first and second reactant streams are combined to form a reaction stream. Initially, the temperature of the reaction stream is maintained sufficiently low to form small cerous hydroxide nuclei. Subsequently the temperature is raised so that oxidation of Ce(III) to Ce(IV) occurs in the presence of the oxidant, and the hydroxide is converted to the oxide, thereby producing a product stream that includes cerium dioxide.
  • the temperature for conversion from the hydroxide to the oxide is preferably in the range of about 50-100° C., more preferably about 60-90° C.
  • the first and second reactant streams are combined at a temperature of about 10-20° C., and the temperature is subsequently increased to about 60-90° C.
  • cerium dioxide nanoparticles in the product stream are concentrated, for example, by diafiltration techniques using one or more semi-porous membranes.
  • the product stream includes an aqueous suspension of cerium dioxide nanoparticles that is reduced to a conductivity of about 3 mS/cm or less by one or more semi-porous membranes.
  • FIG. 3 A schematic representation of a continuous reactor suitable for the practice of the invention is depicted in FIG. 3 .
  • the reactor 40 includes a first reactant stream 41 containing aqueous cerium nitrate.
  • An oxidant such as hydrogen peroxide is added to the reactant stream by means of inlet 42 , and the reactants are mixed by mixer 43 a .
  • To the resulting mixture is added stabilizer via inlet 45 , followed by mixing by mixer 43 b .
  • the mixture from mixer 43 b then enters mixer 43 c , where it is combined with a second reactant stream containing ammonium hydroxide from inlet 44 .
  • the first and second reactant streams are mixed using a mixer 43 c to form a reaction stream that may be subjected to mechanical shearing by passing it through a perforated screen.
  • mixer 43 c comprises a colloid mill reactor, as described previously, that is provided with inlet ports for receiving the reactant streams and an outlet port 45 .
  • the temperature of the mixer 43 c is maintained at a temperature in the range of about 10° C. to about 25° C.
  • the mixture from 43 c enters a reactor tube 45 that is contained in a constant temperature bath 46 that maintains tube 45 at a temperature of about 60-90° C.
  • Cerium nanoparticles are formed in the reactor tube 45 , which may include a coil 50 .
  • the product stream then enters one or more diafiltration units 47 , wherein the cerium nanoparticles are concentrated using one or more semi-porous membranes.
  • One or more diafiltration units may be connected in series to achieve a single pass concentration of product, or the units may placed in parallel for very high volumetric throughput.
  • the diafiltration units may be disposed both in series and parallel to achieve both high volume and rapid throughput.
  • stabilizer may be added to the second reactant stream via port 51 rather than to the first reactant stream via port 45 .
  • the product stream of concentrated cerium nanoparticles exiting the diafiltration unit 47 is combined with a stream that includes a nonpolar solvent and at least one surfactant, wherein the surfactant is chosen so that a reverse micelle is formed in the emulsion, as described below.
  • cerium dioxide nanoparticles allow better control of the production of particle nuclei and their growth relative to that afforded by batch reactors.
  • the nuclei size can be controlled by the initial reagent concentration, temperature, and the ratio of nanoparticle stabilizer to reagent concentrations. Small nuclei are favored by low temperatures, less than about 20° C., and high ratios of nanoparticle stabilizer to reagent concentrations. In this way, very small cerium dioxide nanoparticles having a mean hydrodynamic diameter of less than about 10 nm can be produced in an economical manner.
  • aqueous precipitation medium in which cerium dioxide particles are typically formed to subsequently enhance the activity of the nanoparticles
  • flame temperatures may reach levels as high as 900° C. (1652° F.).
  • 900° C. (1652° F.) At these high temperatures, reduction of cerium and production of oxygen according to equation 1 is very efficient.
  • superheated steam can be generated from the water. This not only will increase the compression ratio, resulting in higher engine efficiency, but will also result in the separation of the fuel wave front into many, very small, high surface area droplets.
  • the invention provides a method for formulating a homogeneous mixture that includes cerium dioxide nanoparticles, a nanoparticle stabilizer, a surfactant, water, and a nonpolar solvent.
  • the nanoparticles have a mean diameter of less than about 10 nm, more preferably less than about 8 nm, most preferably about 6 nm.
  • cerium dioxide nanoparticles can be prepared by various procedures. Typical synthetic routes utilize water as a solvent and yield an aqueous mixture of nanoparticles and one or more salts.
  • cerium dioxide particles can be prepared by reacting the hydrate of cerium (III) nitrate with hydroxide ion from, for example, aqueous ammonium hydroxide, thereby forming cerium (III) hydroxide, as shown in equation (2a).
  • Cerium hydroxide can be oxidized to cerium (IV) dioxide with an oxidant such as hydrogen peroxide, as shown in equation (2b).
  • the analogous tris hydroxide stoichiometry is shown in equations (3a) and (3b).
  • the species Ce(OH) 2 (NO 3 ) or (NH 4 ) 2 Ce(NO 3 ) 5 may initially be present, subsequently undergoing oxidation to cerium dioxide.
  • the cerium dioxide particles are formed in an aqueous environment and combined with one or more nanoparticle stabilizers.
  • the cerium dioxide nanoparticles are either formed in the presence of the stabilizer(s), or a stabilizer(s) is added shortly after their formation.
  • Useful nanoparticle stabilizers include alkoxysubstituted carboxylic acids, a-hydroxyl carboxylic acids, pyruvic acid, and small organic polycarboxylic acids. Examples of alkoxysubstituted carboxylic acids include 2-(methoxy)ethoxy acetic acid and 2-[2-(2-methoxyethoxy)ethoxy]acetic acid (MEEA).
  • the nanoparticle stabilizer includes a compound of formula (Ia) or formula (Ib), as described above.
  • the reaction mixture includes, in addition to cerium dioxide nanoparticles, one or more salts, for example, ammonium nitrate and unreacted cerium nitrate.
  • the stabilized particles can be separated from these materials and salts by washing with 18 Mohm water in an ultrafiltration or diafiltration apparatus. Low ionic strength ( ⁇ 3 mS/cm) is highly desirable for the formation and stabilization of retained water in a micellar state.
  • the washed, stabilized cerium dioxide nanoparticles may be concentrated, if desired, using a semi-porous membrane, for example, to form an aqueous concentrate of the nanoparticles.
  • the particles may be concentrated by other means as well, for example, by centrifugation.
  • the cerium dioxide nanoparticles are concentrated by diafiltration.
  • the diafiltration technique utilizes ultrafiltration membranes, which can be used to completely remove, replace, or lower the concentration of salts in the nanoparticle-containing mixture.
  • the process selectively utilizes semi-permeable (semi-porous) membrane filters to separate the components of the reaction mixture on the basis of their molecular size.
  • a suitable ultrafiltration membrane would be sufficiently porous so as to retain the majority of the formed nanoparticles, while allowing smaller molecules such as salts and water to pass through the membrane. In this way, the nanoparticles and the associated bound stabilizer can be concentrated.
  • the materials retained by the filter, including the stabilized nanoparticles are referred to as the concentrate or retentate, the discarded salts and unreacted materials as the filtrate.
  • Pressure may be applied to the mixture to accelerate the rate at which small molecules passes through the membrane (flow rate) and to speed the concentration process.
  • Other means of increasing the flow rate include using a large membrane having a high surface area, and increasing the pore size of the membrane, but without an unacceptable loss of nanoparticles.
  • the membrane is selected so that the average pore size of the membrane is about 30% or less, 20% or less, 10% or less, or even 5% or less than that of the mean diameter of the nanoparticles.
  • the pore diameter must be sufficient to allow passage of water and salt molecules. For example, ammonium nitrate and unreacted cerium nitrate should be completely or partially removed from the reaction mixture.
  • the average membrane pore size is sufficiently small to retain particles of 3 nm diameter or greater in the retentate. This would correspond to a protein size of approximately 3 kilodaltons.
  • the concentrate includes stabilized nanoparticles and residue water.
  • the concentration of cerium dioxide nanoparticles is preferably greater than about 0.5 molal, more preferably greater than about 1.0 molal, even more preferably greater than about 2.0 molal.
  • the concentrate is combined with one or more surfactants and a nonpolar solvent to form a homogeneous mixture.
  • the surfactant is chosen so that a reverse micelle consisting of an aqueous, stabilized cerium dioxide nanoparticles dispersed in a nonpolar medium is formed.
  • Reverse micellar solutions consisting of particles in an aqueous environment dispersed in a nonpolar solvent, have been described previously in, for example, Ying, et al., in U.S. Pat. No. 6,869,584 and U.S. Patent Appl. Publ. No. 2005/0152832, the disclosures of which are incorporated herein by reference.
  • the former may be incorporated into the structure of the latter to varying extents.
  • the stabilized cerium dioxide nanoparticles are added, with mixing, to a solution of the surfactant and a co-surfactant and a nonpolar solvent at a temperature in the range of about 25° C. to about 0° C.
  • Suitable nonpolar solvents include, for example, hydrocarbons containing about 6 to 20 carbon atoms, for example, pentane, heptane, octane, decane and toluene, and hydrocarbon fuels such as gasoline, biodiesel, and diesel fuels.
  • Useful surfactants include nonylphenyl ethoxylates having the formula, C 9 H 19 C 6 H 4 (OCH 2 CH 2 ) n OH, wherein n is 4-6.
  • Other surfactants that contain both an ether group and an alcohol group includes compounds of formula (Ic), in which R 3 represents a substituted or unsubstituted alkyl group, and m is an integer of 1-8.
  • carboxylate surfactants such as the salts of stearic acid, palmitic acid, and oleic acid may be useful as surfactants.
  • R 2 independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic group
  • X and Z independently represent H or a counterion such as Na + , or K +
  • p is 1 or 2.
  • the reverse-micelle forming agent includes an anionic surfactant and a nonionic co-surfactant.
  • useful co-surfactants include aliphatic alcohols, for example, pentanol and hexanol and their geometric isomers.
  • cerium dioxide nanoparticle dispersions using a reverse micelle formation allows the aqueous nanoparticle stabilizing agent(s) to be independently optimized from that of the surfactant(s).
  • a desirable reverse-micellar composition is effective for lowering the cold pour cloud point of diesel fuel, that is, the temperature at which wax crystals begin to form and the diesel fuel begins to gel.
  • the cold pour cloud point see Langer et al., U.S. Pat. No. 6,368,366 and U.S. Pat. No. 6,383,237, the disclosures of which are incorporated herein by reference.
  • the cerium dioxide nanoparticle concentrate preferably includes high resistivity water, that is, water having a resistivity of about 1-18 mega ohm per cm, preferably about 18 mega ohm per cm. Pure water has a resistivity of 18.3 mega ohm per cm.
  • Resistivity is the reciprocal of conductivity, which is the ability of a material to conduct electric current.
  • Conductivity instruments can measure conductivity by including two plates that are placed in the sample, applying a potential across the plates (normally a sine wave voltage), and measuring the current.
  • the basic unit of conductivity is the siemens (S), or milli-Siemens (mS). Since cell geometry affects conductivity values, standardized measurements are expressed in specific conductivity units (mS/cm) to compensate for variations in electrode dimensions.
  • micellar composition it is desirable that very few ions be present in the cerium dioxide concentrate to conduct electricity. This situation can be achieved by concentrating the cerium dioxide particles through diafiltration to a conductivity level of less than 5 mS/cm, preferably to 3 mS/cm or less.
  • the present invention is further directed to a method for formulating a homogeneous mixture including cerium dioxide nanoparticles, at least one nanoparticle stabilizer and at least one surfactant, water, and a nonpolar solvent.
  • a first step provides an aqueous mixture including stabilized cerium dioxide nanoparticles, wherein molecules of the nanoparticle stabilizer are closely associated with the nanoparticles.
  • a second step includes concentrating the stabilized cerium dioxide nanoparticles while minimizing the ionic strength of the suspension to form an aqueous concentrate that is relatively free of anions and cations.
  • a third step includes combining the concentrate with a nonpolar solvent, containing a surfactant, thereby forming a substantially homogeneous mixture that is a thermodynamically stable, multicomponent, single phase, reverse (“water in oil”) micellar solution.
  • the substantially homogeneous mixture contains water at a level of preferably about 0.5 wt. % to about 20 wt. %, more preferably, about 5 wt. % to about 15 wt. %.
  • the cerium dioxide nanoparticles have a mean hydrodynamic diameter of preferably less than about 10 nm, more preferably less than about 8 nm, most preferably about 6 nm. Desirably, the cerium dioxide nanoparticles have a primary crystallite size of about 2.5 nm ⁇ 0.5 nm and comprise one or at most two crystallites per particle edge length.
  • the aqueous mixture is advantageously formed in a colloid mill reactor, and the nanoparticle stabilizer may comprise an ionic surfactant, preferably a compound that includes a carboxylic acid group and an ether group.
  • the nanoparticle stabilizer may comprise a surfactant of formula (Ia),
  • R represents hydrogen or a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic group
  • R 1 represents hydrogen or an alkyl group
  • Y represents H or a counterion
  • n 0-5.
  • R represents a substituted or unsubstituted alkyl group
  • R 1 represents hydrogen
  • Y represents hydrogen
  • n is 2.
  • Another suitable nanoparticle stabilizer comprises a compound of formula (Ib),
  • each R 2 independently represents hydrogen, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic group;
  • X and Z independently represent H or a counterion
  • p 1 or 2.
  • nanoparticle stabilizers are included in the group consisting of lactic acid, gluconic acid enantiomers, EDTA, tartaric acid, citric acid, and combinations thereof.
  • the surfactant may also comprise a nonionic surfactant, preferably a compound comprising an alcohol group and an ether group, in particular, a compound of formula (Ic),
  • R 3 represents a substituted or unsubstituted alkyl group; and m is an integer from 1 to 8.
  • the nonionic surfactant may also comprise a compound of formula (Id),
  • R 3 represents a substituted or unsubstituted alkyl group
  • ⁇ is an aromatic group
  • n is an integer from 4 to 6.
  • the surfactant may also comprise an anionic surfactant, preferably a compound containing a sulfonate group or a phosphonate group.
  • a useful anionic surfactant is sodium bis(2-ethyl-1-hexyl)sulfosuccinate (AOT).
  • the aqueous reaction mixture may further include a co-surfactant, preferably an alcohol.
  • Concentrating the aqueous mixture is preferably carried out using diafiltration, which results in the reduction in conductivity of said concentrated aqueous mixture to about 3 mS/cm or less.
  • the nonpolar solvent included in the substantially homogeneous solution is advantageously selected from among hydrocarbons containing about 6-20 carbon atoms, for example, octane, decane, toluene, diesel fuel, biodiesel, and mixtures thereof.
  • hydrocarbons containing about 6-20 carbon atoms for example, octane, decane, toluene, diesel fuel, biodiesel, and mixtures thereof.
  • one part of the homogeneous mixture is with at least about 100 parts of the fuel.
  • cerium dioxide nanoparticles comprising a core and a shell, wherein the shell comprises a material selected from the group consisting of a transition metal, a lanthanide, a sulfur-containing compound that may include a mercaptide group, and combinations thereof.
  • the core comprises about 90% or less of the nanoparticle by volume
  • the shell comprises about 5% or more of the nanoparticle by volume.
  • the shell comprises lattice sites, and up to about 30% of the lattice sites include a material selected from the group consisting of a transition metal, a lanthanide, a sulfur-containing compound, and combinations thereof.
  • the transition metal is preferably selected from the group consisting of Fe, Mn, Cr, Ni, W, Co, V, Cu, Mo, and Zr, or from the lanthanide series, and combinations thereof. Desirably, the transition metal is capable of binding to iron. It is also desirable that the transition metal be capable of reacting with an oxide of sulfur. In a further embodiment, the transition metal is associated with at least one ligand that comprises sulfur.
  • a composition comprising aqueously suspended cerium dioxide nanoparticles that comprise a core and a shell, wherein the shell includes at least one transition metal, may be subsequently solvent shifted into a non polar medium in which the particles are essentially water free and are incorporable into a lubrication oil.
  • the nanoparticles in the oil act as an adjuvant to further reduce friction of contacting moving engine parts.
  • the potential benefits of the coating include added protection of the engine from thermal stress; for example, CeO 2 melts at 2600° C., whereas cast iron, a common material used in the manufacture of diesel engines, melts at about 1200-1450° C. Even 5 nm ceria particles have demonstrated the ability to protect steel from oxidation for 24 hours at 1000° C., so the phenomenon of size dependent melting would not be expected to lower the melting point of the cerium dioxide nanoparticles of the invention below the combustion temperatures encountered in the engine. See, for example, Patil et al., Journal of Nanoparticle Research, vol. 4, pp 433-438 (2002).
  • An engine so protected may be able to operate at higher temperatures and compression ratios, resulting in greater thermodynamic efficiency.
  • a diesel engine having cylinder walls coated with cerium dioxide would be resistant to further oxidation (CeO 2 being already fully oxidized), thereby preventing the engine from “rusting.” This is important because certain additives used to reduce carbon emissions or improve fuel economy such as, for example, the oxygenates MTBE, ethanol and other cetane improvers such as peroxides, also increase corrosion when introduced into the combustion chamber, which may result in the formation of rust and degradation of the engine lifetime and performance.
  • the coating should not be so thick as to impede the cooling of the engine walls by the water recirculation cooling system.
  • the current invention provides cerium dioxide nanoparticles having a mean hydrodynamic diameter of less than about 10 nm, preferably less than about 8 nm, more preferably 6 nm or even less, that are useful as a fuel additive for diesel engines.
  • the surfaces of the cerium dioxide nanoparticles may be modified to facilitate their binding to an iron surface, and desirably would, when included in a fuel additive composition, rapidly form a ceramic oxide coating on the surface of diesel engine cylinders.
  • a transition or lanthanide metal having a binding affinity for iron is incorporated onto the surface of the cerium dioxide nanoparticles.
  • iron surfaces include those that exist in many internal parts of engines.
  • Suitable transition metals include Mn, Fe, Ni, Cr, W, Co, V, Cu, and Zr.
  • the transition or lanthanide metal ion which is incorporated into the cerium dioxide nanoparticles by occupying a cerium ion lattice site in the crystal, may be introduced as a dopant during the latter stages of the precipitation of cerium dioxide.
  • the dopant can be added in combination with cerous ion, for example, in a single jet manner in which both cerous ion and transition metal ion are introduced together into a reactor containing ammonium hydroxide.
  • the dopant and cerous ion can be added together with the simultaneous addition of hydroxide ion.
  • the doped particles can also be formed in a double jet reaction of cerous ion with dissolved transition metal ion titrated against an ammonium hydroxide steam simultaneously introduced by a second jet. In any event, it is understood that sufficient nanoparticle stabilizer is present to prevent agglomeration of the nascent particles.
  • cerium dioxide nanoparticles are prepared having a core-shell structure.
  • the core of the particle preferably includes at least about 75% more preferably, about 95% or greater of the bulk particle, and may be optionally doped with a metal.
  • the shell, including the outer portion and surface of the particle preferably comprises about 25% or less, more preferably about 10% or less, most preferably about 5% or less, of the particle, and includes a transition or lanthanide metal. Up to about 30% of the Ce +4 lattice sites of the shell may occupied by one or more transition or lanthanide metals. Suitable transition metals include Mn, Fe, Ni, Cr, W, Co, V, Cu, Zr, and Mo, and combinations thereof.
  • the cerium dioxide nanoparticles have a core-shell structure, wherein the shell includes at least one compound comprising sulfur.
  • the sulfur is present so that it is capable of forming a bond with iron.
  • the sulfur contained in the shell of the cerium dioxide particles binds to the iron surface of the combustion chamber of the engine, thereby accelerating the deposition of cerium dioxide on the surface of the combustion chamber.
  • Suitable sulfur compounds include ZnS, MnS, FeS, Fe 2 S 3 , CoS, NiS, and CuS.
  • the sulfur may be part of a transition metal ligand, wherein the metal and its associated ligand are incorporated into the surface of the cerium dioxide nanoparticles.
  • ligands that include a mercaptide group can form sulfur-iron bonds.
  • Sulfur can be incorporated into the cerium dioxide nanoparticles during the aqueous precipitation of CeO 2 , for example, by incorporating with the cerium nitrate hexahydrate reactant the appropriate water soluble transition metal salt (nitrate, sulfate or chloride), together with a labile source of sulfur such as thiosulfate (alternatively, the thiosulfate salt of a transition metal may be used).
  • the cerium hydroxide to the oxide at elevated temperatures, for example, about 70-90° C.
  • the corresponding transition metal sulfide will also form.
  • a transition metal is incorporated into the surface of the cerium dioxide nanoparticles.
  • this metal is chosen so that it is capable of reacting with sulfur and forming a bond to sulfur.
  • the transition metal is present in the reaction mixture during the shell formation of the CeO 2 precursor (cerium hydroxide).
  • Suitable metals include Mn and Fe as well as W, Co, V, Cu, and Mo.
  • Typical aqueous soluble transition metal salts include sulfates, nitrates, and chlorides of these metals.
  • the transition metal-containing nanoparticles can bind sulfur that may be present in the fuel.
  • Iron for example, can react with sulfur dioxide to form Fe 2 S 3 .
  • Removal of sulfur after fuel combustion is very desirable, since many vehicle exhaust systems include particulate traps containing a platinum catalyst that can be poisoned by sulfur. Hence removal of sulfur before it reaches the catalyst can prolong the life of the catalyst.
  • Useful metals for the reduction of sulfur dioxide are also described by Yamashita , et al., U.S. Pat. No. 5,910,466, the disclosure of which is incorporated herein by reference.
  • an emulsion which is a stable mixture of at least two immiscible liquids. Although immiscible liquids tend to separate into two distinct phases, an emulsion can be stabilized by the addition of a surfactant that functions to reduce surface tension between the liquid phases.
  • An emulsion comprises a continuous phase and a disperse phase that is stabilized by a surfactant.
  • a water-in-oil (w/o) emulsion having a disperse aqueous phase and an organic continuous phase, typically comprising a hydrocarbon, is often referred to as a “reverse-micellar composition.”
  • a reverse-micellar composition comprises a disperse phase comprising a cerium (IV) nanoparticle-containing aqueous composition, together with a continuous phase comprising a hydrocarbon liquid and at least one surfactant.
  • a fuel additive composition of the invention comprises a reverse-micellar composition whose aqueous disperse phase includes in situ-formed nanoparticles comprising a cerium (IV) oxidic compound, and whose continuous phase includes a hydrocarbon liquid and a surfactant/stabilizer mixture.
  • the surfactant/stabilizer mixture is effective to restrict the size of the nanoparticles thus formed, preventing their agglomeration and enhancing the yield of the nanoparticles.
  • a reverse-micellar composition comprises: an aqueous disperse phase that includes a free radical initiator, and a continuous phase that includes a hydrocarbon liquid and at least one surfactant.
  • the reverse-micellar composition may include cerium-containing nanoparticles.
  • a fuel additive composition comprises: a continuous phase comprising a hydrocarbon liquid, a surfactant, and optionally a cosurfactant; and forming a reverse-micellar composition comprising an aqueous disperse phase that includes a cetane improver effective for improving engine power during combustion of the fuel.
  • the fuel additive composition optionally further comprises cerium-containing nanoparticles, which may be included in either a separate dispersion or a separate reverse-micellar composition.
  • a water-in-oil emulsion has a small micellar disperse size, and the particulate material is formed within the aqueous disperse phase.
  • the appropriate choice of surfactants and reaction conditions provides for the formation of stable emulsions, the control of particle size distribution and growth, and the prevention of particle agglomeration.
  • the oil phase preferably comprises a hydrocarbon, which may further include oxygen-containing compounds.
  • the disperse aqueous phase is encompassed by a surfactant boundary that isolates and stabilizes the aqueous phase from the organic continuous phase.
  • a surfactant included in the emulsion preferably in the continuous phase to stabilize the reverse micelles can be an ionic surfactant, a non-ionic surfactant, or a combination thereof.
  • Suitable surfactants include, for example, nonylphenyl ethoxylates, monoalkyl and dialkyl carboxylates, and combinations thereof.
  • the difficulties of using two distinct reverse micelles for the cerium-containing reactant and a precipitating agent such as ammonium hydroxide are avoided by the present invention, which provides for the combination of both reactants into a single reverse micelle using a homogeneous precipitation method, wherein a first reactant is homogeneously mixed with a precursor of a second reactant.
  • a suitable first reactant is a
  • Ce +4 -containing compound which may be obtained by oxidation using H 2 O 2 for example, of a Ce +3 -containing compound such as, for example, Ce(NO 3 ) 3 .6H 2 O.
  • a suitable second reactant is ammonia, NH 3 , which can be obtained by the heat- and/or light activated hydrolysis of hexamethylenetetramine, C 6 H 12 N 4 , (HMT), as shown in equation (4):
  • Ce(NO 3 ) 3 (6 H 2 O) is combined with H 2 O 2 to generate a Ce +4 -containing solution.
  • the solution further includes a stabilizer for controlling the size of the cerium-containing nanoparticles.
  • a preferred stabilizer is 2-[2-(2-methoxyethoxy)ethoxy]acetic acid (MEEA).
  • MEEA 2-[2-(2-methoxyethoxy)ethoxy]acetic acid
  • the resulting mixture is then slowly added to an oil phase comprising a surfactant and an organic solvent such as, for example, toluene, octane, decane, gasoline, D2 diesel fuel, ULSD, biodiesel, or combinations thereof.
  • a surfactant such as, for example, toluene, octane, decane, gasoline, D2 diesel fuel, ULSD, biodiesel, or combinations thereof.
  • the new mixture is heated to a temperature just sufficient to effect substantially complete formation of the Ce-containing nanoparticles.
  • the precise temperature required depends on the choice of reverse-micelle surfactant and the concentration of the first reactant and second reactant precursor but is desirably maintained below about 47° C.
  • the reverse-micelle surfactant may also serve to stabilize the Ce-containing nanoparticles.
  • the aqueous Ce +4 -HMT mixture may be premixed with another surfactant different from that used to form the reverse-micellar composition.
  • the aqueous composition may optionally further include a cetane improving agent generally recognized to be a free radical forming species at elevated temperatures.
  • the individual micelles may be small enough to encompass a single cerium-containing nanoparticle or large enough to contain a plurality of the nanoparticles.
  • the micelles have a diameter of preferably about 5 nm to about 50 nm, more preferably about 20 nm.
  • the cerium-containing nanoparticles have a diameter of preferably about 1 nm to about 15 nm, more preferably about 2 nm to about 10 nm.
  • the CH 2 O generated in the aqueous phase by the hydrolysis of HMT may be utilized in a subsequent fuel combustion process.
  • the CH 2 O can effect cross-linking within the micelle, strengthening it or increasing its heat-resistance.
  • a fuel additive emulsion formed by the reverse micelle process of the present invention includes water used in the preparation of the cerium-containing nanoparticles. Excess water introduced into a fuel with the cerium-containing emulsion can lead to a loss of engine power. To overcome this problem and thereby improve fuel performance, water can be removed from the cerium-containing aqueous phase and replaced by a cetane improver. Water removed by, for example, diafiltration may be replaced by a water-soluble cetane improving compound.
  • Compounds suitable for this purpose include, for example, 30-50 wt. % aqueous H 2 O 2 , t-butyl hydroperoxide, nitromethane, and low molecular weight alkyl ethers such as dimethyl ether and diethyl ether.
  • Free radical initiators such as, for example, H 2 O 2 are known to be effective cetane improvers for diesel fuel, resulting in reductions in soot and hydrocarbon emission.
  • Cetane number is an indicator of the ignition delay time after injection of fuel into the combustion chamber; alternatively, it can be regarded as being related to the inverse of the ignition time, i.e., the time between the injection of the diesel fuel into the compressed superheated air in the combustion chamber and the actual ignition of the injected fuel stream. The higher the cetane number, the more completely combusted the fuel and the less soot production, as ignition delay gives rise to the formation of soot.
  • equation (7) represents the dominant reaction path for the decomposition of peroxide at temperatures above 727° C., not the thermolytic reaction generating water and oxygen, as shown in equation (8).
  • Maganas et al. U.S. Pat. No. 6,962,681
  • the disclosure of which is incorporated herein by reference describes a system wherein catalytically reactive particles of silica or alumina interact with the moisture in combustion exhaust gases to generate hydroxyl radicals, which are returned to the site of combustion and increases the efficiency of combustion, resulting in reduced soot formation.
  • Hashimoto et al. U.S. Patent Application Serial No. 2006/0185644, the disclosure of which is incorporated herein by reference, describes a fuel composition that includes 95-99.5 wt. % of a base fuel and 0.1-5 wt. % of an additive compound selected from the group consisting of an organic peroxide such as di-t-butyl peroxide, a nitrate ester such as n-pentyl nitrate, a nitrite ester such as n-pentyl nitrite, and an azo compound such as 2,2-azobis(2,4-dimethylvaleronitrile).
  • an additive compound selected from the group consisting of an organic peroxide such as di-t-butyl peroxide, a nitrate ester such as n-pentyl nitrate, a nitrite ester such as n-pentyl nitrite, and an azo compound such as 2,2-azobis(2,4-di
  • a fuel-borne additive in which the reverse micelle contains only a free radical precursor could be used to great advantage with a nanoparticulate lubricity enhancing agent introduced as a component of the lubrication oil.
  • reverse micellar compositions having very small disperse particle diameters, preferably about 5 nm to about 50 nm, more preferably about 10 nm to about 30 nm, are very effective, as their disintegration and attendant release of superheated steam helps to mix the additive-containing diesel fuel with air in the combustion chamber, resulting in more complete fuel combustion.
  • the free radical initiators included in the reverse micelle in accordance with the present invention have substantial water-solubility.
  • U.S. Pat. No. 3,951,934 discloses azo-bis compounds, as well as combinations of water-soluble peroxides with tertiary amines, sulfites, and bromates.
  • U.S. Pat. No. 5,248,744 teaches azo-bis compounds as well as peroxydisulfates and organic peroxides.
  • U.S. Pat. No. 6,391,995 discloses the use of water-soluble azo initiators, including four compounds commercially available from Wako Chemicals, Dallas Tex.
  • Puchin et al. USSR patents 236,987 and 214,710 (1970), discloses that poly(dimethyl(vinylethynyl)methyl) t-butyl peroxide at a 0.01% level, i.e. 100 ppm, gives a A cetane % additive ratio of 1000, corresponding to a cetane improvement of 10.
  • the references also disclose “other additives” that may be small mono esters incorporated into aqueous micelles, or even long chain fatty acid mono esters (high cetane rating) that would not require incorporation as a reverse micelle but might act as a surfactant for a reverse micelle emulsion.
  • a fuel additive composition of the present invention may comprise more than one type of reverse micelle.
  • one type of reverse micelle may include a cetane improver
  • a second type reverse micelle may include cerium-containing nanoparticles together with associated reverse micellar phase water that may be at least partially replaced by a free radical initiator such as hydrogen peroxide or, more preferably, a stabilized hydrogen peroxide.
  • a cerium-containing fuel additive composition includes a surfactant/stabilizer mixture that preferably includes a combination of at least one non-ionic surfactant with at least one anionic surfactant, or a combination of a single-charged anionic surfactant and a multiple-charged anionic surfactant.
  • the effect of the combination of surfactant/stabilizer compounds is to restrain the size of the nanoparticles, prevent their agglomeration, and enable an increase in the concentration of reactants, thereby producing a higher yield of nanoparticles.
  • the surfactant/stabilizer combination may have the added benefit of aiding in the solvent shift process from the aqueous polar medium to the non-polar oil medium.
  • the charged surfactant compound plays a dominant role in the aqueous environment.
  • the charged compound is likely to be solubilized into the aqueous phase and washed out, and the uncharged compound becomes more important in stabilizing the reverse micelle emulsion.
  • Dicarboxylic acids and their derivatives so called “gemini carboxylates”, where the carboxylic groups are separated by at most two methylene groups, are also useful cerium dioxide nanoparticle stabilizers. Additionally, C 2 -C 8 alkyl, alkoxy and polyalkoxy substituted dicarboxylic acids are advantageous stabilizers.
  • nanoparticle stabilizer compounds preferably comprise organic carboxylic acids such as, for example, 2-[2-(2-methoxyethoxy)ethoxy]acetic acid (MESA) and ethylenediaminetetraacetic acid (EDTA), lactic acid, gluconic acid, tartaric acid, citric acid, and mixtures thereof.
  • organic carboxylic acids such as, for example, 2-[2-(2-methoxyethoxy)ethoxy]acetic acid (MESA) and ethylenediaminetetraacetic acid (EDTA), lactic acid, gluconic acid, tartaric acid, citric acid, and mixtures thereof.
  • a reverse-micellar composition in accordance with the present invention comprises an aqueous disperse phase that includes a free radical initiator, preferably water-soluble, and a continuous phase that includes a surfactant, an optional co-surfactant, and a hydrocarbon liquid, preferably selected from among toluene, octane, decane, D2 diesel fuel, ULSD, biodiesel, and mixtures thereof In general, hydrocarbons containing about 6-20 carbon atoms are useful.
  • the aqueous disperse phase of the composition comprises micelles having a mean diameter of preferably about 5 nm to about 50 nm, more preferably about 3 nm to about 10 nm.
  • Free radical initiators suitable for inclusion in the aqueous dispersed phase may be selected from the group consisting of: hydrogen peroxide, organic hydroperoxides, organic peroxides, organic peracids, organic peresters, organic nitrates, organic nitrites, azobis compounds, persulfate compounds, peroxydisulfate compounds, and mixtures thereof.
  • Preferred azobis compounds are selected from the group consisting of 2-2′-azobis(2-methylpropionamidine) dihydrochloride; 4-4′-azobis(4-cyanovaleric) acid; 2-2′azobis[2-methyl-N-(2-hydroxyethyl)propionamide]; 2-2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, and mixtures thereof.
  • the free radical initiator in the aqueous dispersed phase comprises stabilized hydrogen peroxide or t-butyl hydroperoxide.
  • the aqueous disperse phase may further comprise, in addition to the aforementioned peroxides, a compound selected from the group consisting of a tertiary amine compound, a sulfite compound, a bromate compound, and mixtures thereof.
  • the reverse-micellar composition may further comprise boric acid or a borate salt in the aqueous disperse phase, and the hydrocarbon liquid preferably comprises diesel fuel.
  • the hydrocarbon liquid preferably comprises diesel fuel.
  • a lubricating oil that optionally contains cerium-containing nanoparticles may be used in conjunction with a fuel containing the reverse-micelle fuel additive.
  • the reverse micellar composition of the invention preferably includes as a radical initiator stabilized hydrogen peroxide or t-butyl hydroperoxide in the aqueous phase at a level of 30%, 40%, or even 50% or greater by weight.
  • the ratio of water to hydrocarbon by weight is greater than or equal to about 5%, about 10%, or preferably, greater than or equal to about 15% by weight.
  • the reverse micellar composition includes an alcohol such as hexanol, and/or an alkoxylate surfactant such as Triton N-57.
  • a method for improving the performance of a diesel engine includes adding to diesel fuel, for example, D2 diesel or biodiesel, a reverse micellar composition comprising an aqueous first disperse phase that includes a free radical initiator and a first continuous phase that includes a first hydrocarbon liquid and at least one first surfactant.
  • Suitable free radical initiators such as hydrogen peroxide or t-butyl hydroperoxide, suitable hydrocarbon solvents preferably containing about 6 to about 20 carbon atoms, and suitable surfactants were described above.
  • Preferred surfactants include only the elements C, H, and O.
  • the aqueous disperse phase includes about 20 wt. %, or 30 wt. %, or more preferably 40 wt.
  • the modified diesel fuel includes less than 500 ppm water unless accompanied by an equal amount of free radical initiator.
  • a useful reverse micellar composition for use as a diesel fuel additive includes an aqueous disperse phase that includes a boric acid or a borate salt, and a continuous phase that includes a surfactant and a hydrocarbon liquid.
  • useful borate salts include, for example, sodium borate and potassium borate.
  • useful hydrocarbon liquids include toluene, octane, decane, D2 diesel fuel, biodiesel, and mixtures thereof. In general, hydrocarbons containing about 6-20 carbon atoms are useful.
  • Suitable surfactants include Aerosol AOT; however, as already mentioned, preferred surfactants include only the elements C, H, and O.
  • the aqueous disperse phase of the composition comprises micelles having a mean diameter of, preferably, about 5 nm to about 50 nm, more preferably, about 10 nm to about 30 nm.
  • a method for improving diesel engine performance includes the addition of an additive as described above to diesel fuel to obtain modified diesel fuel.
  • an additive when used in combination with diesel fuel, may provide improved diesel fuel mileage, reduced diesel engine wear, or reduced pollution or a combination of these features.
  • Motor oil is used as a lubricant in various kinds of internal combustion engines in automobiles and other vehicles, boats, lawn mowers, trains, airplanes, etc.
  • engines there are contacting parts that move against each other at high speeds, often for prolonged periods of time.
  • Such rubbing motion causes friction, forming a temporary weld, which absorbs otherwise useful power produced by the motor and converting the energy to useless heat. Friction also wears away the contacting surfaces of those parts, which may lead to increased fuel consumption and lower efficiency and degradation of the motor.
  • a motor oil includes a lubricating oil, cerium dioxide nanoparticles, desirably having a mean diameter of less than about 10 nm more preferably 5 nm, and optionally, a surface adsorbed stabilizing agent.
  • Diesel lubricating oil is essentially free of water, preferably less than 300 ppm, but may be desirably modified by the addition of a cerium dioxide-containing reverse-micellar composition in which the cerium dioxide has been solvent shifted from its aqueous environment to that of an organic or non-polar environment.
  • the cerium dioxide compositions include nanoparticles having a mean diameter of less than about 10 nm more preferably about 6 nm, as already described.
  • a diesel engine operated with modified diesel fuel and modified lubricating oil provides greater efficiency and may, in particular, provide improved fuel mileage, reduced engine wear or reduced pollution, or a combination of these features.
  • Metal polishing also termed buffing, is the process of smoothing metals and alloys and polishing to a bright, smooth mirror-like finish. Metal polishing is often used to enhance cars, motorbikes, antiques, etc. Many medical instruments are also polished to prevent contamination in marks in the metals. Polishing agents are also used to polish optical elements such as lenses and mirrors to a surface smoothness within a fraction of the wavelength of the light they are to manage. Smooth, round, uniform cerium dioxide particles of the present invention may be advantageously employed as polishing agents, and may further be used for planarization (rendering the surface smooth at the atomic level) of semiconductor substrates for subsequent processing of integrated circuits.
  • Nanoparticles, or quantum dots, are being considered for many potential applications. Because of their small size, on the order of 1- 20 nm, these nanoparticles have properties different from their bulk versions, 100 nm and larger. They exhibit novel electronic, magnetic, optical, chemical, and mechanical properties that make them attractive for many technological applications. Those nanoparticles that fall into the semiconductor material category are being considered for biological labeling and diagnostics, light emitting diodes, solid-state lighting, photovoltaic devices, and lasers. Cerium dioxide nanoparticles are wide-gap semiconductors that are potentially useful in such applications. Furthermore, suitably doped versions of cerium dioxide nanoparticles could extend the range of applications.
  • the second property involves the utility of the Ce 3+ /Ce 4+ redox couple.
  • Reactive free radical species such as the hydroxyl radical (OH) that can cause cellular damage in the body can be chemically reduced to the relatively harmless hydroxyl anion (OHF) by Ce 3+ .
  • the oxygen radical anion O2. ⁇
  • Ce 4+ another cellular damaging radical species
  • Suitably engineered nanoparticulate ceria, along with other nanomaterials, may be used as a biotag exploiting surface enhanced Raman spectroscopy for fields such as immunodiagnostics, molecular diagnostics and proteomics.
  • the mixer was a colloid mill manufactured by Silverson Machines, Inc., modified to enable reactants to be introduced directly into the mixer blades by way of a peristaltic tubing pump.
  • the mixer was set to 5,000 rpm, and 8.0 gm of 30% H 2 O 2 was added to the reactor vessel. Then 16 ml of 28%-30% NH 4 OH, diluted to 40 ml, was pumped into the reactor vessel by way of the mixer head in about 12 seconds.
  • the initially clear solution turned an orange/brown in color.
  • the reactor vessel was moved to a temperature controlled water jacket, and a mixer with an R-100 propeller was used to stir the solution at 450 rpm.
  • the pH was 3.9 at 25° C.
  • the cerium dioxide particles were collected, the excess solvent evaporated off, and the gravimetric yield, corrected for the weight of MEEA, was determined to be 26%.
  • the size distribution of the cerium dioxide particles (plotted in FIG. 4 ), determined by dynamic light scattering, indicated a particle size having a mean intensity weighted hydrodynamic diameter of about 6 nm. Over two dozen replicated precipitations and independent measurements of these precipitations gave a mean intensity weighted size of 5.8 nm+/ ⁇ 0.4 nm (one standard deviation). Thus, the reaction precipitation scheme is robust. Additionally, the size distribution is substantially monomodal, i.e., only one maximum, with most of the particles falling in the range 5.2 nm to 6.4 nm. Feature 55 of the size distribution is a binning artifact.
  • a transmission electron microscope (TEM) was also used to analyze the cerium dioxide particles.
  • a 9 microliter solution (0.26M) was dried onto a grid and imaged to produce the image 60 , shown in FIG. 5 .
  • the dark circular features 61 are the imaged particles. The particles show no signs of agglomeration, even in this dried-down state. In solution, the particles would be expected to show even less propensity to agglomerate.
  • the gradicule ( 61 ) represents 20 nm; it is clear from FIG. 5 that the mean particle size is quite small, less than 10 nm. From several micrographs such as these, particles were individually sized and the mean was calculated to be 6.7 ⁇ 1.6 nm. This independently corroborates the sizing data measured by dynamic light scattering.
  • FIG. 6 shows an X-Ray powder diffraction pattern 70 of a sample of the dried cerium dioxide nanoparticles, together with a reference spectrum 71 of cerium dioxide, provided by the NIST (National Institute of Standards and Technology) library.
  • the line positions in the sample spectrum match those of the standard spectrum.
  • the two theta peak widths were very wide in the sample spectrum, which is consistent with a very small primary crystallite size and particle size.
  • the primary crystallite size is calculated to be 2.5 ⁇ 0.5 nm (95% confidence of 5 replicas)
  • Example 1 was repeated, except that in Example 1a an equivalent molar amount of succinic acid was substituted for the MEEA stabilizer. A brown precipitate that readily settled was obtained, which is an indication of very large particles (several tens of microns), The same experiment was repeated each time substituting an alternative stabilizer (malonic acid—Example 1b, glycerol—Example 1c, ethyl acetoacetate—Example 1d). In each case, a readily settling brown precipitate was obtained, indicating the failure to obtain nanoparticles. For Example 1e, lactic acid at twice the molar concentration was substituted for the MEEA stabilizer.
  • Quasi-inelastic dynamic light scattering measurements revealed a mean hydrodynamic diameter particle size of 5.4 nm when the hydroxide was doubled, and 5.7 nm when the hydroxide was increased by 75%.
  • Mixtures of EDTA (which by itself produces no particles) and lactic acid at a ratio of about 20%/80% also gave particles of CeO 2 with a hydrodynamic diameter of 6 nm.
  • the optimal EDTA: lactic acid ratio of 1:4 was used, but at twice the overall concentration of this stabilizer mixture, which resulted in a decrease in the mean particle size to 3.3 nm.
  • This quantity of hydroxide is equivalent to twice the number of moles of cerium solution, so the initially nucleated precipitate was presumably the bis-hydroxyl intermediate.
  • the ammonium hydroxide solution was single jetted into the reactor in the reaction zone defined by the mixer blades and perforated screen.
  • the hydroxide was added via a single jet just subsurface into the reactor in a position remote from the active mixing zone of the colloid mixer. After the usual heat treatment and filtration, the intensity weighted diameter of the CeO 2 particles produced at the actively mixed zone was 6.1 nm, with a polydispersity of 0.129.
  • the diameter of the particles produced via the second method i.e., sub-surface introduction of the of the ammonium hydroxide at a position remote from the reaction zone, was essentially the same, 6.2 nm, but the polydispersity was much greater, 0.149.
  • the size frequency distribution can be narrowed by mixing in the high shear region of the colloid mill.
  • Example 2 The conditions of this experiment follow that of Example 2, except that the cerium ion was not in the reactor but was separately introduced via a jet into the reaction zone simultaneously with the jetting of the ammonium hydroxide solution.
  • Three molar stoichiometric ratios of hydroxide ion to cerium ion were explored: 2:1, 3:1 and 5:1
  • the following table summarizes the intensity weighted particle size diameters and polydispersities obtained by the quasi-inelastic dynamic light scattering technique.
  • Example 2 The effect of low temperature nucleation at 20° C., followed hydroxide conversion to the oxide at 70° C., versus an isothermal precipitation in which both nucleation and conversion were conducted at 70° C. was investigated using the reagent conditions specified in Example 2.
  • the preferred double jet method was employed (separate jets for cerium ion and hydroxide ion, both introduced into the reactive mixing zone of the colloid mixer).
  • the ammonium hydroxide concentration was at the 128 gm, i.e., 2 ⁇ level or a OH:Ce molar stoichiometric ratio of 2:1.
  • Quasi-inelastic dynamic light scattering measurements revealed that the particles made at the lower temperature precipitation had an intensity weighted hydrodynamic diameter of 5.8 nm, with a polydispersity of 0.117, and a yield of 54.6%, while the isothermal precipitation gave larger particles, 8.1 nm, that were more widely distributed, with a polydispersity of 0.143, in comparable yield.
  • Particle sizes were determined for 19 of the large (9.5-liter) batches prepared as described above.
  • the average particle hydrodynamic diameter was 5.8 nm, with a standard deviation of 0.40.
  • Average particle sizes measured for 207-ml and 1.5-liter batches have generally fallen in the range of 5.2-6.4 nm, well within +/ ⁇ two standard deviations of 5.8 nm (95% confidence level). Therefore it is reasonable to conclude that the particles from the two smaller batches are of essentially the same size as those of the large batches.
  • cerium dioxide dispersion prepared as described in Example 1, was added slowly to a mixture of D2 diesel fuel, surfactant Aerosol AOT, and 1-hexanol co-surfactant, resulting in a clear reddish brown colored solution that can be employed as a fuel concentrate.
  • the concentrate is 14% by volume cerium dioxide dispersion; the remaining volume is 1.72% 1-hexanol co-surfactant, 18.92% surfactant Aerosol AOT, and 65.36% diesel D2 diluents.
  • the final additivized D2 fuel has nominally a concentration of 42 ppm (by weight) of CeO 2 and 258 ppm water and 361 ppm Aerosol AOT.
  • the diesel engine is a model #DH186FGED forced air cooled 4 stroke with a rated maximum power output of 10 HP.
  • a portion of the exhaust is drawn through a porous filter medium by the action of a downstream in-line vacuum pump. Diesel particulate matter is collected on the filter media for 150 seconds, after which time its percent grey scale is measured (Adobe Photoshop). The percent grey scale is taken as a measure of the amount of soot collected.
  • the grey scale level increases as the amount of soot present on the filter media increases.
  • the diesel engine was operated for over an hour using normal D2 (low sulfur 500 ppm) fuel to equilibrate it. Towards the end of this time, diesel particulate matter was collected on a filter media for 150 seconds. The percent grey scale of the filter, which correlates with the amount of particulate material present, was measured at 70%, a figure typical for these operating conditions and collection times.
  • the engine was turned off; the fuel tank was drained of regular D2, and then partially filled and drained twice with additivized diesel fuel. The tank was then filled to the two-thirds level with additivized diesel fuel. The engine was then operated with the additivized D2 fuel for over an hour to equilibrate it to the new fuel.
  • This example illustrates that the internal working parts of the engine have been conditioned by the nanoparticulate CeO 2 in a time scale of approximately one hour. Conditioning involves incorporating CeO 2 into the walls and pistons of the engine.
  • the CeO 2 is assisting in carbon combustion by providing oxygen according to the following reaction:
  • D2 diesel fuel (2320 mL) and co-surfactant, 1-pentanol (200 mL) were placed in a 6 liter Erlenmeyer flask.
  • the surfactant, AOT (800 g) which was broken into small particles before addition, was then added in 40 gm portions to the flask with magnetic stirring. Following addition of the AOT, the resulting clear solution was allowed to stand for 1 hour. During this time, the solution changed from a light amber color to an orange color as the microemulsion formed.
  • a 500-mL dispensing burette containing 525 mL of the aqueous CeO 2 solution (nominal 1.0 M CeO 2 stabilized with 1.5 M MEEA) was mounted over the flask. The first 400 mL of this solution was added as a slow steady stream with stirring. As the aqueous CeO 2 was added, a slime-like cloud surrounded the vortex. The addition was stopped every 100 mL to allow the solution to clear. Initially, the solution required about 1 minute to clear between 100-mL additions, but after 200 mL had been added, the solution cleared more rapidly. A slower addition rate for the last 125 mL was used; addition was stopped every 50 mL to allow the solution to clear. Addition of aqueous CeO 2 over a 90 minute period results in a deep orange-brown solution, that was allowed to equilibrate for 12 hours, during which time the color had changed from orange-brown to greenish-brown.
  • a “cetane improved” formulation that included reverse micelles containing 220 ppm hydrogen peroxide and 220 ppm water suspended in ultra low sulfur diesel was run at Griffith Energy from October 18 to Nov. 17, 2006, using both a control and test 12-liter diesel, class 8 tractors.
  • mpg miles per gallon
  • mpg data were downloaded from each of the Volvo truck on board computers (“Trip Manager”) and fit to a linear regression model that explained 80% of the mpg variation. The data are presented in the table below. The greatest improvements on day 21 and day 35 are underestimates of the true potential of the formulation, as non-treated days were averaged into the weekly results, due either to beginning the treatment mid-week (day 20) or encountering filter plugging (day 28).
  • Test Data Environmental Energy Technologies (EET) Static Engine Test-EET diesel generator specifications are as follows:
  • the diesel generator tank was drained and flushed of old fuel two times before refueling with new D2 diesel fuel.
  • the engine was brought to a steady state at the beginning of each day's test by running at 30% load for a warm-up period of approximately 10 to 20 minutes, which allowed drainage of old fuel from the engine fuel. Following warm-up, testing was performed for the given load by drawing exhaust at a fixed flow rate through filter papers for a duration of 150 seconds per sample. An estimate of diesel particulate matter (soot) and the effect of the fuel formulation was made by measuring the optical reflectance of the filter paper that had entrained the soot. Between fuel changes, the engine was given approximately 5 minutes to reach steady state operating conditions. For tests requiring the fuel additive, the engine was turned off, drained and flushed twice with premixed fuel containing the fuel additive emulsion.
  • the following formulation makes 1.0 L of a 12.7 v % of a 50 w % aqueous hydrogen peroxide solution stabilized in a Triton N57/1-hexanol/diesel microemulsion.
  • This formulation when diluted 1/500 in ultra low-sulfur diesel, will contain 150 ppm (mg/L) H 2 O 2 active ingredient and 150 ppm (mg/L water).
  • the following formulation makes 1.0 L of a 30 v % t-HYDRO solution (tertiary butyl hydroperoxide) stabilized in a oleic acid/ethanolamine/1-hexanol/diesel microemulsion.
  • This formulation when diluted 1/500 in ultra low-sulfur diesel will contain 390.6 ppm (mg/L) active ingredient (t-butylhydroperoxide).
  • Lubricity was determined by measuring wear on a ball bearing rubbed on a plate coated with fuel containing the respective fuel additives. Wear was determined by the depth, in mm, of the average scar imparted by rubbing. Neat fuel, without an additive, gave a 0.35 mm scar. Test results for fuel with a commercial additive, Platinum PlusTM; a comparative fuel additive including 10 nm particles; and the inventive fuel additive including 5 nm particles were 0.32, 0.31, and 0.245 mm respectively. Low wear numbers correlate with greater lubricity. Thus, the inventive small particles afford a 30% improvement in lubricity.

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  • Solid Fuels And Fuel-Associated Substances (AREA)
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US12/440,182 2006-09-05 2007-09-04 Cerium dioxide nanoparticle-containing fuel additive Abandoned US20100199547A1 (en)

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US13/444,129 Abandoned US20130047945A1 (en) 2006-09-05 2012-04-11 Method of conditioning an internal combustion engine
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