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Definitions

• This invention relates generally to fuel oil compositions; specifically to stabilization of either Renewable Fuel feed stocks or the blends of Petroleum based fuels with such Renewable Fuels.
• renewable Fuels are gaining greater market acceptance as a cutter stock to extend Petroleum Diesel market capacity.
• the blends of Renewable Fuels with Petroleum Diesel are being used as a fuel for diesel engines, utilized for heating, power generation, and for locomotion with ships, boats, as well as motor vehicles.
• Bio Diesel The Renewable Cutter stock portion of a blended fuel is commonly known as Bio Diesel.
• Bio Diesel is defined as fatty acid alkyl esters of vegetable or animal oils.
• Common oils used in Bio Diesel production are Rapeseed, Soya, Palm
• Bio Diesel is prepared by reacting whole oils with alcohols (mainly methanol) in the presence of a catalyst (acid or base), usually sodium hydroxide.
• a catalyst usually sodium hydroxide.
• This method of preparing Bio Diesel known as the CD process, is described in numerous patent applications (see, e.g., DE-A 4 209 779, U.S. Pat. No. 5,354,878, EP-A-56 25 04, the entire teachings of which are incorporated herein by reference).
• Bio Diesel is a legally registered fuel and fuel additive with the U.S.
• Bio Diesel has many positive political and environmental attributes, it also has certain negative characteristics which must be taken into consideration when utilizing the material as an alternative fuel or as a blend stock for Petroleum Diesel. In order for blended fuels to receive greater market acceptance, the end user must have confidence that the fuels will be uniform, stable and will cause no harm to existing equipment.
• Bio derived fuels are inherently more oxidatively unstable as compared to petroleum based fuels.
• the inherent instability is attributed to the abundance of olefinic (unsaturated) materials available in the Bio fuel as compared to Petroleum based fuels.
• common #2 Diesel contains less than 5% olefins where as bio feeds such as soy are composed of greater than 85% olefins.
• Bio Diesel is also affected by environmental factors which influence its in-use and in-storage storage stability. These environmental factors include (i) water content, (ii) surface area exposed to the atmosphere, (iii) transparency of the storage container (exposure to sun light), (iv) presence of microorganisms, (v) prior processing of the fuel (Total Acid Value TAV), (vi) exposure to free metals during transport or storage, and (vii) the presence or absence of natural preservatives (such as Tocopherols).
• environmental factors include (i) water content, (ii) surface area exposed to the atmosphere, (iii) transparency of the storage container (exposure to sun light), (iv) presence of microorganisms, (v) prior processing of the fuel (Total Acid Value TAV), (vi) exposure to free metals during transport or storage, and (vii) the presence or absence of natural preservatives (such as Tocopherols).
• Water also is an integral component in facilitating biological growth.
• the chemical mechanism of light derived hydro peroxide formation is different than free radical peroxide formation.
• Presence of free metals in the bulk fuel catalyzes both the formation and decomposition of peroxides.
• Examples of particularly active oxidation catalysts are copper and manganese, and their complexes.
• Metals can enter the system through processing, transport, or storage of the Bio Diesel or Bio Diesel / Petroleum Diesel.
• Natural preservatives such as Tocopherols (vitamin E derivatives) are present in many natural oils. However, these materials are sometimes removed in processing of the whole oil. This is done intentionally to produce an added value product for resale, or unintentionally due to thermal decomposition or bleaching.
• Generally Bio fuels and their blends are thermally stable. However, prolonged storage at elevated temperatures, causes an increase in rates of other degradation processes (microbial, hydrolytic, and/or oxidation) resulting in enhanced storage instability.
• the environmental storage factors and Bio fuel olefin composition greatly affects the instability of the bulk Bio Diesel or Bio Diesel / Petroleum Diesel blends.
• the degradation products of oxidation such as precipitates and gums can block engine nozzles or generate undesired deposits which can lead to subsequent engine damage.
• the oxidation of Bio fuels and Bio / Petroleum fuel blends and their subsequent use are of great concern to the fuel producers, engine manufacturers and end fuel users.
• the composition of the Petroleum fuel to which Bio Diesel is subsequently blended is also an important factor in fuel instability.
• the present invention is directed to a fuel oil composition, specifically to the stabilization of Renewable Fuel feed stocks or the blends of Petroleum based fuels with such Renewable Fuels. Further, the invention is also directed to methods for increasing stabilization of stored fuel oil.
• the invention describes a fuel oil composition for use as, e.g., a fuel in diesel engines.
• the composition comprises a Renewable component, a Petroleum based component, and a Multifunctional Stabilizer Package.
• Another embodiment of the invention is directed toward a method for enhancing the in use and in storage stability of said fuel oil, by adding to the fuel oil either a Bio Diesel blending stock or a Bio Diesel / Petroleum Diesel fuel blend, an additive formulation comprising at least one additives selected from the groups comprising Free Radical Chain Termination Agents, Free Radical Decomposition Agents, Acid Scavengers, Photochemical Stabilizer, Gum Dispersants, and a Metal S equestering Agents .
• Fig. 1 is a pictorial representation of the in house oxidation testing apparatus.
• Fig. 2 is a graphical representation of the affect of Free Radical Chain
• Fig. 3 is a graphical representation of the affect of Peroxide
• Fig. 4 is a graphical representation of the affect of Acid Scavengers on Renewable Fuel stability.
• Fig. 5 is a graphical representation of the affect of Photochemical
• Fig. 6 is a graphical representation of the affect of Metal Sequestering
• the present invention is directed to a fuel oil composition; specifically to the stabilized Renewable Fuel feed stocks or the blends of Petroleum based fuels with such Renewable Fuels.
• the invention is also directed to an additive composition for increasing stability of Renewable Fuel feed stocks or the blends of Petroleum based fuels with such Renewable Fuels.
• the invention describes a fuel oil composition for use as, e.g., a fuel in diesel engines.
• the composition comprises a Renewable Bio Feedstock Component, a Petroleum Based Component, and a Multifunctional Stabilizer Package.
• a Renewable Bio Feedstock Component is an organic material that is derived from a natural, replenish able feed stock which can be utilized as source of energy.
• Bio Diesel refers to all mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats.
• Bio Diesel is commonly produced by the reaction of whole oils with alcohols in the presence of a suitable catalyst. Whole oils are natural triglycerides derived from plant or animal sources. The reaction of whole oil with an alcohol to produce a fatty acid ester and glycerin is commonly referred to as transesterification.
• Bio Diesel can be produced by the reaction of a fatty acid with an alcohol to form the fatty acid ester.
• the fatty acid segments of triglycerides are typically composed of
• the Bio Diesel according to the invention may comprise single feed sourced components, or blends of multiple feed stocks derived from vegetable(s), or animal(s) origin.
• the commonly used single or combination feed stocks include, but are not limited to, coconut, corn, palm, rapeseed, safflower, sunflower, soybean, tall oil, tallow, lard, yellow grease, sardine, menhaden, and used cooking oils and fats.
• Suitable alcohols used in either of the esterif ⁇ cation processes can be aliphatic or aromatic, saturated or unsaturated, branched or linear, primary, secondary or tertiary, and may possess any hydrocarbon chain having lengths from about C-I to about C-22.
• the industry and typical choice being identified as methanol.
• Bio Diesel composition is established by specification parameters set forth in ASTM D-6751, the entire teaching of which is incorporated herein by reference.
• the fatty acid ester must meet and maintain the established specification parameters set forth in ASTM D-6751 the regardless of the whole oil feed source or the process utilized for its production.
• Petroleum Based Component is a hydrocarbon derived from refining Petroleum or as a product of Fischer-Tropsch processes. These products are commonly referred to as Petroleum Distillate Fuels.
• Petroleum Distillate Fuels are described to encompass a range of distillate fuel types. These distillate fuels are used in a variety of applications, including automotive diesel engines and in non on-road applications, under both varying and relatively constant speed and load conditions.
• Petroleum Distillate Fuel oils can comprise atmospheric or vacuum distillates.
• the distillate fuel can contain cracked gas oil or a blend of any proportion of straight run or thermally or catalytically cracked distillates.
• the distillate fuel in many cases can be subjected to further processing such hydrogen-treatment or other processes to improve fuel properties.
• the material can be described as a gasoline or middle distillate fuel oil.
• Gasoline is a low boiling mixture of aliphatic, olefmic, and aromatic hydrocarbons, and optionally alcohols or other oxygenated components, Typically, the mixture boils in the range from about room temperature up to about 225 ° C.
• Middle distillates can be utilized as a fuel for locomotion in motor vehicles, air planes, ships and boats; as burner fuel in home heating and power generation and as fuel in multi purpose stationary diesel engines.
• Engine fuel oils and Burner fuel oils generally have flash points greater than 38 ° C.
• Middle distillates fuels are higher boiling mixtures of aliphatic, olefinic, and aromatic hydrocarbons and other polar and non-polar compounds having a boiling point up to about 350 ° C.
• Middle distillates fuels generally include, but are not limited to, kerosene, jet fuels, and various diesel fuels. Diesel fuels encompass Grades No. 1 -Diesel, 2-Diesel, 4-Diesel Grades (light and heavy), Grade 5 (light and heavy), and Grade 6 residual fuels. Middle distillates specifications are described in ASTM D-975, for automotive applications (the entire teaching of which is incorporated herein by reference), and ASTM D-396, for burner applications (the entire teaching of which is incorporated herein by reference). [0049] Middle distillates fuels for aviation are designated by such terms as
• Jet fuels are defined by U.S. military specification MIL-T-5624-N, the entire teaching of which is incorporated herein by reference and JP-8 is defined by U.S. Military Specification MIL-T83133-D the entire teaching of which is incorporated herein by reference. Jet A, Jet A-I and Jet B are defined by ASTM specification D-1655 and Def. Stan. 91 91 the entire teachings of which are incorporated herein by reference. [0050] The different fuels described (Engine fuels, Burner fuels and Aviation
• Fuels each have further to their specification requirements (ASTM D-975, ASTM D-396 and D-1655 respectively), allowable Sulfur content limitations. These limitations are generally on the order of up to 15 ppm of Sulfur for On-Road fuels, up to 500 ppm of Sulfur for Off-Road applications and up to 3000 ppm of Sulfur for Aviation fuels. [0051]
• Sulfur content limitations specifically in D-975 on road fuel) were instituted in order for the fuel to be compatible with modern engine technologies (NOx traps, particulate traps, catalyst systems), and to limit adverse environmental consequences of burning sulfur rich fuels.
• Fuel used for off road use (Marine, Power, Home Heating) is currently exempted from the 15 ppm limit, but will be regulated for Sulfur content by 2010.
• the mixed fuel is defined as "Bio / Petroleum Fuel Blends”.
• the Bio / Petroleum Fuel Blends are mixtures of Bio Diesel with Petroleum based fuels or fuels derived from Fischer-Tropsch processes. These blends are designated by a Bxx notation, where the xx denotes the Renewable Bio Feedstock Component percent composition of the blend.
• the blends are sometimes available under the name Bio Diesel, although strictly speaking Bio Diesel customarily designates 100 % Bio content (BlOO).
• the blending requirements for Bio fuels in a given end use application can be dictated by Federal and/or State Mandates, or can be market driven due to Federal and/or State Incentives.
• the blended fuel composition can contain the Renewable Bio
• Feedstock Component between about 0.5 % (B.5) - to about 50% (B50) by volume.
• B.5 0.5 %
• B50 50%
• B2 B20
• B20 B20
• higher blends maybe utilized in the future.
• Off-Road use such as Home Heating oil, Power Generation and
• the Renewable Bio Feedstock Component use range in these applications can be as high as 99.9% (B99.9).
• the Petroleum Based Component content of the blend is generally in the range of about 99.5% to about 50% for On-Road applications.
• the Petroleum Based Component content in Off-Road applications will vary dependent upon the end use requirements.
• the range of use of the Petroleum Based Component is typically between about .1 % to about 95%.
• Another aspect of the present invention is the stability of Bio Diesel or Bio / Petroleum Fuel Blends.
• Stability means resistance of Bio Diesel or Bio / Petroleum Fuel Blends during In-storage, In- Vehicle, or In-Engine to changes in composition as a result of exposure to environmental and storage factors.
• Multifunctional Stabilizer Package includes additives selected to increase the stability of Bio Diesel or Bio / Petroleum Fuel Blends.
• Multifunctional Stabilizer Package are: (i) odor (from volatile degradation products), (ii) increase in Total Acid Values (TAV), (iii) increase in Viscosity, (iv) changes in color, and (v) increase in the propensity for formation of precipitates and /or gums.
• TAV Total Acid Values
• Viscosity iv
• changes in color iv
• Suitable additives utilized in the invention to affect the in-use and in- storage stability of Bio Diesel and Bio / Petroleum Fuel Blends are: (i) Free Radical Chain Termination Agents, (U) Peroxide Decomposition Agents, (Hi) Acid Scavengers, (iv) Photochemical Stabilizers, (v) Gum Dispersants, and (vi) Metal Sequestering Agents.
• Each additive type or family in the Multifunctional Stabilizer Package is specifically chosen to counteract or intercede in a specific degradation pathway. Although these additives function in the mode selected, it is recognized that certain additives may also possess dual functions. An example of such dual capability is tertiary amines. These amines may concurrently function as Peroxide Decomposition Agents (PDA) and as an Acid Scavengers (AS).
• PDA Peroxide Decomposition Agent
• AS Acid Scavengers
• the first group of chemicals suitable for the formulation is Free Radical Chain Termination Agents (FRCTA). These additives function mainly to retard the rate of propagation of peroxides.
• a non exclusive list of suitable examples in this family include hindered phenols (2,6-di-tertbutyl phenol, 2,6-di-t-butyl-4- methylphenol (BHT), 2,4-dimethyl-6-t-butylphenol, Octyl Gallate, t- butylhydroquinone (TBHQ), ter/-butyl-4-hydroxyanisole (BHA)), phenylenediamines (N, N'-di-sec-butyl-p-phenylenediamine and N-sec-butyl-p- phenylenediamine), and Nitro aromatics (Nitro Benzene, Di-Nitrobenzene, Nitro- Toluene, Nitro-Napthalene, and Di-Nitro-Napthalene and alkyl nitro benzenes and poly aroraatics).
• BHT 2,6-di-tertbutyl phenol
• BHT 2,6-di-t
• PDA Peroxide Decomposition Agents
• the alkyl group exemplified for each functional class is (C 8 ) octyl, however, other chain lengths in the range of about C 4 -C 30 such as butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, uneicosyl, docosyl, tricosyl, and tetracosyl, and their combinations, are also suitable.
• the specific families include: tri-alkyl phosphorous compounds such as trioctyl phosphate; alkyl sulfur compounds such as octanethiol, octane sulfide and octanedisulfide; and tertiary nitrogen compounds such as the dimethyl octyl amine, dioctyl methyl amine, trioctyl amine.
• tri-alkyl phosphorous compounds such as trioctyl phosphate
• alkyl sulfur compounds such as octanethiol, octane sulfide and octanedisulfide
• tertiary nitrogen compounds such as the dimethyl octyl amine, dioctyl methyl amine, trioctyl amine.
• the tertiary amines are described by the formula depicted in Scheme 1.
• R, R',R" can be, alkyl - linear, branched, saturated, unsaturated, C 1 . 30 ; aromatic; , poly alkoxy, or cyclic, R 5 R' can also contain other hetero atoms such as O, N, S, and P, and their resultant functional groups, and
• R' and R can be incorporated in a cyclic system containing 3-12 members.
• the amine functional class may also include tertiary poly amines.
• the tertiary poly amines are described by the formula depicted in Scheme 2: SCHEME 2
• R, R' can be alkyl - linear or branched; Cuo, aromatic, cyclic, polycyclic, poly alkoxy, or carbonyl;
• R,R' can also contain other hetero atoms such as O, N, S, and P, and their resultant functional groups; *
• R and R' can be incorporated in a ring system containing 3-12 members; X can be 1 - 6; and
• Y can be 1 - 6.
• the carbonyl moiety can bridge the polyamine moiety with other organic functionalities. These functionalities can include: amides, imides, imidazolines, carbamates, ureas, imines, and enamines.
• the parent amine or poly amine can also be converted to their corresponding alkoxylates.
• the alkoxylates are products derived from the reaction of 1 -100 molar equivalents of an alkoxylating agent with the Nitrogen moiety.
• the required alkoxylating agents are chosen from the group comprising: ethylene oxide, propylene oxide, butylene oxide and
• the alkoxylates can be produced from a single alkoxylating agent or alternatively from a mixture of agents.
• the alkoxylate derived from mixtures of alkoxylating agent's can be prepared by stepwise addition of the agents to the amine to form block polymers, or can be added as mixed agents to form random block / alternating alkoxylates.
• These oxyalkylates can also be further derivatized with organic acids to form esters.
• a non exclusive list of examples in this family include: primary, secondary, and tertiary amines, and their derivatives.
• the amine nitrogen in this family can be attached to a linear, branched, saturated, unsaturated, or a cyclic, hydrocarbon, to aromatic or poly aromatic groups, to hydrogen's, or to a combination of these groups.
• Each hydrocarbon group attached to the nitrogen atom can comprise about C 4 -C 30 atoms.
• the groups can be defined as butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, uneicosyl, docosyl, tricosyl, and tetracosyl.
• Scavengers are polyamines.
• Suitable polyamines of the present invention are the polyethylene poly amines such as EDA (ethylene diamine), DETA (diethylene triamine), TETA (triethylene tetra amine) and their higher homologs; their alkyl analogs (as exemplified, but not limited to, N-coco-ethylenediamine, N-oleyl- ethylenediamine, and N-butyl-ethylenediamine), and their analogs based on other industrially available spacers such as propyl and hexyl (as exemplified, but not limited to, dipropylenetriamine, and bis-heaxamethylnetriamine); and their subsequent derivatives such as; ester amines, amido amines, imido amines, imidazolines, carbamates, ureas, imines, and enamines.
• Scheme 3 depicts a general formula describing Acid Scavengers SCHEME 3
• R, R' can be H, alkyl - linear, branched, saturated, unsaturated, C 1- 30 ; aromatic, cyclic, , poly alkoxy and carbonyl, R, R' can also contain other hetero atoms such as O, N, S, and P, and their resultant functional groups,
• R' and R' can be incorporated in a cyclic system containing 3-12 members Z can be R or
• X can be 1 - 6, and Y can be 1 — 6.
• Photochemical Stabilizers These additives function primarily to react with Singlet Oxygen generated by interaction of light and oxygen in the presence of sensitizers. Photo-oxidation cannot be inhibited by additives which function as Free Radical Chain Termination Agents such as BHT, BHA and tocopherols. [0074] Photo-oxidation can be interrupted by introducing a molecule which reacts more quickly with singlet oxygen than the bio ester.
• Non exclusive lists of examples in this family include hindered amine light stabilizers (HALS) such as Piperidines.
• the fifth group of chemicals suitable for the formulation is Gum
• Dispersants function primarily to disperse polymers or high molecular weight compounds either found in the fuel after refining or are the bi- product of oxidation or thermal breakdown.
• a non exclusive list of chemistries which are applicable to perform this function include polymers of ethylene and unsaturated esters; vinyl alcohols, vinyl ethers and their ester with organic acids; propylene, ethylene, isobutylene adducts with unsaturated carboxylic acids (such as maleic and fumaric acids) and their amide or imide derivatives; acrylic acids and their amide or esters derivatives; polystyrene's; and polymers made from combinations of these monomers.
• the sixth group of chemicals suitable for the formulation is Metal Sequestering Agents (MAS). These additives function primarily to chelate metals which can be present in the Bio Diesel or the Bio / Petroleum fuel blends.
• MAS Metal Sequestering Agents
• a non exclusive list of examples in this family includes EDTA (ethylenediamine tetraacetic acid), Citric Acid, and the industry standards DMD (N,N-disalicylidene-l ,2-propane diamine).
• EDTA ethylenediamine tetraacetic acid
• Citric Acid Citric Acid
• DMD N,N-disalicylidene-l ,2-propane diamine
• the Free Radical Chain Termination Agent can be present in the formulation between about 0.0 to about 100%, the Free Radical Decomposition Agent can be present in the formulation between 0-100%, the
• Photochemical Stabilizer can be present in the formulation about 0.0 to about 100%, and the Metal Sequestering Agent can be present in the formulation between about 0.0 to about 25% of the total stabilizer composition.
• the- package contains between about 25 to about 85% Free radical Chain Termination Agent, between about 15 to about 65% Free radical Decomposition Agent, between about 0.0 to about 10% Photochemical Stabilizer, and between about 1 to about 3% of the Metal Sequestering Agent.
• the invention further provides a process of dosing the previously described additives to stabilize Bio and Bio / Petroleum fuel blends. These additives can be added to the BlOO, and the BlOO can be subsequently blended with a petroleum based fuel, or the additive can be directly added to the Bio / Petroleum blended fuel.
• the additive package dosing rate is directly related to environmental conditions (such as humidity, temperature of storage, exposure to light), fuel handling, and storage conditions (such as surface area exposed to air, duration of storage, stressing from prior processing, impurities in the system including microbes, metals and water), the specific makeup of the bio feed (fatty acid composition) and the petroleum base fuel (crude slate and processing), and their respective blending ratios.
• environmental conditions such as humidity, temperature of storage, exposure to light
• fuel handling, and storage conditions such as surface area exposed to air, duration of storage, stressing from prior processing, impurities in the system including microbes, metals and water
• storage conditions such as surface area exposed to air, duration of storage, stressing from prior processing, impurities in the system including microbes, metals and water
• specific makeup of the bio feed fatty acid composition
• the petroleum base fuel crude slate and processing
• the effective range in which the additive provides protection for in-use and in-storage stability of Bio and Bio / Petroleum blends is between about 0.005 to about 3% by volume of the BlOO or the Bio / Petroleum fuel blends.
• Another aspect of the invention is the handling properties of the additive composition / package.
• the package should not only function to enhance in-use and in-storage stability of the Bio fuel and Bio fuel / Petroleum fuel blends, but should also poses certain properties to enable its use in the fuel market.
• the additive package should be compatible with fuel system components, it should be handle able (low enough viscosity to be pump able), and fluid at the temperature of use in northern winter climates. Generally, fuel additives are required to be liquid at approximately -40 C.
• the selected additive formulation in the present invention distinctly addresses the various aspects of instability in both Bio fuels and Bio / Petroleum fuel blends by significantly inhibiting instability mechanisms (oxidative instability, hydrolytic instability, and thermal instability), and substantially diminishing changes in the fuel (acidity, viscosity, color, odor, and gum formation propensity) thereby dramatically increasing the in-storage and in-use stability of Bio fuels and Bio / Petroleum fuel blends.
• the Multifunctional Stability Package also addresses all handle ability requirements for an additive to be utilized in the petroleum industry.
• electrostatic charges can be frictionally transferred between two dissimilar, nonconductive materials. When this occurs, the electrostatic charge thus created appears at the surfaces of the contacting materials. The magnitude of the generated charge is dependent upon the nature of and, more particularly, the respective conductivity of each material. Electrostatic charging is known to occur when solvents and fuels flow through conduits with high surface area or through "fine" filters. The potential for electrostatic ignition and explosion is probably at its greatest during product handling, transfer and transportation. Thus, the situations which are of greatest interest to the petroleum industry are conditions where charge is built up in or around flammable liquids, and the possibility of discharge leading to incendiary sparking, and perhaps to a serious fire or explosion.
• Low temperature operability / cold flow additives are used in fuels to enable users and operators to handle the fuel at temperatures below which the fuel would normally cause operational problems.
• Distillate fuels such as diesel fuels tend to exhibit reduced flow at low temperatures due in part to formation of waxy solids in the fuel.
• the reduced flow of the distillate fuel affects transport and use of the distillate fuels in refinery operations and internal combustion engine. This is a particular problem during the winter months and especially in northern regions where the distillates are frequently exposed to temperatures at which solid formation begins to occur in the fuel, generally known as the cloud point (ASTM D 2500, the entire teachings of which are incorporated herein by reference) or wax appearance point (ASTM D 31 17, the entire teachings of which are incorporated herein by reference).
• Lubricity improver's increase the lubricity of the fuel, which impacts the ability of the fuel to prevent wear on contacting metal surfaces in the engine. A potential detrimental result of poor lubricating ability of the fuel can be premature failure of engine components (for example, fuel injection pumps).
• Corrosion Inhibitors are a group of additives which are utilized to prevent or retard the detrimental interaction of fuel and materials present in the fuel with engine components.
• the additives used to impart corrosion inhibition to fuels generally also function as lubricity improvers. These additives coat the surfaces of mowing metal parts to inhibit interaction of the metals with water. This coating also functions as a lubricating barrier between the mowing metal parts and results in diminished wear.
• Cetane Improvers are used to improve the combustion properties of middle distillates. As discussed in U.S. Pat. No. 5,482,518, the entire teachings of which are incorporated herein by reference, fuel ignition in diesel engines is achieved through the heat generated by air compression, as a piston in the cylinder moves to reduce the cylinder volume during the compression stroke. In the engine, the air is first compressed, then the fuel is injected into the cylinder.
• the alteration of fuel spray patterns can result in non-uniform distribution and/or incomplete atomization of fuel resulting in poor fuel combustion.
• the accumulation of deposits is characterized by overall poor drivability including hard starting, stalls, rough engine idle and stumbles during acceleration.
• irreparable harm may result which may require replacement or non-routine maintenance.
• irregular combustion could cause hot spots on the pistons which can result in total engine failure requiring a complete engine overhaul or replacement.
• Dyes and Markers are materials used by the EPA (Environmental)
• Anti-Icing Additives are mainly used in the Aviation industry and in cold climates. They work by combining with any free water and lowering the freeze point of the mixture to inhibit ice crystal formation.
• Biocides are used to control micro organisms such as bacteria and fungi (yeasts, molds) which can contaminate fuels.
• the causes of Micro-Organism problems in fuels are generally attributed to fuel system cleanliness, specifically water removal from tanks and low point in the system.
• Demulsifiers / Anti Haze additives are mainly added to the fuel to combat cloudiness problems which can be caused by the distribution of water in a wet fuel by dispersant used in stability packages.
• the present invention addresses the various causes (environmental and fuel factors) of degradation associated with storage and in-use instability of Bio feed stocks and Bio / Petroleum fuel blends.
• the invention by the use of a specifically chosen additive types or families (Free Radical Chain Termination Agents, Free Radical Decomposition Agents, Acid Scavengers, Photochemical Stabilizers, Gum Dispersants, and Metal Sequestering Agents) is designed to counteract or eliminate various specific modes / degradation pathways responsible for fuel instability.
• the invention is further described by the following illustrative but non-limiting examples.
• the oxidative stressing apparatus used to qualitatively rate Renewable Fuels, blends of Renewable Fuels and Petroleum Fuels, and additives for such fuels was developed in house. The apparatus is depicted in Figure 1.
• In-House Oxidation Apparatus The oxidation testing apparatus is composed of a constant temperature oil bath (to stress the samples in order to accelerate oxidative degradation), test tubes (containing the Bio or Bio Petroleum blends), and a air delivery system (composed of a gas flow regulator, to control the [00104]
• the In-House method was used to demonstrate the stability enhancement of additive components on Bio, and Bio / Petroleum fuel blends.
• Free Radical Chain Termination Agents were used to demonstrate the stability enhancement of additive components on Bio, and Bio / Petroleum fuel blends.
• Test tubes containing Soy Bl OO and 100 mg/1 of FRCTA were stressed using the In-House stability method. The samples were then evaluated using the UV analysis method for fuel stability. Results are shown in Figure 1.
• Test tubes containing the soy B 100 and stability additives (%) were prepared as per Table 2.
• the affect of acid concentration on bio fuels stability was evaluated.
• the acidity diminished bio diesel was prepared by neutralizing a Soy B 100 with .06 N NaOH.
• the acid value of the starting Soy and acid diminished Soy were .66 mg KOH/g and .22 mg KOH/g respectively.
• Test tubes containing the two soy B 100's and stability additives (%) were prepared as per Table 3. Table 3
• test tubes marked xx were exposed to sunlight (stored in a sunny window).
• the remaining tube (5) was wrapped with aluminum foil to protect against light exposure. All the tubes were left open to air. After two weeks of exposure to sun light, the contents of the tubes were stressed using the In-House stability method.
• the test tubes were sampled every two hours and evaluated using the UV analysis method for fuel stability.
• Figure 4 contains the results of the evaluation.
• test tubes marked xx was exposed to sunlight (stored in a sunny window).
• the remaining tubes (2, 3, and 4) were wrapped with aluminum foil to protect against light exposure. All the tubes were left open to air. After two weeks of exposure the contents of the tubes were stressed using the In-House stability method.
• the tubes were sampled every two hours and evaluated using the UV analysis method for fuel stability.
• Figure 5 contains the results of the evaluation.
• Test tubes containing BlOO soy and additives (%) were prepared as per Table 6.
• Bio fuel degradation by copper In comparing sample 1 and sample 5, it can be seen that he blank sample without copper was stable at two hours of stressing where as the sample containing copper exhibited a substantial level of degradation. The same result can be seen between sample 4 and sample 6.
• sample 2 which only contains a Free Radical Chain Termination Agent
• sample 4 which contains a Free Radical Chain Termination Agent as well as a Peroxide Decomposition Agent. This enhanced stability may indicate a synergy between the selected components.

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