WO2007014266A2 - Fuel and lubricant additives and methods for improving fuel economy and vehicle emissions - Google Patents
Fuel and lubricant additives and methods for improving fuel economy and vehicle emissions Download PDFInfo
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- WO2007014266A2 WO2007014266A2 PCT/US2006/029016 US2006029016W WO2007014266A2 WO 2007014266 A2 WO2007014266 A2 WO 2007014266A2 US 2006029016 W US2006029016 W US 2006029016W WO 2007014266 A2 WO2007014266 A2 WO 2007014266A2
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- oil
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- fatty acid
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M109/00—Lubricating compositions characterised by the base-material being a compound of unknown or incompletely defined constitution
- C10M109/02—Reaction products
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/286—Esters of polymerised unsaturated acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/402—Castor oils
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/102—Polyesters
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbased sulfonic acid salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/50—Emission or smoke controlling properties
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/54—Fuel economy
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Definitions
- the invention relates to additives for motor fuels that improve combustion engine performance, especially in terms of efficiency and emissions.
- the invention also relates to additives for lubricants that improve performance of both ferrous and non-ferrous metal components of engines, guns, or other machinery.
- the invention may also relate to additives for cutting fluids used in machining and fabricating, as well as mining and other similar cutting, shearing, and grinding applications that benefit from ease of cutting and lower temperatures.
- the invention may also relate to additives for pour point depressants.
- the invention may find other applications in various fuels, oils, esters, grease, pasty compounds such as cosmetics, as well as other fluids and semi-solids.
- Objects of the invention include improving the combustion performance of fuels, so that fuel economy is increased and harmful emissions are reduced. Further objects of the present invention include improving the lubricating value of fuels, and improving performance of lubricants in high velocity contact of metals. Other objects of some embodiments of the invention include enhancing pour point depression in diesel fuels. Invented compositions of matter are provided as additives for fuels and lubricants, wherein said additives enhance said combustion performance and lubrication, and fulfill some or all of the above objects.
- the additives of the invention comprise a calcium-containing component, castor oil, a suspension agent, an optional castor supplement/partial replacement, and, in many embodiments, a polyalphaolefin component.
- Preferred calcium-containing components are overbased calcium sulfonate, calcium carbonate, and other liquids and powders containing calcium sulfonate and/or calcium carbonate.
- Preferred suspension agents (also called herein "bonding agents”) are fatty acid esters, triglycerides or other, with a pour point/melt point between about 5 degrees C and 50 degrees C.
- Especially-preferred suspension agents are waxy esters of ricinoleic acid, palm oil, palm-olein, coconut oil, and jojoba oil.
- Preferred castor supplement/partial-replacements include sulfated castor oil, soy methyl ester, canola oil, and pour point depressant.
- the invented additives may be formulated from components only from the above lists, or may include other components such as conventional fuel additive packages, and the additives may be used with fuels that themselves include other additive packages.
- the invented additives may be formulated from components only from the above lists, or may include other components such as conventional lubricant additive packages, and the additives may be used with lubricants that themselves include other additive packages.
- the invented additives may be formulated from components only from the above lists, or may include other components; the invented additives may be used to enhance pour point depressants used with biodiesel fuel or diesels containing biodiesel, and 006/029016
- the invented additive is mixed with the pour point depressant before the mixture is added to a biodiesel or biodiesel-containing fuel.
- Embodiments of the invented composition may be formulated for use alone, blended into fuels, lubricants, treatments, or cutting oils, or blended into additives or pour point depressants for said fuel, lubricants, treatments, or cutting fluids.
- Embodiments of the invented composition may improve combustion and/or operation of combustion engines, resulting in improved miles per gallon and/or improved emissions.
- Embodiments of the invented additives may improve fuel lubricity, resulting in less engine wear and increased engine efficiency.
- Additives according to the invention comprise a calcium-containing component; castor oil; a suspension agent; an optional castor supplement/partial replacement, and, in many embodiments, a polyalphaolefm component.
- the calcium component may be calcium sulfonate, preferably an overbased calcium sulfonate, but the inventors have also found that calcium carbonate may be effective, in place of, or in addition to, calcium sulfonate.
- Many calcium sulfonates and overbased calcium sulfonates are known (see, for example, U.S. Patent 5,505,867 Related Art), and are available commercially, for example, from Crompton Corporation/Great Lakes Corporation
- Particularly preferred calcium sources are C-400TM or C-400-CTM or C-400- CLRTM overbased calcium sulfonates from Crompton Corporation/Great Lakes Corporation (Chemtura). Crompton C-400TM or C-400-CTM or C-400-CLRTM have been found to be excellent calcium sources in the form of liquids that do not exhibit calcium particle size problems by plugging fuel filters.
- the inventors have experimented with magnesium sulfonates, and have found them to be effective, except that they typically leave deposits in combustion chambers on the head, valves, spark plugs, etc., to the point that the deposits on the spark plugs "ground out” the spark plugs. Therefore, including magnesium sulfonates instead of, or in addition to, calcium sulfonates may not be practical and are therefore not preferred.
- the inventors have experimented with barium sulfonates, but have not found them to be effective, for example, because they appear to decompose at the temperatures of interest in combustion engines to produce undesirable emissions. In preferred embodiments, therefore, only calcium- containing components are used, rather than other alkaline earth components and rather than other alkaline earth sulfonates.
- polyalphaolefin compounds are preferably not hydrogenated for use in the preferred additives.
- Specific examples of preferred polyalphaolefin compounds that have been effective in the below-described tests and examples are SYNTONTM PAOs (such as SYNTON-40TM and SYNTON-80TM) available from Crompton Corporation/Great Lakes Corporation (Chemtura), and DURASYNTM PAO' s available from BP Amoco.
- the suspension agents are believed to be critical in keeping the calcium-containing component, whether calcium organic (example: sulfonate) or inorganic (example: carbonate) salt, in suspension in the vegetable oils of the preferred additives, and also in the final fuel-additive blends and the final lubricant-additive blends.
- the inventors note, in the case of overbased calcium sulfonate being suspended in additive-fuel or additive-lubricant mixtures of the invention, that both inorganic (the carbonate "overbased" portion of the overbased calcium sulfonate) and organic (the sulfonate portion of the overbased calcium sulfonate) calcium are being suspended.
- suspension agent seems to nearly "bind” the calcium to the other components to keep the calcium in suspension, and, hence, the name "bonding agent.”
- the inventors do not necessarily believe that the calcium is covalently bound to the "bonding agent” or to the castor 'oil, castor supplement/replacement, or the PAO, but they use this "bonding agent" terminology as indicative of the surprising results achievable by using the suspension agents.
- the preferred suspension agents comprise one or more of the following: 1) polymerized ester(s) of ricinoleic acid (polymerized ester(s) of 12-Hydroxy Oleic Acid), 2) polymerized ester(s) of 12-Hydroxy Stearic Acid, 3) palm oil 4) palm-olein, 5) coconut oil, and 6) jojoba oil.
- Partiuclarly preferred suspension agents are: T/US2006/029016
- Acme Wax 225TM from Acme Hardesty Co. (an example, of items no. 2 above, having a 45 degree Centigrade melting point); palm oil #701 (41 degrees C melting point), #710 (41 degrees C melting point), #720, and #730 (28 degrees C melting point) from Columbus Foods; palm-olein #725 (21 degrees C melting point); and coconut oils #92 (34 degrees C melting point) and #76 (26 degrees C melting point) also from Columbus Foods.
- a less preferred suspension agent is jojoba oil (preferably only cis-jojoba, that naturally occuring jojoba, with about 7 degrees C melting point), wherein it is less-preferred particularly because of its cost and low availability.
- Acme Wax 224TM wax ester may comprise dimers, trimers, and oligmers, with the chain lengths being greater than 30 carbons (dimers and higher numbers of polymerized monomers), and typically greater than 40 carbons (trimers and higher numbers of polymerized monomers).
- a representation of the general chemical structure of Acme Wax 225TM is portrayed in Figure 2, wherein one may see the saturation in the structure (that is, the carbon-carbon single bonds throughout each of the polymerized monomers) and the plurality of hydroxy groups bonded to the carbon chains (here, one per monomer).
- Acme Wax 225TM wax ester may comprise dimers, trimers, and oligmers, with the chain lengths being greater than 30 carbons (dimers and higher numbers of polymerized monomers), and typically greater than 40 carbons (trimers and higher numbers of polymerized monomers).
- castor oil component conventional castor oil, as available from many commercial sources, is effective.
- the castor oil component optionally may be supplemented, or a portion but not all of the castor oil may be replaced, with one or more of the castor supplement/partial replacement components.
- the preferred castor supplement/partial replacement components are sulfated castor oil, canola oil, soy methyl ester, and pour point depressant (preferably a plant-oil-based pour point depressant, such as Rho-Max 10 - 310TM, currently available from RHOMAX in Montreal, and reported to be a rapeseed oil derivative being the one preferred by the inventors).
- Sulfated castor oil for example, "75% sulfated" is preferred, and is also available from Acme Hardesty Co., Blue Bell, PA, U.S.A.
- a wide range of formulations are expected to be effective for the additive, for example, a "three group" formulation (noting that in such formulations polyalphaolefins are not added) may be within the following ranges:
- Group 1 Calcium component, 10 - 50 LV-%, including calcium sulfonate and/or calcium carbonate;
- Group 2 Polyalphaolefin, 0 LV-%;
- Group 3 Castor oil, including optional castor supplement/partial replacement: 10 - 60 LV-%;
- Group 4 Suspension Agent, 1 - 25 LV-%.
- Group 1 Calcium component, 10 - 50 LV-%, such as calcium sulfonate and/or calcium carbonate;
- Group 2 Polyalphaolefin, 15 - 75 LV-%;
- Group 3 Castor oil, including optional castor supplement/partial replacement, 10 - 60 LV-%;
- the blending process is best done by adding Group 4 to the Group 1 component(s), and blending these two components/groups very well before adding any other groups. After blending the Groups 1 and 4, Group 3 and optionally Group 2 component(s) may be added.
- a thorough blending of components from Groups 1 and 4, before any other components are added, is believed by the inventors to be very important to keeping all the components of the additive in solution/suspension, and in keeping the additive in proper solution/suspension with the oil, fuel, or lubricant into which the additive is placed. While the components may be at a range of temperatures during the blending process, it is preferred that the components be blended at about room temperature up to about 100 - 140 degrees F.
- blend and “mixture” and “add” herein may be done with various methods and various equipment, and is not intended to require a particular method, particular equipment, or duration of mixing.
- multiple of these terms may be used in a single claim, which is for clarity in explaining different steps, but is not intended to imply that the steps require different mixing techniques or equipment.
- the blending/mixing/adding of the various components of the preferred additives with each other, or of the additive to the fuel or lubricant may need to be done with a high speed, high shear, or otherwise energetic mixing technique of equipment, as will be apparent to one of average skill in the art without undue experimentation.
- the preferred three-group additive may consist only of said three groups, and the preferred four-group additive may consist only of said four groups.
- the preferred three-group additive or four-group additive may be blended with additional components, for example, additive packages such as those available commercially, to arrive at a "blended additive.”
- a blended additive may consist of, for example, 80 - 99.99 LV-% of the three group combination and 20 - 0.01 LV-% of "additional components.”
- a blended additive may consist of, for example, 80 - 99.99 LV-% of the four group combination and 20 - 0.01 LV-% of "additional components.”
- the “additional components” may range from a significant portion of the product (at about 20 LV-%, for example) to a very small portion of the product (at about 0.01 LV-%, for example).
- components that may be added to the "three-group additive” or “four-group additive” to form a “blended additive” include, but are not limited to, a pour point suppressant, wintergreen oil, dyes, oil, various esters, and/or various conventional additive packages for fuels or for lubricants. Further, the three-group or four-group additive or the blended additive may be added/blended with other materials, preferably lube oil or fuels, which themselves may already contain other "additives.”
- Effective concentrations of the three-group or four-group additive, or the blended additive, in conventional lube oils are believed to be 0.002- 20.0 LV-% four-group or f ⁇ ve- group or blended additive (0.03 - 20 LV-% being typical) with 99.998 - 80 LV-% lube oil
- Effective concentrations of the three-group or four-group additive, or the blended additive, in combustion engine fuels are believed to be 0.002 - 5.0 LV-% three-group or four-group or blended additive (0.03 - 5 LV-% being typical) with 99.998 - 95 LV-% fuel (99.97 - 95 LV-% being typical), for example.
- Additive (according to one embodiment of the invention): 40 LV-% C-400 Calcium Sulfonate
- This formulation was blended by the methods described above, added to diesel fuel and to gasoline, and run in a variety of engines, as noted in the table below.
- Tests 1 - 9 were performed under no-load conditions, with diesel fuel plus the additive (in a concentration of 1 ounce of additive in 12 gallons of conventional, commercial diesel fuel) compared to the same engine operating on only the diesel fuel.
- Tests 10 and 11 were performed under no-load conditions, with gasoline plus the additive (in a concentration of 1 ounce of additive in 18 gallons of conventional 87 octane, commercial gasoline) compared to the same engine operating with only the gasoline. All emissions results were obtained by means of an analyzer in the vehicle tailpipe, such as a FerretTM, SunTM, or ECOMTM analyzer. Results:
- Test No. 4 The fuel of Test No. 4 with an additional 1 ounce of additive per 10 gallons of fuel.
- Additive (according to one embodiment of the invention): 30 LV-% C-400-c Calcium Sulfonate (Crompton Corporation/Great Lakes Corporation (Chemtura))
- Test No. 1 was performed at 75 mph with conventional, commercial gasoline of 87 octane, and Test no. 2 was performed at 75 mph with the same gasoline plus 1 ounce of additive added per 10 gallons of the gasoline.
- Condition #1 the MAC truck engine was warmed to operating temperature and run at idle at 600 rpm for an additional 15 minutes. Emission readings were taken for 5 minutes during which the readings were stable. The truck engine was then run for 5 minutes at 2000 rpm and 5 minutes of readings were again taken, during which time the readings were again stable.
- Condition #2 additive according to the following formula was added in the proportion of once fluid ounce to 20 gallons of #2 diesel fuel:
- Readings were taken at 600 rpm and 2000 rpm, after running the engine on this Condition #2 fuel-additive blend for 5 minutes.
- Condition #3 PAO (Crompton Synton 40) was added to the MAC truck fuel tank at a rate of one fluid ounce of PAO per 20 gallons of the Condition #2 fuel-additive blend. After running the engine on this Condition #3 PAO-enhanced-fuel-additive blend for 5 minutes, readings were taken at both 600 rpm and 2000 rpm.
- Condition #4 an additional dose of PAO was added to the MAC truck fuel tank at a rate of one fluid ounce of PAO per 20 gallons of Condition #3 PAO-enhanced-fuel-additive blend. After running the engine for 10 minutes (during which time the NOx and CO readings were dropping), the readings became stable and were taken at 600 rpm and at 2000 rpm for this condition.
- Condition #5 an additional dose of PAO was added to the MAC truck fuel tank at a rate of one fluid ounce per 20 gallons of the Condition #4 PAO-enhanced-fuel-additive blend. After running the engine for 10 minutes (during which time the NOx and CO readings were dropping), the readings became stable and were taken at 600 rpm and at 2000 rpm for this condition.
- Additive (according to one embodiment of the invention * ): 40 LV% Calcium Sulfonate (Crompton C-400-CFCTM) 2 LV% Acme Wax 225TM (From Acme Hardesty) 20 LV% Castor Oil (From Acme Hardesty)
- Vehicle first was driven for 30 miles on the highway. Next the vehicle was allowed to idle for 20 minutes.
- the vehicle has a port welded to the exhaust pipe (in from of the catalytic converter) to measure emissions prior to the effects of the catalytic converter
- Additive (according to one embodiment of the Invention): 48 LV%- Calcium Sulfonate (Crompton C-400-CLR) 48 LV%- Castor Oil (From Acme Hardesty) 4 LV% - Palm-Olein (From Columbus Foods)
- Palm-Olein was added to the sulfonate and vigorously stirred with a hand held blender until it appeared to be thoroughly blended. Castor oil was then added and blended as well.
- the vehicle has a port welded to the exhaust pipe (in from of the catalytic converter) to measure emissions prior to the effects of the catalytic converter.
- Vehicle first was driven for 80 miles on the highway using baseline fuel. Next the vehicle was allowed to idle for 20 minutes. Baseline measurements were taken at 30 second intervals for 10 minutes. The same procedure was used to evaluate during the experimental condition, wherein the above composition of additive with palm-olein was added to the baseline fuel at a rate of one ounce to 15 gallons. Mean and median were calculated for the first and second half of the observation as well as for the total observation.
- Additive (according to one embodiment of the invention ' ) : ) 48 LV% Calcium Sulfonate (Crompton C-400-CFCTM 4 LV% Coconut Oil 92 (from Columbus Foods) 48 LV% Castor Oil (From Acme Hardesty)
- the vehicle has a port welded to the exhaust pipe (in from of the catalytic converter) to measure emissions prior to the effects of the catalytic converter.
- Vehicle first was driven for 80 miles on the highway on baseline fuel. Next the vehicle was allowed to idle for 20 minutes. Baseline measurements were taken at 30 second intervals for
- Second half 6 611 . .116655 4 4..2244 1 144..88 4 411
- the vehicle has a port welded to the exhaust pipe (in from of the catalytic converter) to measure emissions prior to the effects of the catalytic converter.
- Vehicle first was driven for 80 miles on the highway with the baseline fuel. Next the vehicle was allowed to idle for 20 minutes. Baseline measurements were taken at 30 second intervals for 10 minutes. The same procedure was used to evaluate during the experimental condition, after the above composition of additive with calcium carbonate was added to the baseline fuel at a proportion of one ounce to 24 gallons. Mean and median were calculated for the first and second half of the observation as well as for the total observation.
- the mower was then filled with three pints of Condition A fuel (below); engine was started and mower deck immediately engaged. RPM was held at 4400. A "Snap On” Tachometer was used to check the RPM. The engine was run until all of the three pints was burned and the engine stopped. A watch was set to measure the running time of this condition.
- the mower was then filled with three pints of Condition B fuel (below); engine was started and mower deck immediately engaged. RPM was held at 4400.
- a "Snap On” Tachometer was used to check the RPM. The engine was run until all of the three pints was burned and the engine stopped. As above, a watch was set to measure the running time of this condition.
- Soy Methyl Ester 29 LV% Equaling 100 LV-% additive.
- Condition A ran for 2910 seconds
- Vehicle fuel tank was filled with fuel and then vehicle was driven on a particular route. The vehicle was then refueled at the same station with the same baseline fuel and a composition of additive was added with the fuel, and the same route was followed by the vehicle to test the baseline fuel with that particular additive. Each time the fuel ran low in the tank, the procedure repeated, refueling with baseline fuel and adding alternative compositions of additive.
- the four variations were:
- Case #4 Additive (according to one embodiment of the invention): Formulation follows, in LV%, Added at rate of 1 fluid ounce per 20 gallons of baseline fuel. 48% Calcium Sulfonate 48% Castor Oil 4% Palm Oil
- Vehicles A and B were run with baseline, midgrade gasoline, and then the same vehicles were operated with the same baseline gasoline plus the additive above (1 ounce per 20 gallons) for Control A and Test B.
- Additive (according to one embodiment of the invention): 40 LV% Calcium Sulfonate (Crompton C-400 - CLRTM) 33 LV% Soy Methyl Ester (Cenex B-100 Biodiesel) 20 LV% Castor Oil (from Acme Hardesty)
- Additive " according to one embodiment of the invention): 40 LV% Calcium Sulfonate (Crompton C-400 - CLR)TM 33 LV% Soy Methyl Ester (Cenex B-100 Biodiesel) 20 LV% Castor Oil (from Acme Hardesty)
- Additive (according to one embodiment of the invention): 40 LV% Calcium Sulfonate (Crompton C-400 - CLR)TM 33 LV% Soy Methyl Ester (Cenex B-IOO Biodiesel) 20 LV% Castor Oil (from Acme Hardesty) 5 LV% Sulfated Castor Oil (from Acme Hardesty) 2 LV % Acme Wax 224TM (from Acme Hardesty)
- Second tank was baseline fuel (diesel) plus 1 fluid ounce additive per 20 gallons (this second tank may be considered a conditioning treatment).
- Third tank was same baseline fuel plus 1 fluid ounce additive per 20 gallons.
- Additive (according to one embodiment of the invention') : 48 LV%- Calcium Sulfonate (Crompton C-400-CLR) 48 LV%- Castor Oil (From Acme Hardesty) 4 LV% - Coconut Oil 92 (From Columbus Foods)
- Blending Procedure The Coconut oil was added to the sulfonate and vigorously stirred with a hand held blender until it appeared to be thoroughly blended. Castor oil was then added and blended as well.
- the vehicle With fuel tanks nearly empty, the vehicle was filled with 87 octane fuel at the Tesoro Station in Detroit Lakes, MN. It was the driven with the cruise control on at 65 miles per hour in fourth gear, on four lane highways for 345.9 miles. The vehicle was then refueled at the same station, with the additive added to the fuel tank in the proportion of 1 ounce per 20 gallons, and the driving repeated on the same route under the same conditions.
- Additive (according to one embodiment of the invention):: Calcium Sulfonate: 40 LV% PAO: 20 LV% Castor Oil: 20 LV% Jojoba Oil: 1 LV% Soy methyl ester: 19 LV% Equaling 100 LV% Additive
- Condition A hand-loaded cartridge (described above) was fired and velocity measured.
- Condition B identical to Condition A above except the cartridges were first put in the above-described Additive and the Additive with cartridges "soaking" therein were heated to 200 degrees F. After several minutes at 200 degrees F, the cartridges were removed, wiped clean, cooled, hand-loaded, and fired.
- Condition A 2768 feet per second.
- Condition B 2916 feet per second.
- Additive (according: to one embodiment of the invention):: Calcium sulfonate: 40 LV% PAO: 20 LV% Castor Oil: 20% Jojoba Oil: 1 LV% Soy Methyl Ester: 19 LV% Equaling 100 LV % Additive
- condition A The saw was used to remove mortar between bricks on an existing wall. Water was used as a coolant.
- Condition B The saw was used to remove mortar between bricks on an existing wall, as in Condition A. Water, treated with PB 10 sulfur chlorinated water- soluble cutting oil, was used as a coolant. Treatment rates: 1 oz per gallon of water
- Condition C The saw was used to remove mortar between bricks on an existing wall, as in Conditions A and B. Water, treated with the Condition B water soluble cutting oil and the Additive listed above, was used as a coolant. Treatment rates: 1 oz of the Additive was added to 4 oz PB 10. One ounce of the blend of Additive plus PB- 10 was added per gallon of water.
- Water soluble oil as a coolant (Condition B) resulted in an average 31 degree F lower temperature compared to Condition A.
- Additive plus Water Soluble Oil resulted in a temperature 70 degrees F lower than Condition A, and a temperature 39 degrees F lower than Condition B.
- Additive (according to one embodiment of the invention ' ):: 48%- Calcium Sulfonate (Crompton C-400-CLRTM) 4% - Palm Oil (From Columbus Foods) 48%- Castor Oil (From Acme Hardesty)
- the bearing test produced a 28 second ran (compared to about 3 sec. above) until film strength failed and bearings welded, stalling the machine.
- An additive according to embodiments of the invention was blended from: 1 fluid ounce C-400-CLRTM calcium sulfonate; 1 cc ounce Acme Wax 224TM; and 1 fluid ounce castor oil.
- Palm Oil as suspension agents palm Oil as suspension agents.
- Samples A and B were put in similar containers and brought to lower temperatures. Viscosity and pourability were visually checked.
- Sample A became cloudy at about 25 degrees F and turned to a solid at
- Sample B showed some clouding at -10 degrees F, but continued to pour well at —20 degrees F (that is, poured in a manner similar to Sample A when Sample A was at 70 degrees F). Pourability of Sample B remained at this level with no observable change for a period of two weeks. The sample was then diluted with 50% soy methyl ester (that is, 50 LV% more B-100 was added), and identical results were noted.
- Calcium-Containing Component preferably calcium sulfonate and/or calcium carbonate 30 - 50 LV%
- Calcium-Containing Component preferably calcium sulfonate and/or calcium carbonate 30 - 50 LV%
- While many additives may comprise the above components and percentages, some embodiments may consist of the above components and percentages (that is, totaling 100 LV% with no additional ingredients).
- embodiments of the invented compositions of matter have been shown to reduce harmful emissions from combustion fuels (gasoline, diesel, biodiesel, and gasoline-ethanol) and to increase miles per gallon performance.
- Embodiments of the additives, and methods of using them in fuels may reduce NOx, VOCs, HC, smoke and odor from combustion fuels, with NOx emissions being particularly improved by additives according to embodiments of the invention containing PAO, and with smoke and odor being particularly improved in diesel applications according to embodiments of the invention.
- the inventors believe, therefore, that automobile, bus, truck, airplane, train, heavy equipment, generators, etc. benefit from the invented additive.
- the immediate effect is seen in terms of reduced harmful and unpleasant emissions, and the longer-term effect is seen in that metal surfaces appear to be changed, at least temporarily, so that an engine run with the invented additive in its fuel continues for a time to exhibit improved performance (compared to pre-additive operation) even when changed back to the original (pre-additive) fuel.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Lubricants (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2006272625A AU2006272625A1 (en) | 2005-07-25 | 2006-07-25 | Fuel and lubricant additives and methods for improving fuel economy and vehicle emissions |
US11/996,721 US20080295391A1 (en) | 2005-07-25 | 2006-07-25 | Fuel and Lubricant Additives and Methods for Improving Fuel Economy and Vehicle Emissions |
EP06800354A EP1934316A2 (en) | 2005-07-25 | 2006-07-25 | Fuel and lubricant additives and methods for improving fuel economy and vehicle emissions |
MX2008001185A MX2008001185A (en) | 2005-07-25 | 2006-07-25 | Fuel and lubricant additives and methods for improving fuel economy and vehicle emissions. |
CA002616382A CA2616382A1 (en) | 2005-07-25 | 2006-07-25 | Fuel and lubricant additives and methods for improving fuel economy and vehicle emissions |
BRPI0613965-5A BRPI0613965A2 (en) | 2005-07-25 | 2006-07-25 | additives for fuels and lubricants to improve their characteristics and processes for obtaining them |
JP2008524103A JP2009503194A (en) | 2005-07-25 | 2006-07-25 | Fuel and lubricant additives and methods for improving fuel economy and vehicle emissions |
EA200800423A EA200800423A1 (en) | 2005-07-25 | 2006-07-25 | ADDITIVES TO LUBRICANT OILS AND FUELS AND METHODS TO SAVE FUEL AND REDUCE EMISSIONS OF EXHAUST GASES |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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US70242005P | 2005-07-25 | 2005-07-25 | |
US60/702,420 | 2005-07-25 | ||
US78209106P | 2006-03-13 | 2006-03-13 | |
US60/782,091 | 2006-03-13 |
Publications (2)
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WO2007014266A2 true WO2007014266A2 (en) | 2007-02-01 |
WO2007014266A3 WO2007014266A3 (en) | 2007-08-02 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/US2006/029016 WO2007014266A2 (en) | 2005-07-25 | 2006-07-25 | Fuel and lubricant additives and methods for improving fuel economy and vehicle emissions |
Country Status (10)
Country | Link |
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US (1) | US20080295391A1 (en) |
EP (1) | EP1934316A2 (en) |
JP (1) | JP2009503194A (en) |
KR (1) | KR20080032200A (en) |
AU (1) | AU2006272625A1 (en) |
BR (1) | BRPI0613965A2 (en) |
CA (1) | CA2616382A1 (en) |
EA (1) | EA200800423A1 (en) |
MX (1) | MX2008001185A (en) |
WO (1) | WO2007014266A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010012763A1 (en) * | 2008-07-31 | 2010-02-04 | Shell Internationale Research Maatschappij B.V. | Liquid fuel compositions |
Families Citing this family (8)
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KR101044217B1 (en) * | 2008-09-18 | 2011-06-29 | 금종자원개발주식회사 | Ion fuel (for bunker C oil) |
FR2941707A1 (en) * | 2009-02-04 | 2010-08-06 | Inter Meca | Use of jojoba oil as an extreme pressure additive and in lubricant, which is useful in a process of lubrication for machining operation or assembly of metals |
JP5028701B2 (en) * | 2009-08-07 | 2012-09-19 | 協同油脂株式会社 | Grease composition for constant velocity joint and constant velocity joint |
US9169454B2 (en) * | 2011-08-25 | 2015-10-27 | Sabatino Nacson | Lubricating oil formulation |
CN105936837B (en) * | 2016-03-30 | 2017-09-26 | 王严绪 | Full esters environmental protection diesel oil antiwear additive and preparation method thereof |
DE102020111392A1 (en) * | 2020-04-27 | 2021-10-28 | Klüber Lubrication München Se & Co. Kg | Lubricant composition and its use |
JP7191394B2 (en) * | 2020-08-31 | 2022-12-19 | 丸山化成株式会社 | engine oil additive |
WO2024246587A1 (en) | 2023-06-02 | 2024-12-05 | Mohammad Nassouh Al Helwani Iman | An efficient composition for improving lubrication performance of motor oil |
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US2824836A (en) * | 1954-11-01 | 1958-02-25 | Exxon Research Engineering Co | Lubricating oil compositions |
GB1383198A (en) * | 1971-02-16 | 1975-02-05 | Shell Int Research | Hot rolling of metals |
US4451266A (en) * | 1982-01-22 | 1984-05-29 | John D. Barclay | Additive for improving performance of liquid hydrocarbon fuels |
US4428850A (en) * | 1982-01-28 | 1984-01-31 | Texaco Inc. | Low foaming railway diesel engine lubricating oil compositions |
US4664821A (en) * | 1984-11-13 | 1987-05-12 | Wynn Oil Company | Lubricant additive concentrate containing isomerized jojoba oil |
US4575382A (en) * | 1985-06-21 | 1986-03-11 | Texaco Inc. | Thermal stabilized vegetable oil extended diesel fuels |
GB9114236D0 (en) * | 1991-07-02 | 1991-08-21 | Exxon Chemical Patents Inc | Fuel oil treatment |
US5413725A (en) * | 1992-12-18 | 1995-05-09 | The Lubrizol Corporation | Pour point depressants for high monounsaturated vegetable oils and for high monounsaturated vegetable oils/biodegradable base and fluid mixtures |
US5338471A (en) * | 1993-10-15 | 1994-08-16 | The Lubrizol Corporation | Pour point depressants for industrial lubricants containing mixtures of fatty acid esters and vegetable oils |
US5826369A (en) * | 1993-12-07 | 1998-10-27 | Barto/Jordan Company, Inc. | Chlorophyll based fuel additive for reducing pollutant emissions |
US5505867A (en) * | 1994-07-06 | 1996-04-09 | Ritter; Clyde G. | Fuel and Lubrication oil additive |
GB9714828D0 (en) * | 1997-07-15 | 1997-09-17 | Exxon Chemical Patents Inc | Improved fuel oil compositions |
US6409778B1 (en) * | 1997-11-21 | 2002-06-25 | Rohmax Additives Gmbh | Additive for biodiesel and biofuel oils |
US20030097782A1 (en) * | 2001-03-22 | 2003-05-29 | Jordan Frederick L. | Method and composition for using organic, plant-derived, oil-extracted materials in diesel fuels for reduced emissions |
US6620772B2 (en) * | 2001-07-13 | 2003-09-16 | Renewable Lubricants, Inc. | Biodegradable penetrating lubricant |
US20040142827A1 (en) * | 2001-11-29 | 2004-07-22 | Palazzotto John D. | Sulfur containing lubricating oil additive system particularly useful for natural gas fueled engines |
US6713439B2 (en) * | 2002-06-05 | 2004-03-30 | Infineum International Ltd. | Energy conserving power transmission fluids |
US6586374B1 (en) * | 2002-07-18 | 2003-07-01 | Primrose Oil Company | Engineered synthetic engine oil and method of use |
US6790813B2 (en) * | 2002-11-21 | 2004-09-14 | Chevron Oronite Company Llc | Oil compositions for improved fuel economy |
-
2006
- 2006-07-25 WO PCT/US2006/029016 patent/WO2007014266A2/en active Application Filing
- 2006-07-25 KR KR1020087003889A patent/KR20080032200A/en not_active Withdrawn
- 2006-07-25 MX MX2008001185A patent/MX2008001185A/en unknown
- 2006-07-25 EA EA200800423A patent/EA200800423A1/en unknown
- 2006-07-25 BR BRPI0613965-5A patent/BRPI0613965A2/en not_active Application Discontinuation
- 2006-07-25 US US11/996,721 patent/US20080295391A1/en not_active Abandoned
- 2006-07-25 EP EP06800354A patent/EP1934316A2/en not_active Withdrawn
- 2006-07-25 JP JP2008524103A patent/JP2009503194A/en active Pending
- 2006-07-25 AU AU2006272625A patent/AU2006272625A1/en not_active Abandoned
- 2006-07-25 CA CA002616382A patent/CA2616382A1/en not_active Abandoned
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010012763A1 (en) * | 2008-07-31 | 2010-02-04 | Shell Internationale Research Maatschappij B.V. | Liquid fuel compositions |
Also Published As
Publication number | Publication date |
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US20080295391A1 (en) | 2008-12-04 |
JP2009503194A (en) | 2009-01-29 |
MX2008001185A (en) | 2008-04-07 |
KR20080032200A (en) | 2008-04-14 |
EP1934316A2 (en) | 2008-06-25 |
WO2007014266A3 (en) | 2007-08-02 |
CA2616382A1 (en) | 2007-02-01 |
EA200800423A1 (en) | 2008-06-30 |
AU2006272625A1 (en) | 2007-02-01 |
BRPI0613965A2 (en) | 2011-02-22 |
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