US20140101987A1

US20140101987A1 - Bio-additive for diesel fuel jet fuel, other fuels and lubricants

Info

Publication number: US20140101987A1
Application number: US14/136,543
Authority: US
Inventors: Clyde Ritter
Original assignee: REAL TECHNOLOGIES LLC
Current assignee: REAL TECHNOLOGIES LLC
Priority date: 2011-12-27
Filing date: 2013-12-20
Publication date: 2014-04-17

Abstract

Compositions and methods of making bio-additives for diesel fuel, jet fuel and other fuels and lubricant formulations are presented. The compositions include a first polyalphaolefin, a second polyalphaolefin, a polyolefinic ester, a calcium overbased sulfonate, and a bean oil or seed oil. The fuel additives can be added to any fuel and result in advantages, such as a lower cloud point and a better lubricated engine.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation-in-Part of application Ser. No. 13/726,584, filed Dec. 27, 2012 (Attorney Docket Number 89-4), entitled “BIO-ADDITIVE FOR DIESEL FUEL, JET FUEL, OTHER FUELS AND LUBRICANTS” which claims priority benefit of U.S. Provisional Patent Application No. 61/580,589, filed Dec. 27, 2011 (Attorney Docket Number 89-2), entitled “BIO-ADDITIVE FOR DIESEL FUEL, JET FUEL, OTHER FUELS AND LUBRICANTS”, by Clyde Ritter; this application is also a Continuation-in-Part of application Ser. No. 13/937,951 (docket #89-5), entitled, “FUEL ADDITIVE AND METHOD FOR USE,” filed Jul. 9, 2013, by Clyde Ritter, which in turn claims priority benefit of U.S. Provisional Patent Application No. 61/669,345 (Docket #89-3), entitled “FUEL ADDITIVE AND METHOD FOR USE,” filed Jul. 9, 2012, by Clyde Ritter. The entire contents of all of the above applications are incorporated herein by reference.

FIELD

This specification relates generally to biodiesel formulations and methods of use.

BACKGROUND

The subject matter discussed in the background section should not be assumed to be prior art merely as a result of its mention in the background section. Similarly, a problem mentioned in the background section or associated with the subject matter of the background section should not be assumed to have been previously recognized in the prior art. The subject matter in the background section merely represents different approaches, which in and of themselves may also be inventions.
Biodiesel has been designated an alternative fuel by the U.S. Department of Energy and the U.S. Department of Transportation, and is registered with the U.S. Environmental Protection Agency as a fuel and fuel additive. Biodiesel can be used in any diesel engine (when blended with conventional diesel) and is compatible with existing petroleum distribution infrastructure.
Specifications for biodiesel have been implemented in various countries around the world. In the U.S., the specifications have been implemented through the American Society of Testing and Materials (ASTM). The ASTM specification for diesel is ASTM D975 and the ASTM standard for biodiesel is ASTM D6751. It is noted that the standard for biodiesel is as a blendstock for blending into conventional diesel and is not meant to be a specification for B100 alone. It is noted that both No. 1 and No. 2 petroleum diesel fuel (i.e., D1 and D2) can be blended with biodiesel for various reasons, including the need for lower temperature operation.
Previously produced biodiesel fuels have a number of problems that make them less desirable for use in fuels, including short shelf life, too much sulfur, the requirement for costly bonding agents, and a high cloud point.

SUMMARY

Methods of making bio-additives for diesel fuel, jet fuel and other fuels and lubricant formulations are presented which include a first polyalphaolefin, a second polyalphaolefin, a polyolefinic ester, a calcium overbased sulfonate, and a bean oil or seed oil. The fuel additives can be added to any fuel and result in advantages such as a lower cloud point.
Any of the above embodiments may be used alone or together with one another in any combination. The one or more implementations encompassed within this specification may also include embodiments that are only partially mentioned or alluded to or are not mentioned or alluded to at all in this brief summary or in the abstract. Although various embodiments may have been motivated by various deficiencies with the prior art, which may be discussed or alluded to in one or more places in the specification, the embodiments do not necessarily address any of these deficiencies. In other words, different embodiments may address different deficiencies that may be discussed in the specification. Some embodiments may only partially address some deficiencies or just one deficiency that may be discussed in the specification, and some embodiments may not address any of these deficiencies.

BRIEF DESCRIPTION OF THE FIGURES

In the following drawings like reference numbers are used to refer to like elements. Although the following figures depict various examples of the invention, the invention is not limited to the examples depicted in the figures.

FIG. 1 shows a flowchart of an embodiment of a method of making a biodiesel fuel additive.

FIG. 2 shows a flowchart of an embodiment of a method of using the biodiesel fuel additive in FIG. 1.

FIG. 3 shows a diagram of an embodiment of a system for making a biodiesel fuel additive.

DETAILED DESCRIPTION

Although various embodiments of the invention may have been motivated by various deficiencies with the prior art, which may be discussed or alluded to in one or more places in the specification, the embodiments of the invention do not necessarily address any of these deficiencies. In other words, different embodiments of the invention may address different deficiencies that may be discussed in the specification. Some embodiments may only partially address some deficiencies or just one deficiency that may be discussed in the specification, and some embodiments may not address any of these deficiencies.
Biodiesel is the name given to a variety of ester-based oxygenated fuels made from vegetable oils, fats, greases and other sources of triglycerides. Biodiesel is a clean-burning diesel replacement fuel that can be used in compression ignition (CI) engines and is manufactured from renewable non-petroleum-based sources, including: organic fats and oils (such as virgin vegetable oil), recycled oil (such as used fryer oil and grease trap materials), camelina sativa oil (false flax or wild flax oil), and animal fats (such as lard and beef tallow), for example. Non-limiting examples of these feedstocks include soybean oil, peanut oil, coconut oil, palm oil, canola oil (which can also be referred to as rapeseed oil), algae oil, jatropha oil, animal fat tallow, waste vegetable grease, and other similar sources.
The basic biodiesel reaction involves a transesterification process to convert triglycerides in the feed stock to methylesters. The transesterification process typically involves the reaction of a raw oil (source of triglycerides) with methanol or ethanol and an alkaline catalyst, such as sodium hydroxide or potassium hydroxide. Excess methanol is typically used to ensure that the process is driven to completion.
The alcohol and catalyst are mixed first and then the alcohol/catalyst mixture is mixed with the raw oil and allowed to react. Once the reactants are thoroughly mixed, the reaction begins and the raw oil begins to separate into methylester and glycerin (otherwise known as glycerol). Because the methylester is less dense than the glycerin, methylester floats to the top of the glycerin and can be separated from the glycerin by pumping the methylester off the top or by draining the glycerin off the bottom. A centrifuge or other separation means can also be used to separate the methylester from the glycerin by-product. Thereafter, the methylester is purified to produce the biodiesel product.
In this specification, biofuels are designated by the letter “B” followed by one to three digits, where the “B” indicates that the fuel includes a biodiesel, and the one to three digits that follow indicate what percentage of the fuel that is biofuel. Thus, B23 represents a fuel that 23 percent biofuel. Biodiesel is produced in pure form (100% biodiesel or “B100”), but is typically blended with conventional diesel at low levels between about 2% (B2) and about 20% (B20) in the U.S. and can be blended at higher levels in other parts of the world. While B2 biodiesels fuels can be used in conventional diesel engines without modification, higher level blends above approximately B5 (and up to B100) can require special handling and fuel management as well as vehicle modifications, such as the use of heaters (especially in colder climates) and different seals/gaskets that come into contact with the fuel. The level of care needed depends on a variety of factors, including: the engine, manufacturer, and climate conditions, among others.
FIG. 1 shows a flow chart of an embodiment of a method of making a biodiesel fuel additive B100 in which a fuel additive is produced having the properties provided herein.
Formulations of biodiesel fuel additives 100 can include a first polyalphaolefin, a second polyalphaolefin, a polyolefinic ester, a calcium overbased sulfonate, and a bean oil or seed oil. In other formulations the biodiesel fuel additive does not have all of the elements or features listed and/or has other elements or features instead of or in addition to those listed.
In step 102 one or more first polyalphaolefins are added and in step 104 one or more second polyalphaolefins are added. In at least one embodiment, the first polyalphaolefin centistoke number (kinematic viscosity) is different from the second polyalphaolefin centistoke number. Polyalphaolefins are polymers produced from a simple olefin (also called an alkene with the general formula C_nH_2n. The polyalphaolefin can be any polyalphaolefin having a centistoke value of from about 2 to about 13. In some formulations, the first polyalphaolefin can be chosen from the group including: 2 centistoke, 3 centistoke, 4 centistoke, 5 centistoke, 6 centistoke, 7 centistoke, 8 centistoke, 9 centistoke, 10 centistoke, 11 centistoke, 12 centistoke, or 13 centistoke. In some formulations, the second polyalphaolefin can also be chosen from the group including 2 centistoke, 3 centistoke, 4 centistoke, 5 centistoke, 6 centistoke, 7 centistoke, 8 centistoke, 9 centistoke, 10 centistoke, 11 centistoke, 12 centistoke or 13 centistoke. In some formulations, the first and second polyalphaolefin are chosen to have different centistoke values. In some formulations, the first polyalphaolefin has a 6 centistoke value and the second polyalphaolefin has a 2 centistoke value. The first polyalphaolefin can be included in the formulation for the biodiesel fuel additive at a percentage by volume of from about 4.5% to about 99.5%, including: 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43, 43.5, 44, 44.5, 45, 45.5, 46, 46.5, 47, 47.5, 48, 48.5, 49, 49.5, 50, 50.5, 51, 51.5, 52, 52.5, 53, 53.5, 54, 54.5, 55, 55.5, 56, 56.5, 57, 57.5, 58, 58.5, 59, 59.5, 60, 60.5, 61, 61.5, 70, 71.5, 72, 72.5, 73, 73.5, 74, 74.5, 75, 75.5, 76, 76.5, 77, 77.5, 78, 78.5, 79, 79.5, 80, 80.5, 81, 81.5, 82, 82.5, 83, 83.5, 84, 84.5, 85, 85.5, 86, 86.5, 87, 87.5, 88, 88.5, 89, 89.5, 90, 91.5, 92, 92.5, 93, 93.5, 94, 94.5, 95, 95.5, 96, 96.5, 97, 97.5, 98, 98.5, and 99%, for example. In some formulations, the first polyalphaolefin is included in the formulation for the biodiesel fuel additive at a percentage by volume of from about 20 to 80%. In some formulations, the first polyalphaolefin is included at a percentage of from about 30 to 50%. In some formulations, the first polyalphaolefin is included at a percentage of about 40%. In some formulations, the first polyalphaolefin is included at a percentage of from about 20% to about 80%. In some formulations, the first polyalphaolefin is included at a percentage of from about 40% to about 60%. In some formulations, the amount of polyalphaolefin used depends on the desired outcome. For example, emission reduction versus improved fuel economy.
In step 104, a second polyalphaolefin can be included in the formulation. The second polyalphaolefin can be included in the formulation for the biodiesel fuel additive at a percentage by volume of from about 95.5 to about 4.5%, including: 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43, 43.5, 44, 44.5, 45, 45.5, 46, 46.5, 47, 47.5, 48, 48.5, 49, 49.5, 50, 50.5, 51, 51.5, 52, 52.5, 53, 53.5, 54, 54.5, 55, 55.5, 56, 56.5, 57, 57.5, 58, 58.5, 59, 59.5, 60, 60.5, 61, 61.5, 70, 71.5, 72, 72.5, 73, 73.5, 74, 74.5, 75, 75.5, 76, 76.5, 77, 77.5, 78, 78.5, 79, 79.5, 80, 80.5, 81, 81.5, 82, 82.5, 83, 83.5, 84, 84.5, 85, 85.5, 86, 86.5, 87, 87.5, 88, 88.5, 89, 89.5, 90, 91.5, 92, 92.5, 93, 93.5, 94, 94.5, 95, 95.5, 96, 96.5, 97, 97.5, 98, 98.5, and 99%, for example. In some formulations, the second polyalphaolefin is included in the formulation for the biodiesel fuel additive at a percentage by volume of from about 5 to 80%. In some formulations, the second polyalphaolefin is included at a percentage of from about 5 to 30%. In some formulations, the second polyalphaolefin is included at a percentage of about 10%. In some formulations, the second polyalphaolefin is included at a percentage of about 30%. In some formulations, the second polyalphaolefin is included at a percentage of from about 20% to about 80%. In some formulations, the second polyalphaolefin is included at a percentage of from about 40% to about 60%.
In step 106, at least one polyolefinic ester is included in the formulation of the fuel additive. Polyolefinic esters are a type of jet engine lube oil (for example HATCO product #3212, 3214, 1625 and mil-PRF type C/I). The polyolefinic ester can be included at a percentage by volume of about 4.5 to about 5.5%, including 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, 5.4, and 5.5%. In some formulations of the biodiesel fuel additive, the polyolefinic ester is included at 5%.
In step 108, at least one overbased detergent is included in the formulation of the fuel additive. One common overbased detergent is calcium overbased sulfonate, although other overbased detergents also work. In this specification, an overbased detergent refers to a detergent, which typically a polar hydrophilic head with a hydrocarbon tail, that has been overbased. Overbasing involves incorporating additional base reserve into an originally neutral detergent struction, usually in the form of a colloidally dispersed metal carbonate such as CaCO₃. Overbased detergents impart basicity to the oil to neutralize acids formed during the combustion process and from degradiation of the lubricant. In addition, overbasing detergents impart other performance enhancements, such as decreasing the dynamic coefficient of friction and acting as rust and corrosion inhibitors. Preferably, the excess metal is present over that which is required to neutralize the acids. In this specification, the term “overbased sulfonate” includes any metallic salt of sulfonic acid compound(s) having “a metal content in excess of that which would be present according to the stoichiometry of the metal and the acidic organic compound reacted with the metal” including compounds designated as “superbased sulfonates”, “overbased petroleum sulfonates”, “overbased alkaline-earth sulfonates”, and “natural-based”, “synthetic based”, or “natural-synthetic blend” overbased sulfonates, for example. Calcium overbased sulfonates are detergents that can be diesel additives and are designed to clean metal surfaces within an engine and prevent the build-up of deposits. The C400-C™ Overbased Sulfonate is manufactured by Surpass Chemicals Limited, 10 Chemical court, West Hill, Ontario Canada, M1E3X7 and marketed by Witco Corporation, One American Lane, Greenwich Conn., USA 06831-2559. The calcium overbased sulfonate can be used at a particle size of from about 50 to about 100 angstroms, including 55, 60, 65, 70, 75, 80, 85, 90, and 95 angstroms or mixtures thereof. The calcium overbased sulfonate can be included in the formulation for the biodiesel fuel additive at a percentage by volume of about 4.5 to about 80.5%, including: 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43, 43.5, 44, 44.5, 45, 45.5, 46, 46.5, 47, 47.5, 48, 48.5, 49, 49.5, 50, 50.5, 51, 51.5, 52, 52.5, 53, 53.5, 54, 54.5, 55, 55.5, 56, 56.5, 57, 57.5, 58, 58.5, 59, 59.5, 60, 60.5, 61, 61.5, 70, 71.5, 72, 72.5, 73, 73.5, 74, 74.5, 75, 75.5, 76, 76.5, 77, 77.5, 78, 78.5, 79, 79.5, and 80%. In some formulations, the calcium overbased sulfonate is included at a volume of from about 5 to about 25%. In some formulations, the calcium overbased sulfonate is included at a volume of 5%. In some formulations, the calcium overbased sulfonate is included at a volume of 25%. In some formulations, the calcium overbased sulfonate is included at a volume of 40%. In some formulations, the calcium overbased sulfonate (C-400) is used at a percentage that reduces visible smoke from the diesel or other equipment.
In step 110, at least one bean oil or seed oil is included in the formulation of the fuel additive. At least one bean oil or seed oil can be included, such as castor oil, soybean oil, peanut oil, coconut oil, palm oil, canola oil, rapeseed oil, camelina sativa oil, jatropha oil, or combinations thereof. The bean oil or seed oil can be included at a percentage by volume of about 19.5% to about 20.5%, including 19.6%, 19.7%, 19.8%, 19.9%, 20%, 20.1%, 20.2%, 20.3%, 20.4%, and 20.5%, for example. In some formulations, the bean oil or seed oil is included at 20%. In some formulations, the bean oil or seed oil is castor oil. In some formulations, the castor oil is used at a concentration that reduces measured emissions.
In step 112, the ingredients or formulation is mixed. In step 112 the mixture is mixed at a temperature of between about 70° F. to about 80° F. until the components are completely mixed (e.g., the composition is homogeneous). In an embodiment, the method of mixing can include any appropriate method including mechanical stirring at a low to medium speed. In at least one embodiment, the mixing is by continuous mild mechanical agitation. The method of mixing may use any type of mixer or agitator. In at least one embodiment, standard rotational mixing equipment (e.g., a paint mixer) is used. In some embodiments, the first polyalphaolefin, a second polyalphaolefin, a polyolefinic ester, a calcium overbased sulfonate, and bean oil or seed oil are admixed at a temperature of from about 72° F. to 78° F., including 73° F., 74° F., 75° F., 76° F., and 77° F. In some embodiments the first polyalphaolefin, a second polyalphaolefin, a polyolefinic ester, a calcium overbased sulfonate, and bean oil or seed oil are admixed at about 76° F.
In some embodiments, the method involves premixing the polyalphaolefins (PAO) and then adding the polyolefinic ester (POE) making a PAO/POE blend (PAO/POE), admixing 10% of the PAO/POE blend with the calcium overbased sulfonate, slowly adding the bean oil or seed oil to the mix, mixing thoroughly, and adding the remaining PAO/POE blend. In some embodiments, adding the PAO/POE blend improves emissions, makes the biodiesel fuel additive relatively impervious to temperature extremes (having a wider temperature range in the fuel is usable than were the biodiesel fuel not added), and lowers the cloud point character.
In some embodiments, the biodiesel fuel additive is stored at a temperature of about 70-74° F., including 71° F., 72° F., and 73° F. In some embodiments, the biodiesel fuel additive is stored at a temperature of about 72° F. In some embodiments, the biodiesel fuel additive is stored at room temperature (e.g., 68° F. to 77° F.).
In another embodiment, although depicted as distinct steps in FIG. 1, steps 102-112 may not be distinct steps. In other embodiments, method 100 may not have all of the above steps and/or may have other steps in addition to or instead of those listed above. The steps of method 100 may be performed in another order. Subsets of the steps listed above as part of method 100 may be used to form their own method.
The method of preparing a biodiesel fuel additive B100, comprises admixing a first polyalphaolefin, a second polyalphaolefin, a polyolefinic ester, a calcium overbased sulfonate, and a bean oil or seed oil. In other formulations, the biodiesel fuel additive does not have all of the elements or features listed and/or has other elements or features instead of or in addition to those listed. In some embodiments, the bean oil or seed oil is castor oil.
FIG. 2 shows a flow chart of an embodiment of a method of using a fuel additive 200 in which a fuel additive is used alone or admixed with a fuel.
In step 210, the type of engine is identified in which the fuel additive will be used. The engine might be a diesel engine, an automobile engine (a gas engine) or a jet engine. The type of engine can influence the composition of the fuel additive. Thus, for example, a jet fuel might have a lower percentage of degummed lipid acid or ester and/or castor bean oil (see, for example, Example 3). A decision can be made at this point whether to use the fuel additive alone as the fuel or to use a fuel composition of the fuel additive mixed with a fuel.
The fuel additive can be mixed with a fuel to create a fuel composition. In step 220, the fuel additive is mixed with a fuel. In some embodiments the fuel additive is admixed with before-market or after-market fuels. In some embodiments, the fuel additive is admixed with conventional diesel, biofuels, avgas, automobile gas, jetfuel and/or engine oil at about 2 to about 99%, including 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, and 99%, for example. In some embodiments, the fuel additive is admixed with regulated or unregulated diesel at about 2 to about 20%. In some embodiments, the fuel additive is admixed with biodiesel at about 2 to about 20%. In some embodiments, the fuel additive is admixed with avgas at 1 oz. per 10 gallons, including: 1 oz. per 5 gallons, 6 gallons, 7 gallons, 8 gallons, 9 gallons, 10 gallons, 11 gallons, 12 gallons 13 gallons, 14 gallons and 15 gallons. In some embodiments, the fuel additive is admixed with automobile gas and/or jet fuel at 1 oz. per 15 gallons fuel, including: 1 oz. per 5 gallons, 6 gallons, 7 gallons, 8 gallons, 9 gallons, 10 gallons, 11 gallons, 12 gallons 13 gallons, 14 gallons, 15 gallons, 16 gallons, 17 gallons, 18 gallons, 19 gallons, and 20 gallons.
In some embodiments, the biodiesel fuel additive is admixed with conventional diesel at about 2 to about 20%. In some embodiments, the biodiesel fuel additive is admixed with avgas at 1 oz. per 10 gallons. In some embodiments, the biodiesel fuel additive is admixed with aircraft engine oil at 1 oz. per 2 quarts (qts). In some embodiments, the biodiesel fuel additive is admixed with automobile gas and/or jet fuel at 1 oz. per 15 gallons fuel.
In step 230, the fuel additive is used alone as a fuel. The fuel additive can be used in any appropriate engine. The fuel additive can be directly added to the fuel tank in the engine.
In step 250, the fuel additive is added to an engine. The fuel additive can be added to any type of engine discussed herein.
In another embodiment, although depicted as distinct steps in FIG. 2, steps 210-250 may not be distinct steps. In other embodiments, method 200 may not have all of the above steps and/or may have other steps in addition to or instead of those listed above. The steps of method 200 may be performed in another order. Subsets of the steps listed above as part of method 200 may be used to form their own method.
In some embodiments, each of the steps of the method is a distinct step. In another embodiment, although depicted as distinct steps in the above description, may not be distinct steps. In other embodiments, the above method may not have all of the above steps and/or may have other steps in addition to or instead of those listed above. The steps of the above method may be performed in another order. Subsets of the steps listed above as part of method may be used to form their own method.
FIG. 3 illustrates a block diagram of an embodiment of a system for making a bio-fuel additive 300 in which a bio-additive is produced having the properties provided herein. System 300 can include container for a first centistoke polyalphaolefin 310; a container for a second centistoke polyalphaolefin 320; container for polyolefinic ester 330; container for calcium overbased sulfonate 340; container for bean oil or seed oil 345; controller 350, pumps 355 a-d, vat 390, and stirring apparatus 395. In other embodiments, environment 300 can not have all of the components listed and/or can have other elements instead of, or in addition to, those listed above.
Reference to biofuel additives 300 and biodiesel fuel additives is not intended to limit the additive to a particular fuel or to an additive. The biodiesel fuel additive can be used in any fuels discussed herein and/or that would be enhanced by the fuel additive. The word biofuel additive, biodiesel fuel additive, biodiesel additive, fuel additive, and biodiesel formulations may interchangeably with one another anywhere in the specification to obtain different embodiments. Further, the biodiesel fuel additive may be used alone as a fuel.
Examples of formulations of a biodiesel fuel additive 300 are provided that can be used blended with another fuel or oil. In some formulations the biodiesel fuel additive is blended with conventional biodiesel fuel (or oil) at concentrations of from about 1% to about 99% by volume (e.g., from 1% to 99%). Some formulations of the biodiesel fuel additive can be blended with conventional biodiesel fuel at 2% (B2) to 20% (B20) for use in conventional biodiesel engines throughout the world. Higher level blends (5% —B5 and higher) can be used in conventional diesel engines with some modifications, including: adding a heater to keep the biofuel above a certain temperature, different seals/gaskets may be needed to prevent the blend with the biodiesel from leaking, separation from petroleum fuels at low temperatures, special handling, and fuel management.
While the biodiesel fuel additive 300 has utility as a biodiesel fuel and/or additive, it can also be used as a fuel additive in other types of fuels or oils without limitation, including: jet fuel, avgas (aviation gasoline), kerosene, lubrication oil, and fuel for any 2-stroke engine. In addition, the biodiesel fuel additive can also be used in engine oils without limitation.
The system for making a fuel additive 300 can be an industrial process that includes a system for preparing the ingredients (the first polyalphaolefin; the second polyalphaolefin; the polyolefinic ester; the calcium overbased sulfonate; and the bean oil or seed oil). The industrial process can also include a system for storing the ingredients in a tank and adding the amount of each ingredient depending on the specific fuel additive being produced (e.g., a fuel additive for an avgas). The amount of each ingredient can be measured using a computer to program the addition. The industrial process can also include stirring the ingredients to make a homogeneous mixture. The system may also include a facilities for mixing the fuel additive with a fuel.
The container for first polyalphaolefin 310 provides a holding place for the ingredient before it is mixed with the other ingredients that make up the fuel additive. The container 310 can be a tank or any suitable holding container. The types of polyalphaolefins that can be used are discussed with reference to FIG. 1. The container 310 can be any type of container as long as container 310 does not change the chemistry of the first polyalphaolefin. In other words, the container may be composed of an inert material. Alternatively, the container can be coated with an inert material. The container can include one or more pipes or flexible tubes that allow for movement of the first polyalphaolefins into a central mixing bowl or vat. The movement of the materials as well as how much of the material is added, may be controlled with one or more pumps that may be activated by a central computer.
The container for second polyalphaolefin 320 includes a holding place for one or more second polyalphaolefins before the ingredient is mixed with the other ingredients to make up the fuel additive. The container for the second polyalphaolefin 320 can be configured to work like the container for the first polyalphaolefin 310.
The container for polyolefinic ester 330 and the container for calcium overbased sulfonate 340 can be produced and attached to the vat or mixing container substantially as described for the container for the first and second polyalphaolefins 310.
The container for the bean oil or seed oil 345 can be produced and attached to the vat or mixing container substantially as described for the container for the first and second polyalphaolefins 310. However, because the content of the container is an oil, the container may not need to be coated with a specialized material. Since the order of addition of the ingredients to produce the fuel additive is not important, the ingredients can be directly added to the vat and/or the pipes can be configured as a single pipe with each ingredient added to a central pipe on the way to the vat. Alternatively, each ingredient may enter the vat via a separate pipe.
The controller 350 functions to monitor and control the process of mixing the ingredients in the specified ratio. The controller 350 can function to control the pumps and control the amount of each ingredient that is added to the vat. The pumps that are attached to the pipes or tubes for each of the ingredients can be controlled by the controller. The ingredients, including the first polyalphaolefin, the second polyalphaolefin, the polyolefinic ester, the calcium overbased sulfonate, and the bean or seed oil can be added in the specific percentages discussed in FIG. 1 for each type of fuel additive. The controller 350 can control the amount of each ingredient to be allowed into the pipes and finally poured into the vat to produce the fuel additive. The controller 350 can be programmed to allow different percentages of each ingredient into the central vat. Thus, for example, the controller can be programmed to produce the fuel additive in Example 1 to have 40% 6 centistoke polyalphaolefin, 30% 2 centistoke polyalphaolefin, 5% polyolefinic ester, 5% calcium overbased sulfonate, and 20% castor oil. In at least one embodiment, the controller 350 can also sense whether the containers for each ingredient (310, 320, 330, 340 and 345) have less than the amount of the ingredient for a vat of the fuel additive. Although there may be a range of percentages of each ingredient that works well for different uses, the system may ensure that there is a good quality control, so that the customer gets the same fuel additive each time.
In at least one embodiment, the controller 350 includes a sensor feedback mechanism for each ingredient. A sensor detects the amount of the particular ingredient leaving the pipe into the vat and/or the percentage of that ingredient in the vat. Then, controller 350 adjust the flow of the ingredient to ensure that the intended amount of the ingredient is added to the vat and/or the mixture in the vat has the intended percentage of that ingredient. Controlling the flow of the ingredient may include increasing and/or decreasing the flow of the ingredient in the vat. Controlling the flow of the ingredient may also turning the pump and opening an valve to start adding the desired ingredient or shutting the valve and turning off the pump to stop adding the ingredient. In at least one embodiment, the controller 350 includes a sensor feedback mechanism for each ingredient for determining whether the tank storing the ingredient is empty and/or low.
The pumps 355 a-d work with the controller 350 to precisely add the amount of each ingredient to the vat. The pumps can be any type of pump. In at least one embodiment, the pumps 355 a-d are activated by the controller 350.
The vat 390 can be any type of container that allows for the mixing of the ingredients to make up the fuel additive. For example, the vat 390 can be an industrial size mixing bowl. The vat 390 can include a temperature control and/or refrigeration or heating device as needed. The vat 390 can include a stirring apparatus to allow for complete mixing of the ingredients. The stirring apparatus can be any type of industrial mixer or agitator. In at least one embodiment, standard rotational mixing equipment (a paint mixer) is used. The vat 390 can be of a size that allows for mixing a large amount of fuel additive for use alone or as a fuel additive.
The stirring apparatus 395 can be contained within the vat 390 or can be added to the vat 390 to mix the ingredients completely, but at a slow to moderate speed. The stirring apparatus can be controlled by the controller 350 or by separate means. In at least one embodiment, a timer can be added to the stirring apparatus to control the amount of time that the ingredients are mixed to a homogeneous mixture. In at least one embodiment, a speed control can be added to the stirring apparatus to control and/or change the speed of mixing.
In an embodiment the fuel additive can be stored alone at room temperature (e.g., approximately 72° F.) for up to 6 months. In another embodiment, the fuel may be stored for up to 7, 8, 9, 10, 11, or 12 months. The biodiesel fuel additive can be stored mixed with fuel at room temperature for up to 6 months including 7, 8, 9, 10, 11, and 12 months. The fuel additive can be stored for at least 6 months at −10° F. and +90° F., with no visible affects.
Synthetic biodiesel fuel additives are provided in Examples 1 and 2.

Example 1

Provided in example 1 is a biodiesel fuel additive for emissions reduction and lowering the cloud point of diesel, biodiesel and jet fuel. The biodiesel fuel additive can be blended with bio fuels to include 100% biodiesel, where the percentage represents the percentage of biodiesel by volume. The biodiesel fuel additive is a synthetic product because the biodiesel fuel additive is chemically refined from components other than crude oil. The cloud point is significant in the U.S. because biodiesels produced from different feedstocks can perform differently in different geographic regions and climates. The cloud point test is performed as part of ASTM 6751 testing to characterize the low temperature operability of diesel fuel. The cloud point test defines the temperature at which a cloud or haze appears in the fuel under prescribed test conditions. The cloud point for biodiesel blends is generally higher than the cloud point is for petroleum diesel fuel. The cloud point for the formula in example 1 was −33° F. The biodiesel fuel additive included:
40%—6 centistoke polyalphaolefin
30%—2 centistoke polyalphaolefin
5%—polyolefinic ester
5%—calcium overbased sulfonate
20%—castor oil
_———
100% total composite mix.
The mixture was mixed at 76° F. The mixture was stored at room temperature (72° F.). The blending procedure involved pre-mixing the 2 and 6 centistoke polyalphaolefin (PAO), then adding the 5% polyolefinic ester (POE). Then the calcium overbased sulfonate was mixed with 10% (by volume) of the PAO/POE blend using standard rotational mixing equipment (a paint mixer). The castor oil was added slowly to the mix and, after thoroughly blending (10 minutes), the remaining PAO/POE blend was added. Without being limited to the following analysis, the polyolefinic ester appears to be the catalyst. No purification was needed and there was no special storage requirement. The formulation involved a metered application of the components.
This formulation specifically lowered the cloud point and reduced the visible smoke from diesel, biodiesel and jet fuel combinations.

Example 2

Provided in example 2 is a second formulation of a biodiesel fuel additive to lower emissions and improve fuel economy of diesel and jet engines using any applicable fuels, straight or bio blends (The % is percentage by volume). The cloud point for the formula shown in Example 2 was −25° F. The biodiesel fuel additive included:
40%—6 centistoke polyalphaolefin
10%—2 centistoke polyalphaolefin
20%—castor oil
5%—polyolefinic ester
25%—calcium overbased sulfonate
_———
100% total composite mix.
The mixture was mixed at 76° F. The mixture was stored at room temperature (72° F.). The blending procedure involved pre-mixing the 2 and 6 centistoke polyalphaolefin (PAO), then adding the 5% polyolefinic ester (POE). Then the calcium overbased sulfonate was mixed with 10% (by volume) of the PAO/POE blend using standard rotational mixing equipment (a paint mixer). The castor oil was added slowly to the mix and after thoroughly blending (10 minutes), the remaining PAO/POE blend was added. Without being limited to the following analysis, the polyolefinic ester appears to be the catalyst. No purification was needed and there was no special storage requirement. The formulation involved a metered application of the components.
The formulation in example 2 was thicker and more expensive than that shown in example 1, but the formulation in example 2 exhibited all of the benefits of the formulation in example 1 as well as improved fuel economy.
Polyalphaolefins are available in several different viscosities stated in centistokes (cts) i.e.; (2 through 13 cts.) All viscocities can be used in the formulation to optimize the formula for different applications. Calcium overbased sulfonates are also varied, though, using the Chemtura product nomenclature, C-400CR is preferred for a biodiesel fuel additive to lower emissions and improve fuel economy of diesel and jet engines.
The formulas shown in Examples 1 and 2 were tested in certified labs and it was found that the formulations in examples 1 and 2 did not take any of the fuels tested out of spec, either ASTM or Mil spec. ASTM diesel fuel testing was performed under D-975 06-B, ASTM tests for gasoline were performed under D-4814, and jet fuels were tested under ASTM D-156, D-4176, D-86, D-1298, D-2386, D-130, D-381, D-1094, D-3948, D-93, D-3241, D-6304, and D-2276.
Both formulations in Examples 1 and 2 withstood storage for 6 months at −10° F. and +90° F., with no visible affects.
Example 3 provides a comparison of the properties of the biodiesel fuel additives as compared to a comparable fuel provided in U.S. Pat. No. 5,505,867.

Example 3

The biodiesel fuel additives shown in Examples 2 and 3 were compared to a comparable fuel additive provided in U.S. Pat. No. 5,505,867. The fuel in U.S. Pat. No. 5,505,867 consisted of 40% overbased sulfonate/10% jojoba oil/50% castor oil blended as taught therein. A variety of properties were tested including shelf life, freezing temperature, behavior at low temperatures, sulfur content, cloud point of fuels when mixed at a variety of concentrations, and lubrication ability. The tests were performed as follows:
Lubrication measures the anti-weld properties at point of contact. Lubrication was measured using the four ball test. In summary, three balls were put in a cylinder and the fourth ball was put on top and was spring loaded (to apply pressure to the other three balls). The biodiesel fuel additive (alone or mixed with fuel) was added, and the bottom of the cylinder was spun to make the balls wear. The number of millimeters of depth of the scar caused by the wearing was measured. Using the biodiesel fuel additives in examples 1 and 2, surprisingly the balls actually wore to a mirror finish, probably as a result of the calcium bonding to the balls. Thus, the calcium can prevent the parts in an engine from sticking.
The emissions test involved using a reference card. The reference card was a card with circles with balls inside. A wafer was placed in the tail pipe forcing the exhaust through the wafer, which had the appearance of the ball with the circle around it. On the reference card, the ball and circle #0 represented no engine running and the one with the highest number #9 was the engine running with nothing to filter the output. Two measurements were taken 20 minutes apart. The first measurement immediately after adding the biodiesel additive was higher than #9.After 20 minutes running with the biodiesel additive, the measurement was reduced to between 2 and 3, showing a significant reduction in emissions. The specific emissions measurements are shown in Tables 1 and 2:

TABLE 1

Properties of Biofuel of USPN 5,505,867

Positive	Negative

Performs as advertised	Shelf life very short - separates in hours
Simple to formulate	Freezes solid at near 0° F.
Keeps biodiesel in suspension	Too much sulfur, cannot be sold in
in diesel fuels at low temps.	regulated fuels
Reduces friction and wear on	Cannot be used in jetfuels. (triglycerides)
all interfacing parts of engine
and fuel delivery systems.
Reduces emissions.	Patent states any calcium in suspension
	Requires costly bonding agent in formula.
	Does not lower cloud point of any fuels

TABLE 2

Properties of new synthetic-based product

Positive	Negative

Indefinite shelf life	The formulation involves
	metered application of
	components
Will not freeze
Lowers cloud point of diesel, biodiesel, jet
fuels and bio-jetfuels by 25° F.
Keeps any biofuels added to diesel and
jetfuels in suspension indefinitely in low
temps.
Preservative for rubber and elastomers in
fuel systems.
Provides superior lubrication for point of
contact metals and all other components in
fuel systems.
Reduces measured emissions from diesel
and jet engines. (measured 14% of carbon
emissions.)
Less costly to formulate than original
product.
Reduces triglycerides by 80% compared to
original product.
Does not take any fuels out of
specifications (ASTM or Mil Spec)

The soot reduction test measured the initial emissions reduction with the new synthetic product (the biodiesel fuel additives in examples 1 and 2) using the ECOM unit. The soot reduction test was performed on the biodiesel fuel additive from Examples 1 and 2 as follows: a Yanmar 20 hp (horsepower) 3 cylinder diesel with a 21.6 compression ratio was installed in a John Deere model 430 Tractor™. The engine had never been exposed to Ca-40 g fuel additive and had 1900 hours total run time as a commercial operation equipment. The first smoke test was a test with no additive applied. The results were in the form of a wafer supplied with the ECOM portable testing unit. A copy of the soot comparison chart was included for graphic comparison. With the additive applied and the engine run for 2 hours prior to testing, the following results were obtained for the emissions and soot tests: the measured toxic emissions recorded a slight reduction in CO₂by 12%, a reduction in NOX by 14%, an increase in O₂by 10%, and a reduction in measured soot by 80% as compared to how the engine ran without the additive.
The reduction in measured soot was very significant. The engine noise was considerably reduced. Odor was reduced to an almost imperceptible level. After 3 hours run time with the biodiesel fuel additive in examples 1 and 2, the engine picked up idle speed and had to be slowed back to 1200 rpm. Thus, engines using the additive in examples 1 and 2 ran significantly more quietly and put out about 10% more oxygen.
The freeze test was performed for 10 months at the temperatures discussed. The test at 90° F. was performed for 3 months. The freeze test can include the pour point and/or the cloud point. The pour point is the lowest temperature at which the fuel or fuel with the product applied is still liquid enough to allow a paddle in a small container submersed in ice and methanol (called the Brookfield test).
The freeze test can also reference the cloud point, which is the temperature at which wax crystals form, clump together and clog fuel filters (fuel filters typically have a 5μ porosity). The cloud point is a better measure of freezing point. Untreated diesel/jet fuels will pour at −40° F., but will cloud up at −8° F. The low temperature degradation of the biodiesel fuel additives in examples 1 and 2 were tested for 10 months and no change was seen. It is likely that there would be no change for much longer, even 10 years.
The actual testing of jet fuel with the fuel additive of example 1 was at −33° F., but it is likely there will be no low temperature degradation up to −42° F. and even −47° F. Cloud point testing was done with diesel/jet fuels having the additive of example 1 applied at 1 oz per 10 gallons fuel.
The pour point of the additives in examples 1 and 2 was tested at −30° F. by the Brookfield method alone (without added fuel). This is because, once added to fuels, the pour point is referencing fuel treated with the additive.

Example 6

2-stroke engines include small, portable, or specialized machine applications such as outboard motors, high-performance, small-capacity motorcycles, mopeds, underbones, scooters, tuk-tuks, snowmobiles, karts, ultralights, model airplanes (and other model vehicles) and lawnmowers. The two-stroke cycle is used in many diesel engines, most notably large industrial and marine engines, as well as some trucks and heavy machinery.
The biodiesel fuel additive taught in example 2 was used in a typical 2 stroke engine at ¼oz per gal of gasoline in a leaf blower with very good results. As a two stroke replacement the biofuel additive increased the efficiency and/or decreased the fuel consumption by 20%. In addition, when the biodiesel fuel additive was used, there was no smoke or odor from the exhaust of the engine. When jet skis were run with the example 2 fuel additive (¼ oz per gallon of gasoline), there was no oil slick on the water. Using the fuel additive from example 2 (¼ oz per gallon of gasoline) did not build deposits in any of the engines tested.

Example 7

Aviation gasoline (Avgas) is a high-octane aviation fuel used to power many aircraft and racing cars. In Avgas, the additive taught in examples 1 and 2 can replace the tetraethyl lead because the formulations taught in examples 1 and 2 perform the same function by controlling combustion as well as lubricity for the valve/seat operation.
The biodiesels taught in examples 1 and 2 were used in jet engines and/or in engine oil following ASTM D-1655-82 Mil spec 85470. The treat rate refers to the amount of additive that is added to the fuel and is given as the amount of additive per the amount of fuel. The “treated fuel”, “treated oil”, etc. means that the fuel or oil includes a dose of the additive. The treat rate for avgas was 1 oz. per 10 gals. Avgas and 1 oz. per 2 quarts (qts) aircraft engine oil (the treat rate for auto gas, diesel and jet fuel is 1 oz. per 15 gals. fuel). There were many improvements shown when using the biodiesels in examples 1 and 2, including 10% improvement in fuel economy. In use, the biodiesel fuel additives from examples 1 and 2 did not build deposits in the combustion chamber. Thus, the synthetic biodiesel of examples 1 and 2 can be used as a replacement for tetraethyl lead in aviation gasoline and can be used to lower the Reid vapor pressure in avgas.
Each embodiment disclosed herein may be used or otherwise combined with any of the other embodiments disclosed. Any element of any embodiment may be used in any embodiment.
Although the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the true spirit and scope of the invention. In addition, modifications may be made without departing from the essential teachings of the invention.

Claims

1. A biodiesel composition comprising:

from about 4.5% to about 95.5% of a first 2-13 centistoke polyalphaolefin;

from about 95.5% to about 4.5% of a second 2-13 centistoke polyalphaolefin;

from about 4.5% to about 5.5% polyolefinic ester;

from about 4.5% to about 80.5% calcium overbased sulfonate; and

from about 19.5% to about 20.5% bean oil or seed oil, wherein the first and second polyalphaolefins have different centistokes values and wherein the particle size of the calcium is between about 50 and 100 angstroms.

2. The biodiesel composition of claim 1, wherein the viscosity value of the first polyalphaolefin is 6 centistoke.

3. The biodiesel composition of claim 1, wherein the viscosity value of the second polyalphaolefin is 2 centistoke.

4. The biodiesel composition of claim 1, wherein the calcium overbased sulfonate is a C-400CR calcium overbased sulfonate.

5. The biodiesel composition of claim 1, wherein the bean oil or seed oil is castor oil.

6. The biodiesel composition of claim 1, wherein the composition has a shelf life of at least 9 months.

7. The biodiesel composition of claim 1, wherein the composition will not freeze up to a temperature of −33° F.

8. The biodiesel composition of claim 1, wherein the addition to diesel, biodiesel, jet fuel, or bio jet fuels lowers the cloud point by at least 10° F.

9. The biodiesel composition of claim 7, wherein the cloud point is lowered by at least 25° F.

10. The biodiesel composition of claim 1, wherein the addition to diesel, biodiesel, jet fuel, or bio jet fuels reduces carbon emissions by at least 10%.

11. The biodiesel composition of claim 9, wherein the addition to diesel, biodiesel, jet fuel, or bio jet fuels reduces carbon emissions by at least 14%.

12. A method of making a biodiesel fuel additive composition comprising:

combining at least

from about 4.5% to about 95.5% of a first 2-13 centistoke polyalphaolefin; with

from about 95.5% to about 5.5% of a second 2-13 centistoke polyalphaolefin; with

from about 4.5% to about 5.5% polyolefinic ester with;

from about 4.5% to about 80.5% calcium overbased sulfonate; and

with from about 19.5% to about 20.5% bean oil or seed oil, wherein the first and second polyalphaolefins have different centistoke values and wherein the particle size of the calcium is between about 50 and 100 angstroms.

13. A method of using a biodiesel fuel additive composition comprising:

adding into a fuel tank of an engine composition including at least

from about 4.5% to about 90.5% of a first 2-13 centistoke polyalphaolefin; with

from about 95.5% to about 4.5% of a second 2-13 centistoke polyalphaolefin; with

from about 4.5% to about 5.5% polyolefinic ester with;

from about 4.5% to about 80.5% calcium overbased sulfonate; and

with from about 19.5% to about 20.5% bean oil or seed oil, wherein the first and second polyalphaolefins have different centistokes values and wherein the particle size of the calcium is between about 50 and 100 angstroms; and

running the engine on contents in the fuel tank.

14. The method of claim 13, wherein the bean oil or seed oil is castor oil.

15. The method of claim 13, wherein the composition is admixed at a temperature of about 76° F.

16. The method of claim 13, wherein the composition is stored at a temperature of about 72° F.

17. The method of claim 13, further comprising mixing the biodiesel fuel additive with conventional diesel at a concentration of about 2% to about 20%.

18. The method of claim 14, wherein the composition is admixed at a temperature of about 76° F.

19. The method of claim 14, wherein the composition is stored at a temperature of about 72° F.

20. The method of claim 14, further comprising mixing the biodiesel fuel additive with conventional diesel at a concentration of about 2% to about 20%.

21. The method of claim 13, further comprising premixing the polyalphaolefins (PAO) and then adding the polyolefinic ester (POE) making a PAO/POE blend (PAO/POE).

22. The method of claim 22, further comprising admixing 10% of the PAO/POE blend with the calcium overbased sulfonate.

23. The method of claim 23, further comprising slowly adding the bean oil or seed oil to the mix.

24. The method of claim 24, further comprising mixing until homogeneous.

25. The method of claim 25, further comprising adding the remaining PAO/POE blend.