JP2009542889A - Stabilizer composition for blends of petroleum and renewable fuels - Google Patents

Abstract

Disclosed is a fuel oil composition comprising a stabilized renewable fuel feedstock or a blend of such renewable and petroleum-based fuels. Also disclosed are additive compositions for increasing the stability of renewable fuel feedstocks or blends of such renewable and petroleum-based fuels.
[Selection] Figure 1

Description

  The present invention relates generally to fuel oil compositions, and more particularly to stabilization of renewable fuel feedstocks or blends of such renewable fuels with petroleum-based fuels.

  Renewable fuels are increasingly accepted in the market as cutter stock to expand the petroleum diesel market. Blends of renewable fuels and petroleum diesel are used as fuel for diesel engines and are used for heating, power generation, and movement in ships, boats and automobiles.

  The renewable cutter stock portion of blended fuel is commonly known as biodiesel. Biodiesel is defined as a fatty acid alkyl ester of vegetable or animal oil. Common oils used in biodiesel production are rapeseed oil, soybean oil, coconut oil, tallow, sunflower oil, and used edible oil or animal fat.

  Biodiesel is prepared by reacting whole oils with alcohol (mainly methanol) in the presence of a catalyst (acid or base), usually sodium hydroxide. This process for preparing biodiesel is known as the CD process and has been described in a number of patent applications (eg German Patent No. 4209779, US Pat. No. 5,354,878, European Patent No. 562504) The entire teachings of which are incorporated herein by reference).

  Biodiesel is a fuel and fuel additive legally registered with the United States Environmental Protection Agency (EPA). In order for a material to be considered biodiesel, this material / fuel must meet the ASTM D6751-03 standard, regardless of the fat or specific process used to produce the additive. The ASTM D6751 standard aims to ensure that the quality of biodiesel is used as a blend stock with a blend level of 20% or less.

  While biodiesel has many political and environmental advantages, there are also disadvantages that must be considered when using this material as an alternative fuel to petroleum diesel or as a blend stock. In order for the blended fuel to be more accepted in the market, the end consumer must be confident that the fuel is uniform, stable and does not harm existing equipment.

  There are three independent storage and use conditions / parameters that must be considered to ensure the homogeneity / stability of bio and bioblend petroleum fuels. In the end-use market, the biofeedstock or bio / petroleum fuel mixture is 1) in storage (temperature is low to medium, 0-49 ° C (32-120 ° F) for extended periods), 2) in the vehicle fuel system ( The temperature is higher depending on the ambient temperature and the engine system, 60-70 ° C. (140-175 ° F., but the fuel is subjected to these higher temperatures for a shorter period of time than normal storage time), And 3) It is required to be stable in the engine (or near the engine) (temperature reaches 150 ° C. (302 ° F.) before injection or recycling, even for a shorter period of time).

  The main factors affecting the stability of biodiesel and biodiesel / petroleum diesel fuel blends in storage, in vehicles and in engines are the biodiesel chemical composition, the environmental conditions of use and storage, and the biodiesel is later blended This is the characteristic of petroleum fuel.

  It is well known that bio-derived fuels are inherently more oxidatively unstable than petroleum-based fuels. The inherent instability is due to the large amount of olefinic (unsaturated) material in biofuels compared to petroleum-based fuels. For example, normal # 2 diesel contains less than 5% olefins, while biofeeds such as soybeans consist of more than 85% olefins.

  When a biodiesel or biodiesel / petroleum diesel blend is exposed to air (oxygen), fuel oxidation occurs. This process is known as “oxidative instability”. As a result of the oxidation of the fuel, further reaction products of alcohols, aldehydes, ketones, carboxylic acids and their functional groups are formed, some of which produce polymers.

  Biodiesel is also affected by environmental factors, which affect storage stability during use and storage. These environmental factors include (i) moisture content, (ii) surface area exposed to the atmosphere, (iii) transparency of the storage container (exposure to sunlight), (iv) presence of microorganisms, (v) fuel Pretreatment (total acid value TAV), (vi) exposure to free metals during transport or storage, and (vii) the presence or absence of natural preservatives (eg, tocopherols).

  Exposure to water also adversely affects the storage stability of biodiesel and biodiesel / petroleum diesel. As a result of the reaction with water, the ester group is hydrolyzed, affecting the increase in the acid value of the bulk composition.

  Water is also an essential component for promoting living body growth. Because microorganisms produce and utilize enzymes (eg, lipases) in these normal metabolic pathways, these organisms digest biofuels and petroleum fuels, resulting in deleterious changes in bulk composition (eg, sludge). Formation).

  Exposure significantly accelerates the rate and extent of oxidation of biofuels and biodiesel petroleum diesel blends. The chemical mechanism of photo-derived hydroperoxide formation differs from free radical peroxide formation. Light-promoted biofuel or biodiesel / petroleum diesel blend oxidation cannot be excluded by the use of conventional antioxidants.

  The presence of free metal in the bulk fuel catalyzes both peroxide formation and decomposition. Examples of particularly active oxidation catalysts. Copper and manganese, and their complexes. Metals can enter the system during processing, transportation, or storage of biodiesel or biodiesel / petroleum diesel.

  Natural preservatives such as tocopherols (vitamin E derivatives) are present in many natural oils. However, these substances may be removed in the processing of whole oil. This is done deliberately to produce value-added products that are resold or unintentionally by pyrolysis or bleaching.

  In general, biofuels and their blends (in the absence of oxygen and water) are thermally stable. However, storage at elevated temperatures for extended periods increases the rate of other degradation processes (microorganisms, hydrolysis, and / or oxidation), resulting in increased storage instability.

  Environmental storage factors and biofuel olefin compositions greatly affect the instability of bulk biodiesel or biodiesel / petroleum diesel blends. Oxidative degradation products, such as precipitates and gums, can clog engine nozzles or produce undesirable deposits, resulting in engine damage. Oxidation of biofuels and bio / petroleum fuel blends and their subsequent use is of great concern to fuel manufacturers, engine manufacturers and end fuel users.

  The composition of petroleum fuels that are later blended with biodiesel is also an important factor in fuel instability. There is data to support the tendency of fuels to form oxidation products compared to individual components in blends of ultra-low sulfur diesel (ULSD) and biodiesel. Specifically, when the fuel blend is subjected to accelerated oxidation (ASTM method D-2274), the amount of gum-like material produced increases.

  One method for improving or controlling fuel stability is to either treat the bioblend stock or the blended bio / petroleum fuel by utilizing a stability additive. It is.

  Although it is generally accepted that biofuels require stabilization, it now describes the use of additives to stabilize various degradation pathways of biofuels or bio / petroleum fuel blends There is little literature.

  In recent years, there are applications that address biostability, but this is a very limited method. US Patent Application No. 200401396649 (named “Process for increasing the storage stability of biodiesel and the use of 2,4-di-tert-butyhydroxytoluene for the healing process” And the use of 2,4-di-tert-butylhydroxytoluene to increase the storage stability of biodiesel) "refers to 2,4-di-tert-butylhydroxytoluene (BHT for stabilizing biodiesel) This application mainly functions as a free radical inhibitor 1 Another recently published U.S. Patent Application No. 20040123517, “Additives and fuel oil compositions”, in part, is free of charge. Describes the use of hindered phenols as radical inhibitors, as this application focuses only on BHT, so this application is also limited in scope.

  These applications do not claim, suggest, or teach the use of combinations of these additives necessary to stabilize many degradation pathways of biofuels or bio / petroleum fuel blends.

German Patent No. 4209779 US Pat. No. 5,354,878 European Published Patent No. 562504 US Patent Application No. 20040139649 US Patent Application No. 20040123517

[Original paragraph 0024]
The present invention addresses the deficiencies of the prior art and, in part, relates to various causes of degradation related to instability during storage and use of biofeedstock and bio / petroleum fuel blends.
[Original paragraph 0025]
The present invention relates to fuel oil compositions, and in particular to stabilization of renewable fuel feedstock or blends of petroleum-based fuels and such renewable fuels. The present invention further relates to a method for increasing the stability of stored fuel oil.

  In one embodiment, the present invention describes a fuel oil composition used as fuel, for example, in a diesel engine. The composition includes a renewable component, a petroleum-based component, and a multifunctional stabilizer package.

  Another embodiment of the present invention is a method for improving stability in the use and storage of said fuel oil, wherein the fuel oil is either a biodiesel blend stock or a biodiesel / petroleum diesel fuel blend, ie free Adding an additive formulation comprising at least one additive selected from the group consisting of radical chain terminators, free radical degrading agents, acid scavengers, photochemical stabilizers, rubber dispersants and sequestering agents. This relates to a method for improving stability.

It is a figure showing an indoor oxidation test apparatus. FIG. 4 is a graph showing the effect of free radical chain terminators on renewable fuel stability It is a graph showing the influence with respect to the renewable fuel stability of a peroxide decomposer. 3 is a graph showing the effect of acid scavengers on renewable fuel stability. It is a graph showing the influence with respect to the renewable fuel stability of a photochemical stabilizer. It is a graph showing the influence with respect to the renewable fuel stability of a sequestering agent.

In describing embodiments of the invention, specific terminology is used for the sake of clarity. However, the present invention is not intended to be limited to the particular terms chosen, and each particular term encompasses all technical equivalents made in a similar manner to accomplish a similar purpose. Then it should be understood. The technical equivalence of additional terms will be readily understood by those skilled in the art relevant to the present invention.
Detailed Description of the Invention
The present invention relates to a fuel oil composition, in particular a stabilized renewable fuel feedstock or blend of petroleum-based fuels and such renewable fuels. The present invention also relates to an additive composition for increasing the stability of a renewable fuel feedstock or a blend of petroleum-based and renewable fuels.

  In one embodiment, the present invention describes a fuel oil composition used as a fuel or the like in a diesel engine. The composition includes a renewable biofeedstock component, a petroleum-based component, and a multifunctional stabilizer package.

  In an embodiment of the invention, the renewable biofeedstock component is an organic material derived from a natural supplementable feedstock that can be used as an energy source. Suitable examples of renewable components include, but are not limited to, biodiesel, ethanol, and biomass. Other renewable compounds are well known to those skilled in the art.

  In an embodiment of the present invention, “biodiesel” refers to all monoalkyl esters of long chain fatty acids derived from vegetable oils or animal fats.

  Biodiesel is usually produced by reacting whole oil with alcohol in the presence of a suitable catalyst. Whole oil is a natural triglyceride derived from plant or animal sources. The reaction in which whole oil is reacted with alcohol to obtain fatty acid ester and glycerin is generally called transesterification. Alternatively, biodiesel can be produced by reacting a fatty acid with an alcohol to form a fatty acid ester.

Fatty acid segments of triglycerides are typically composed of C ₁₀ -C ₂₄ fatty acids, the fatty acid composition may be a single or where a mixture of various chain lengths. The biodiesel of the present invention can include a single feed source component or a blend of multiple feedstocks of plant or animal origin. Commonly used single or combined feedstocks include, but are not limited to, coconut oil, corn oil, coconut oil, rapeseed oil, safflower oil, sunflower oil, soybean oil, tall oil, tallow, lard, yellow Examples include fats and oils, sardine oil, herring oil, and used edible fats and oils.

  Suitable alcohols used in any esterification process may be aliphatic or aromatic, saturated or unsaturated, branched or linear, primary, secondary or tertiary, about C-1 It may have a hydrocarbon chain with a length of about C-22. The industrial and general choice is methanol.

  The biodiesel composition is defined by the specific parameters described in ASTM D-6751 (the entire teachings of which are referenced as part of the present invention). Fatty acid esters must meet and maintain certain established parameters described in ASTM D-6751, regardless of the whole oil source or the process used to produce it.

  The ASTM D-6751 standard outlines the requirements for biodiesel (B100) to be considered a suitable blend stock of hydrocarbon fuels.

  In an embodiment of the present invention, the petroleum-based component is a hydrocarbon derived from refined petroleum or as the product of a Fischer-Tropsch process. These products are commonly referred to as petroleum distillate fuels.

  Petroleum distillate fuel is described to encompass various distillate fuel types. These distillate fuels are used both in variable speed and load conditions and in relatively constant speed and load conditions in a variety of applications, including automotive diesel engines and non-road applications.

  The petroleum distillate fuel oil can include atmospheric or vacuum distillate. The distillate fuel can comprise cracked gas oil or a blend of distillates that have been cracked by any ratio of direct distillation or heat or catalyst. In many cases, the distillate fuel can be subjected to further processing such as hydroprocessing or other processing to improve fuel properties. This material can be called gasoline or middle distillate fuel oil.

  Gasoline is a low boiling mixture of aliphatic, olefinic, and aromatic hydrocarbons, and optionally alcohol or other oxygenated components. Generally, the mixture boils in the range from about room temperature to about 225 ° C.

  Middle distillates can be used as fuel for travel in automobiles, airplanes, ships and boats, as burner fuel for home heating and power generation, and as fuel in multipurpose fixed diesel engines.

  Engine fuel oils and burner fuel oils generally have a flash point higher than 38 ° C. Middle distillate fuels are high boiling mixtures of aliphatic, olefinic, and aromatic hydrocarbons and other polar and nonpolar compounds having boiling points up to about 350 ° C. Middle distillate fuels generally include, but are not limited to, kerosene, jet fuel, and various diesel fuels. Diesel fuel includes grade numbers 1-diesel, 2-diesel, 4-diesel grade (light and heavy), grade 5 (light and heavy), and grade 6 residual fuel. Middle distillate specifications are ASTM D-975 for automotive applications (the entire teachings of which are referred to as part of the present invention) and ASTM D-396 for the burner applications (the entire teachings of which are part of the present invention). To be referred to).

  Aviation middle distillate fuel is indicated by terms such as JP-4, JP-5, JP-7, JP-8, Jet A, Jet A-1, JP-4 and JP-5. Jet fuel is defined by the US military standard MIL-T-5624-N (the entire teachings of which are referred to as part of the present invention), and JP-8 is defined by the US military standard MIL-T83133-D (the entire teachings thereof). Are referred to as part of the present invention). Jet A, Jet A-1 and Jet B are defined by ASTM Standard D-1655 and Defense Standard 91 91 (the entire teachings of which are referenced as part of the present invention).

  The different fuels listed (engine fuel, burner fuel and aviation fuel) each have acceptable sulfur content limits for their specification requirements (ASTM D-975, ASTM D-396 and D-1655, respectively). Have. These limits are generally up to approximately up to 15 ppm sulfur for on-road fuels, up to 500 ppm sulfur for off-road applications, and up to 3000 ppm sulfur for aviation fuels.

  In order to adapt the fuel to modern engine technology (NOx traps, particulate traps, catalyst systems) and to reduce the environmental adverse effects of combustion of sulfur rich fuels, especially sulfur content limits (especially D-975 on-road fuels) (Reference World-Wide Fuel Charter, April 2000, issued by ACEA, Alliance of Automobile Manufacturers, EMA and JAMA, the entire teachings of which are referred to as part of the present invention).

  In the United States, the Environmental Protection Agency (EPA) regulations require ultra-low sulfur (ULS) standards, particularly the sulfur content of on-road fuels that satisfy less than 15 ppm (mass) of sulfur in the final fuel. Similar regulations have been established worldwide.

  Fuel for off-road use (maritime, electricity, home heating) is currently exempted from the 15 ppm limit, but the sulfur content will be regulated by 2010.

  Renewable biofeedstock components and petroleum-based components can then be blended to produce a blended fuel. In an embodiment of the present invention, a blended fuel is defined as a “bio / petroleum fuel blend”. A bio / petroleum fuel blend is a mixture of biodiesel and petroleum-based fuels or fuels derived from the Fischer-Tropsch process. These blends are expressed in Bxx notation, where xx indicates the renewable biofeedstock component composition (%) of the blend. Blends may be available under the name biodiesel, but strictly speaking, biodiesel typically refers to 100% biocomponent (B100).

  Biofuel blending requirements for a given end use may be dictated by federal and / or state directives or may be market driven by federal and / or state encouragement.

  The blended fuel composition may contain from about 0.5 volume% (B.5) to about 50 volume% (B50) of renewable biofeedstock components. In general, current on-road applications in the market range between about B2 and about B20, although higher blends may be available in the future.

  Off-road use, such as home heating oil, power generation and voyage, generally relaxes the restrictions on the renewable biofeedstock component content of the blend. The range of use of renewable biofeedstock components in these applications can be as high as 99.9% (B99.9).

  The petroleum component content of the blend is generally in the range of about 99.5% to about 50% for on-road applications. Petroleum component content varies depending on end use requirements. The range of use of petroleum components is generally between about 0.1% and about 95%.

  Another aspect of the present invention is the stability of biodiesel or bio / petroleum fuel blends. In embodiments of the invention, “stability” refers to the resistance of a biodiesel or bio / petroleum fuel blend to changes in composition during storage, in vehicles, or in engines as a result of exposure to environmental and storage factors. Means.

  In an embodiment of the present invention, the multifunctional stabilizer package includes additives selected to increase the stability of the biodiesel or bio / petroleum fuel blend.

  The compositional changes required to be delayed by the multifunctional stabilizer package are (i) odor (from volatile degradation products), (ii) increase in total acid number (TAV), (iii) increase in viscosity, (iv) Discoloration, and (v) increased tendency for precipitation and / or rubbery material formation.

  The present invention describes an additive combination (multifunctional stabilizer package) to address the problems associated with fuel instability. Suitable additives that affect the stability during use and storage of the biodiesel and bio / petroleum fuel blends used in the present invention are (i) free radical chain terminators, (ii) peroxide decomposers, (Iii) acid scavengers, (iv) photochemical stabilizers, (v) rubber dispersants, and (vi) sequestering agents.

  The species or family of each additive in the multifunctional stabilizer package is specifically selected to counteract or act in a specific degradation pathway. While these additives function in selected manners, it has been recognized that certain additives may also have a dual function. An example of such a dual capacity is a tertiary amine. These amines can simultaneously function as a peroxide decomposer (PDA) and as an acid scavenger (AS).

  The first group of chemicals suitable for formulation are free radical chain terminators (FRCTA). These additives function primarily to slow the rate of peroxide increase. A list of suitable examples in this family includes the hindered phenols (2,6-di-tertbutylphenol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2,4- Dimethyl-6-t-butylphenol, octyl gallate, t-butylhydroquinone (TBHQ), tert-butyl-4-hydroxyanisole (BHA)), phenylenediamine (N, N′-di-sec-butyl-p-phenylene) Diamines and N-sec-butyl-p-phenylenediamine), and nitroaromatic compounds (nitrobenzene, dinitrobenzene, nitro-toluene, nitro-naphthalene, and dinitro-naphthalene and alkylnitrobenzene and polyaromatic compounds). However, it is not limited to these.

A second group of chemicals suitable for formulation is the peroxide decomposer (PDA). These additives function primarily to decompose the already formed peroxide without producing new radical intermediates that can react with oxygen to grow new peroxide. Non-limiting lists of functional types and examples based on specific hydrocarbon chain lengths are described herein. The alkyl group exemplified for each functional group species is (C ₈ ) octyl, but other chain lengths ranging from about C _{4 to} C ₃₀ , such as butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl. Also suitable are undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, uneicosyl, docosyl, tricosyl, and tetracosyl, and combinations thereof.

ここで、スキーム１（化１）の式中、
Ｒ、Ｒ’、Ｒ’’は、アルキル−直鎖、分岐、飽和、不飽和、Ｃ_１−３０、芳香族、ポリアルコキシ、または環状であり、
Ｒ、Ｒ’はまた、他のヘテロ原子（例えば、Ｏ、Ｎ、Ｓ、およびＰ）、並びにそれらから得られる官能基を含有してもよく、
Ｒ’およびＲを、３〜１２員環系に組み入れることができる。 Specific types include tri-alkyl phosphorus compounds such as trioctyl phosphate, alkyl sulfur compounds such as octanethiol, octane sulfide and octane disulfide, and tertiary nitrogen compounds such as dimethyloctylamine, dioctylmethylamine, Trioctylamine is mentioned. Tertiary amines are described by the chemical formula shown in Scheme 1 (Chemical 1).
Scheme 1

Here, in the formula of Scheme 1 (Chemical Formula 1),
R, R ′, R ″ are alkyl-linear, branched, saturated, unsaturated, C _1-30 , aromatic, polyalkoxy, or cyclic;
R, R ′ may also contain other heteroatoms (eg, O, N, S, and P), and functional groups derived therefrom,
R ′ and R can be incorporated into a 3-12 membered ring system.

ここで、スキーム２（化２）の式中、
Ｒ、Ｒ’は、アルキル−直鎖または分岐、Ｃ_１−３０、芳香族、環式、多環式、ポリアルコキシ、またはカルボニルであり、
Ｒ、Ｒ’は、他のヘテロ原子（例えば、Ｏ、Ｎ、Ｓ、およびＰ）、並びにそれらから得られる官能基を含んでもよく、
ＲおよびＲ’は、３〜１２員環系に組み入れることができ、
Ｘは１〜６であり、
Ｙは１〜６である。 Amine functional species also include tertiary polyamines. The tertiary polyamine is described by the formula illustrated in Scheme 2
Scheme 2

Here, in the formula of Scheme 2 (Chemical Formula 2),
R, R ′ is alkyl-linear or branched, C _1-30 , aromatic, cyclic, polycyclic, polyalkoxy, or carbonyl;
R, R ′ may include other heteroatoms (eg, O, N, S, and P), and functional groups derived therefrom,
R and R ′ can be incorporated into a 3-12 membered ring system;
X is 1-6,
Y is 1-6.

  The carbonyl moiety can crosslink the polyamine moiety with other organic functional groups. These functional groups include amides, imides, imidazolines, carbamates, ureas, imines, and enamines. Parent amines or polyamines can also be converted to their corresponding alkoxylates. Alkoxylates are products derived from reaction with 1 to 100 molar equivalents of the alkoxylating agent nitrogen moiety. The required alkoxylating agent is selected from the group comprising ethylene oxide, propylene oxide, butylene oxide and epichlorohydrin, or mixtures thereof. Alkoxylates can be made from one alkoxylating agent or a mixture of drugs. Alkoxylates derived from a mixture of alkoxylating agents can be prepared by stepwise addition of the drug to the amine to form a block polymer, or added as a mixture to produce random block / alternate alkoxylates. Can be formed. These oxyalkylates can be further derivatized with organic acids to form esters.

  In general, it should be understood that any compound containing a P, S, or N atom can be used to meet the needs of the present invention.

  A third group of compounds suitable for formulation are acid scavengers (AS). These additives mainly serve to treat the acid formed in the oxidation process. These scavengers are important to prevent changes in the biodiesel acidity. Increased fuel acidity catalyzes undesired reactions such as hydrolysis of bioesters, decomposition of peroxides present to form aldehydes and ketones, and the reaction of aldol-type chemical reactions of intermediate aldehydes and ketones. Promoting biodiesel degradation by increasing the speed. The products of these reactions are responsible for the formation of solid or rubbery substances in the fuel.

The list of examples in this family includes, but is not limited to, primary, secondary, and tertiary amines, and derivatives thereof. The amine nitrogens of this family can be combined with linear, branched, saturated, unsaturated, or cyclic, hydrocarbon, aromatic or polyaromatic groups, hydrogen, or combinations of these groups. Each hydrocarbon group attached to this nitrogen atom can contain about C _{4 to} C ₃₀ atoms. In the case of saturated alkylamines, this group is butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, uneicosyl, docosyl, tricosyl, And defined as tetracosyl.

ここで、スキーム３（化３）の式中、
Ｒ、Ｒ’は、Ｈ、アルキル−直鎖、分岐、飽和、不飽和、Ｃ_１−３０、芳香族、環状、ポリアルコキシおよびカルボニルであり、
Ｒ、Ｒ’はまた、他のヘテロ原子（例えばＯ、Ｎ、Ｓ、およびＰ）、並びにそれらから得られる官能基を含むことができ、
Ｒ’およびＲ’は、３〜１２員環系に組み入れることができ、
Ｚは、Ｒであるか、または、次の化学式４

であらわされるものであり、化学式４の式中、
Ｘは１〜６であり、
Ｙは１〜６である。 A preferred subclass of amines that can also function as acid scavengers are polyamines. Suitable polyamines of the present invention are polyethylene polyamines such as EDA (ethylenediamine), DETA (diethylenetriamine), TETA (triethylenetetraamine) and their higher homologues, their alkyl analogues (but not limited to N -Exemplified by coco-ethylenediamine, N-oleyl-ethylenediamine, and N-butyl-ethylenediamine), and these industrially available spacer-based analogs such as, but not limited to, propyl and hexyl , Dipropylenetriamine, and bis-hexamethylenetriamine), and their subsequent derivatives such as ester amine, amidoamine, imidoamine, imidazoline, carbamate, urea, imi , And enamine. Scheme 3 (Chemical 3) illustrates a general formula illustrating an acid scavenger.
Scheme 3

Here, in the formula of Scheme 3 (Chemical Formula 3),
R, R ′ are H, alkyl-linear, branched, saturated, unsaturated, C _1-30 , aromatic, cyclic, polyalkoxy and carbonyl;
R, R ′ can also include other heteroatoms (eg, O, N, S, and P), and functional groups derived therefrom,
R ′ and R ′ can be incorporated into a 3-12 membered ring system;
Z is R or the following chemical formula 4

In the formula of chemical formula 4,
X is 1-6,
Y is 1-6.

  A fourth group of chemicals suitable for formulation are photochemical stabilizers (PCS). These additives function to mainly react with singlet oxygen generated by the interaction of light and oxygen in the presence of a sensitizer. Photooxidation cannot be inhibited by additives that function as free radical chain terminators such as BHT, BHA and tocopherol.

  Photooxidation can be interrupted by introducing molecules that react with singlet oxygen more rapidly than bioesters. The list of examples in this family includes, but is not limited to, hindered amine light stabilizers (HALS), such as piperidine.

  A fifth group of chemicals suitable for formulation is rubber dispersant (GD). These additives function primarily to disperse polymers or high molecular weight compounds that are either found in the fuel after refining or are by-products of oxidation or thermal destruction. A non-limiting list of chemicals that can be applied to perform this function includes ethylene and unsaturated esters, vinyl alcohol, vinyl ethers and esters with these organic acids, propylene, ethylene, isobutylene unsaturated carboxylic acids ( For example, adducts with maleic acid and fumaric acid), and their amide or imide derivatives, acrylic acid and their amide or ester derivatives, polystyrene, and polymers made from combinations of these monomers.

  A sixth group of chemicals suitable for formulation are sequestering agents (MAS). These additives primarily function to chelate metals that can be present in biodiesel or bio / petroleum fuel blends. The list of examples in this family includes, but is not limited to, EDTA (ethylenediaminetetraacetic acid), citric acid, and industry standard DMD (N, N-disalicylidene-1,2-propanediamine).

  The components of the multifunctional stabilizer package can be combined in the ratios necessary to effectively stabilize the biodiesel or bio / petroleum blend.

  In general, free radical chain terminators can be present in the formulation between about 0.0 and about 100% of the total stabilizer composition, and free radical degrading agents can be present between 0 and 100% in the formulation. The photochemical stabilizer can be present in the formulation between about 0.0 and about 100%, and the sequestering agent is present in the formulation between about 0.0 and about 25%. can do.

  Generally, the package is about 25 to about 85% free radical chain terminator, about 15 to about 65% free radical degrading agent, about 0.0 to about 10% photochemical stabilizer, and about 1 to about 3%. Contains a sequestering agent.

  The present invention further provides a process for adding said additives to stabilize bio and bio / petroleum fuel blends. These additives can be added to B100 and this B100 can then be blended with the petroleum based fuel or the additive can be added directly to the bio / petroleum blended fuel.

  Additive package dosing rate is dependent on environmental conditions (eg humidity, storage temperature, exposure), fuel processing, and storage conditions (eg surface area exposed to air, storage period, load from previous processing, microorganisms, metals And impurities in the system including water), biofeeds (fatty acid composition) and petroleum-based fuels (crude slate and processing), and their individual blend ratios.

  In general, the effective range in which the additive provides stability protection during use and storage of bio and bio / petroleum blends is from about 0.005 to about 3% by volume B100 or 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 improve stability during use and storage of biofuels and biofuel / petroleum fuel blends, but also have certain properties that allow for use in the fuel market. The additive package must be compatible with the fuel system components, which are handleable (low enough viscosity to be pumpable) at the temperature of use in the northern winter climate. Must be fluid. In general, the fuel additive is required to be liquid at about −40 ° C.

  The formulations selected in the present invention significantly inhibit instability mechanisms (oxidative instability, hydrolytic instability, and thermal instability) and fuel changes (acidity, viscosity, color, odor, and Anxiety of both biofuels and bio / petroleum fuel blends, substantially reducing the tendency to rubbery material formation, thereby dramatically increasing the stability during storage and use of biofuels and bio / petroleum fuel blends Address various aspects of qualitatively. The multifunctional stability package also addresses all handling capacity requirements for additives utilized in the petroleum industry.

  In addition, the multifunctional stability package described herein, for example, (a) electrostatic dissipation / conductivity improving additive, (b) low temperature operability / cold flow additive, (c) corrosion inhibitor, (D) Lubricity improver, (e) cetane improver, (f) detergent, (g) dye and marker, (h) anti-icing additive, (i) biocide, and (j) demulsifier. Combinations with other suitable additives well known to those skilled in the art commonly used in fuel oils, such as / anti-fogging additives, are considered part of this invention.

  Static dissipative / conductive additives are used to minimize the risk of electrostatic ignition in hydrocarbon fuels and solvents. It is well known that static electricity can be moved by friction between two different non-conductive materials. When this happens, the static electricity thus generated appears on the surface of the contact material. The magnitude of the generated charge depends on the nature of each material and more specifically on the respective conductivity. Electrostatic charging is known to occur when solvent and fuel flow in conduits with high surface areas or through “fine” filters. The potential for electrostatic ignition and explosion is probably highest during product handling, transport and transportation. Thus, the situation of greatest concern to the oil industry is a state where charge accumulates in or around the flammable liquid, and the potential for discharge leads to ignition and possibly a serious fire or explosion. Countermeasures designed to prevent the build-up of static electricity on filled containers, such as ground (ie, “earth”) and bonded containers, are typically used. However, it has been recognized that grounding and adhesion alone are insufficient to prevent the accumulation of static electricity in low conductivity, volatile organic liquids. Organic liquids such as distillate fuels such as diesel, gasoline, jet fuel, turbine fuels and kerosene, and light hydrocarbon oils relatively free of contaminants such as organic solvents and cleaning fluids are essentially poor conductors It is. Static electricity accumulates in these fluids. The reason is that the charge moves very slowly through these liquids and takes a considerable amount of time to reach the grounded surface. By the time the charge is dissipated, a high surface potential is achieved, which can cause a spark and consequently ignite or explode. The increased risk posed by low conductivity organic liquids can be addressed by the use of additives to increase the conductivity of the respective fluid. Increasing the conductivity of the liquid will substantially reduce the time required for the charge present in the liquid to be conducted away by the internal surface of the grounded container.

  Low temperature operability / cold flow additives are used in the fuel to allow users and operators to handle the fuel at temperatures below which the fuel normally causes operational problems. Distillate fuels, such as diesel fuels, tend to decrease in flow rate at low temperatures, in part due to the formation of waxy solids in the fuel. The reduction in distillate fuel flow affects the refining process and the transport and use of distillate fuel in internal combustion engines. This is the case in winter, particularly at the temperature at which solid formation begins in the fuel (generally the cloud point (ASTM D 2500, the entire teaching of which is referred to as part of the present invention) or the wax appearance point (ASTM D 3117, all of its The teaching is referred to as part of the present invention and is particularly problematic in the north where the distillate is often exposed to a temperature called the formation of waxy solids in the fuel. And thus clog transport lines such as refined pipes and engine fuel supply lines, and under low temperature conditions during distillate fuel consumption, wax precipitation and gelation clog engine fuel filters, as in diesel engines, As a result, the engine can become inoperable.

  Lubricity modifiers increase the lubricity of the fuel, which affects the ability of the fuel to prevent wear on contact metal surfaces in the engine. A possible adverse effect of insufficient fuel lubrication capability can be an early failure of an engine component (eg, a fuel injection pump).

  Corrosion inhibitors are a group of additives that are utilized to prevent or retard the harmful interaction of fuel and materials present in the fuel with engine components. Additives used to provide corrosion inhibition for fuels generally also function as lubricity improvers. These additives coat the surface of the drive metal part and suppress the interaction of the metal with water. This coating also functions as a lubrication barrier between the drive metal parts, resulting in reduced wear.

  Cetane improvers are used to improve the combustion characteristics of middle distillates. As discussed in US Pat. No. 5,482,518 (the entire teachings of which are referred to as part of the present invention), fuel ignition in a diesel engine is caused by the piston in the cylinder moving during the compression stroke. This is achieved by the heat generated by air compression when the cylinder volume decreases. In the engine, air is first compressed and then fuel is injected into the cylinder. When fuel comes into contact with heated air, it evaporates and eventually begins to burn when it reaches the autoignition temperature. When additional fuel is injected during the compression stroke and the first flame occurs, the fuel burns almost instantaneously. Thus, it takes some time from the start of fuel injection to the appearance of a flame in the cylinder. This time is usually referred to as “ignition delay” and must be relatively short to avoid “diesel knock”. The main factor contributing to diesel fuel performance and “diesel knock” is the cetane number of diesel fuel. A diesel fuel with a high cetane number has a shorter ignition delay than a diesel fuel with a low cetane number. Accordingly, high cetane number diesel fuel is desirable to avoid diesel knock. Most diesel fuels have a cetane number in the range of about 40 to about 55. The relationship between ignition delay and cetane number is described in “How Do Diesel Fuel Ignition Improvers Work”, Clothier et al., Chem. Soc. Rev, 1993, pages 101-108, the entire teachings of which are incorporated herein by reference. Cetane improvers have been used for many years to improve the ignitability of diesel fuel.

  Detergents are additives that can be added to hydrocarbon fuels to prevent or reduce deposit formation, or to remove or modify deposits that have formed. It is generally known that certain fuels tend to form deposits that can clog the fuel injectors and affect the fuel spray pattern of the injectors. Changes in the fuel spray pattern result in uneven fuel distribution and / or incomplete atomization, resulting in poor fuel combustion. Accumulation of deposits is characterized by overall poor operational potential, including high load starting, stalling, rough engine idling, and tripping during acceleration. In addition, if deposit build-up proceeds without checking, irreparable damage occurs, which requires replacement or non-scheduled maintenance. In extreme cases, irregular combustion results in hot spots on the pistons that result in overall engine failure and require complete engine overhaul or replacement.

  Dyes and markers are materials used to monitor and track fuel by the EPA (Environmental Protection Agency) and IRS (National Tax Agency). Since 1994, the main use of dyes in fuels is the non-taxable “off-road” intermediate distillate as defined in the Federal Regulatory Standards, Title 26, Part 48.4082-1 (26 CFR 48.4082-1). Due to the dyeing or marking of the fed fuel directed by the federal government. Dyes are also used in aviation gasoline, and the red, blue and yellow dyes indicate the octane grade of aviation gasoline. Markers are used to identify, track or mark petroleum products without imparting a visible color to the processed product. One of the main uses of markers in fuel is in heating oil.

  Anti-icing additives are mainly used in the aviation industry and in cold climates. These act by binding to free water and lowering the freezing point of the mixture to suppress crystal formation.

  Biocides are used to control microorganisms that can contaminate the fuel, such as bacteria and fungi (yeast, mold). The cause of microbial problems in fuels is generally due to the cleanliness of the fuel system, particularly water removal from tanks and low points in the system.

  The demulsifier / antifogging additive is added to the fuel primarily to counter the fogging problem that can be caused by the distribution of water in the wet fuel due to the dispersant used in the stability package.

  The general chemical reactions and compositions of these additive families that serve to impart the desired fuel properties are well known in the art. One of ordinary skill in the art to which this invention pertains can readily select additives to achieve the desired improvement in fuel properties.

  The present invention addresses various causes of degradation (environment and fuel elements) associated with instability during storage and use of biofeedstock and bio / petroleum fuel blends. By using specifically selected additive types or families (free radical chain terminators, free radical degrading agents, acid scavengers, photochemical stabilizers, rubber dispersants, and sequestering agents), the present invention Designed to combat or eliminate the various specific modes / cracking paths that are responsible for fuel instability.

  The invention is further illustrated by the following illustrative but non-limiting examples. Examples include bio and bio / petroleum of various components of the multifunctional stabilizer package (free radical chain terminators, peroxide decomposers, acid scavengers, photochemical stabilizers, rubber dispersants, and sequestering agents). Describes the impact on stability of the fuel blend during storage and use.

  An oxidative load device used to quantitatively evaluate renewable fuels, blends of renewable and petroleum fuels, and additives for such fuels was developed indoors. This device is illustrated in FIG.

Indoor oxidation equipment:
The oxidation test equipment consists of a constant temperature oil bath (to load the sample to promote oxidative degradation), a test tube (containing a bio or bio petroleum blend), and an air delivery system (... It is composed of a flow control device.
(There is no paragraph [00101] through [00103] in the original text)
(The original paragraph [00104] is the translated paragraph [0096]. Hereafter, the paragraph numbers are shifted.)

  An indoor method was used to demonstrate improved stability of the additive to bio and bio / petroleum fuel blends.

Free radical chain terminator The delay on free radical increase and its subsequent effect on biofuel stability were investigated. An indoor stability method was used to load a test tube containing soy B100 and 100 mg / l FRCTA. Samples were then evaluated for fuel stability using UV analysis. The results are shown in FIG.

  The data in FIG. 1 shows that FRCTA has a market effect on biofuel stability.

Peroxide decomposer The impact of peroxide decomposition on biofuel stability was evaluated. Test tubes containing soybean B100 and stability additive (%) were prepared according to Table 2.

  The soy B100 sample was loaded using the indoor stability method. Samples were then evaluated for fuel stability using UV analysis. FIG. 2 includes the results of the evaluation.

  The data in FIG. 2 shows that there is a substantial impact on stability depending on the amount and type of FRCTA and PDA used in the formulation. It is clear that test tube 3 (75% FRCTA, 25% PDA blend) was most effective in addressing biofuel instability. From this data it can also be seen that there exists an optimal blend of two additive types / family to improve its synergistic effect and to improve its performance as a biofuel stabilizer.

Acid Scavenger The effect of acid concentration on biofuel stability was evaluated. Biodiesel with reduced acidity was prepared by neutralizing soybean B100 with 0.06 N NaOH. The acid values of the starting and acid-lowered soybeans were 0.66 mg KOH / g and 0.22 mg KOH / g, respectively. Test tubes containing two soy B100s and stability additives (%) were prepared as shown in Table 3.

  The soy B100 sample was loaded using the indoor stability method. Samples were then evaluated for fuel stability using UV analysis. FIG. 3 includes the results of the evaluation.

  The data in FIG. 3 shows that acid content has a substantial effect on biodiesel stability. It can be seen that the lower acidity samples show a higher level of stability compared to the untreated samples (1 and 4). This data further shows the impact on stabilization with additives having acid scavenging ability. This effect is demonstrated by comparing samples 2 and 3 with base sample 1 with reduced acidity, and it is clear that the use of acid scavenging formulations further improves biofuel stability. is there.

Photochemical Stabilizer To illuminate a set of test tubes containing the B100 soy sample (added with additives (%) as shown in Table 4 to a part thereof) on the effect of light on biodiesel stability. It was evaluated by.

  Tubes marked with XX were exposed to sunlight (stored in a sunny window). The remaining test tube (5) was covered with aluminum foil and protected from exposure. All test tubes were exposed to the atmosphere. After exposure to sunlight for 2 weeks, the contents of the test tube were loaded using the indoor stability method. Test tubes were sampled every 2 hours and evaluated for fuel stability using UV analysis. FIG. 4 includes the results of the evaluation.

  The data in FIG. 4 shows that exposure to direct sunlight has a slight effect on biofuel. From a comparison of samples 1 and 5, it can be seen that the exposure reduced the stability of the biofuel, but not to a great extent. Samples with added additives show improved stability, but it is not clear whether this is due to inhibition of destabilization by light.

As a parallel experiment, the influence of aging (aeration) was also evaluated. As shown in Table 5, additives (%) were added to a set of test tubes A containing B100 soybean samples.

  Test tubes with the XX symbol were exposed to sunlight (stored in a sunny window). The remaining test tubes (2, 3, and 4) were covered with aluminum foil and protected from exposure. All test tubes were exposed to the atmosphere. After 2 weeks exposure, the test tube contents were loaded using the indoor stability method. Test tubes were sampled every 2 hours and evaluated for fuel stability using UV analysis. FIG. 5 includes the results of the evaluation.

  The data in FIG. 5 shows that there is a substantial impact on biofuel stability when exposed to air and stored for extended periods of time. Compared to this sample, the test tubes containing dual mode stabilizers (FRCTA and PDA) were superior to single mode (FRCTA) stabilizers in preventing degradation due to long term storage.

屋内安定性法を用いて、大豆Ｂ１００サンプルに負荷を加えた。ＵＶ分析法を用いて燃料安定性についてサンプルを評価した。図６は評価の結果を含む。 Metal ion sequestering agent The influence of metal (copper) contamination on biofuel stability was evaluated. Test tubes containing B100 soy and additives (%) were prepared according to Table 6.

The soy B100 sample was loaded using the indoor stability method. Samples were evaluated for fuel stability using UV analysis. FIG. 6 includes the results of the evaluation.

  The data in FIG. 6 shows that copper has a significant impact on the rate of biofuel degradation. Comparing sample 1 and sample 5, it can be seen that the blank without copper is stable under a load of 2 hours, while the sample containing copper exhibits a substantial level of degradation. The same result is seen between sample 4 and sample 6. The biofuel in Sample 6 has the same stabilizer composition and processing rate as Sample 4, but Sample 6 was substantially more stable than Sample 4 containing the metal contaminant (copper). It is also interesting to note the improved stability in the presence of copper between Sample 2 containing only the free radical chain terminator and Sample 4 containing the free radical chain terminator and peroxide decomposer. This improved stability indicates a synergy between the selected components. Overall, radical chain terminators, peroxide decomposers and sequestering agents work best to increase biofuel stability.

  The examples shown clearly show that there are many factors that contribute to the various mechanisms of instability of biofuels and bio / petroleum fuel blends. Therefore, it is important to properly select and combine additives to fully address these diverse instability processes.

  Although certain preferred embodiments of the present invention have been disclosed in detail, it should be understood that various modifications can be made without departing from the spirit of the following claims.

Claims (36)

(A) a renewable biofeedstock component;
(B) petroleum components;
(C) a multifunctional stabilizer package;
A fuel oil composition comprising:   Wherein the renewable biofeedstock component is a product of transesterification of a naturally occurring plant or animal whole oil with an alcohol, or an ester of a fatty acid and an alcohol derived from a naturally occurring oil. 2. The fuel oil composition according to claim 1, characterized as biodiesel.   The natural oil is from the group consisting of soybean oil, coconut oil, rapeseed oil, linseed oil, coconut oil, corn oil, cottonseed oil, edible oil, sunflower oil, safflower oil, tallow, lard, yellow oil, fish oil and blends thereof The fuel oil composition according to claim 2, which is selected.   The fuel oil composition according to claim 2, wherein the alcohol is selected from the group consisting of linear, branched, alkyl, aromatic, primary, secondary, tertiary, and polyol.   The fuel oil composition according to claim 1, wherein the petroleum component is middle distillate fuel, heavy fuel oil, jet fuel, or Fischer-Tropsch oil.   The fuel oil composition of claim 1, wherein the petroleum-based component of the fuel oil contains less than about 5000 ppm (mass) of sulfur.   The fuel oil composition of claim 1, wherein the petroleum-based component of the fuel oil contains less than about 500 ppm (mass) of sulfur.   The fuel oil composition of claim 1, wherein the petroleum-based component of the fuel oil contains less than about 17 ppm (mass) of sulfur.   The fuel oil composition of claim 1, wherein the content of the renewable biofeedstock component of the fuel oil is from about 0% to about 100% by volume of the final fuel.   The fuel composition according to claim 1, wherein the content of the renewable biofeedstock component of the fuel oil is from about 1% to about 30% by volume of the final fuel.   The fuel oil composition of claim 1, wherein the content of the petroleum-based component of the fuel oil is from about 0.1% to about 100% by volume of the final fuel.   The fuel oil composition of claim 1, wherein the content of the petroleum-based component of the fuel oil is from about 70% to about 99% by volume of the final fuel. The multifunctional stabilizer package is
(A) a free radical chain terminator,
(B) a peroxide decomposer,
(C) acid scavenger,
(D) a photochemical stabilizer,
2. The fuel oil composition of claim 1, wherein the fuel oil composition is a suitable combination of one or more members of the group consisting of (e) a rubber dispersant and (f) a sequestering agent.   14. The fuel oil composition according to claim 13, wherein the free radical chain terminator is selected from the group consisting of alkylphenols, alkylphenylenediamines, quinones, and nitro compounds.   The alkylphenol is alkylphenol (2,6-di-tertbutylphenol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2,4-dimethyl-6-tert-butylphenol, tert-butyl-4. -Hydroxyanisole (BHA)), dihydroxybenzene (1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 1,2-dihydroxybenzene), trihydroxybenzene (1,2,3 trihydroxybenzene), 1-3 15. The fuel oil composition according to claim 14, wherein the fuel oil composition is selected from the group consisting of polycyclic aromatic compounds containing one hydroxyl group and a gallic acid derivative (octyl gallate).   The fuel oil composition according to claim 14, wherein the alkylphenylenediamine is selected from the group consisting of N, N'-di-sec-butyl-p-phenylenediamine and N-sec-butyl-p-phenylenediamine. .   The quinone compound is selected from the group consisting of 2,3,5-trimethylbenzoquinone, 2,3-dimethylbenzoquinone, 2,3-dimethoxy-5-methylbenzoquinone, 2-methylnaphthoquinone, t-butylhydroquinone (TBHQ). The fuel oil composition according to claim 14.   The fuel oil composition according to claim 14, wherein the nitro compound is selected from the group consisting of nitrobenzene, dinitrobenzene, nitrotoluene, nitronaphthalene, and dinitronaphthalene.   The fuel oil composition according to claim 13, wherein the peroxide decomposer is selected from the group consisting of a sulfur compound, a nitrogen compound, and a phosphorus compound. The nitrogen compound has the general formula:

A fuel oil composition according to claim 19 represented by
In this general formula:
R, R ′, R ″ are any of alkyl-linear, branched, saturated, unsaturated C _1-30 , aromatic, cyclic, polyalkoxy, polycyclic,
R, R ′ may also contain other heteroatoms such as O, N, S and P, and functional groups derived therefrom,
20. The fuel oil composition according to claim 19, wherein R and R 'can alternatively be incorporated into a cyclic system containing 3-12 atoms.   14. The fuel oil composition of claim 13, wherein the acid scavenger is selected from the group consisting of primary, secondary and tertiary amines, and derivatives thereof. The acid scavenger has the general formula:

A fuel oil composition according to claim 13 represented by
In this general formula:
R, R ′ is any one of H, alkyl-linear, branched, saturated, unsaturated C _1-30 , aromatic, cyclic, polyalkoxy, and carbonyl,
R, R ′ may also contain other heteroatoms such as O, N, S and P, and functional groups derived therefrom,
R ′ and R ′ can be incorporated into a 3-12 membered ring system;
Z is R or the following formula

It is represented by
The fuel oil composition according to claim 13, wherein X is 1 to 6 and Y is 1 to 6.   14. The fuel oil composition according to claim 13, wherein the photochemical stabilizer is selected from the group consisting of hindered amine light stabilizers.   The rubber dispersant is an ethylene and unsaturated ester, vinyl alcohol, vinyl ether and an ester thereof with an organic acid, propylene, ethylene, an isobutylene adduct with an unsaturated carboxylic acid (for example, maleic acid or fumaric acid) and the like. 14. A polymer dispersant selected from the group consisting of amide or imide derivatives, polymers of acrylic acid and their amide or ester derivatives, polystyrene, and polymers prepared from combinations of these monomers. Fuel oil composition.   The fuel oil composition of claim 13, wherein the sequestering agent is selected from the group consisting of DMD, citric acid, and ethylenediaminetetraacetic acid (EDTA).   The fuel oil composition according to claim 13, wherein the sequestering agent is DMD.   The free radical chain terminator is present from about 0 to about 100% in the formulation of the multifunctional stabilizer package, the free radical degrading agent is present from 0 to 100% in the formulation, and the photochemical stabilizer is 14. The fuel oil composition of claim 13, wherein the fuel oil composition is present from about 0.0 to about 100% and the sequestering agent is present in the formulation from about 0 to about 25%.   The free radical chain terminator is preferably present in about 25 to about 85% in the formulation of the multifunctional stabilizer package, and the free radical degrading agent is present in the formulation from about 15 to about 65%, 14. The fuel oil composition of claim 13, wherein a photochemical stabilizer is preferably present in the formulation from about 0.0 to about 10% and the sequestering agent is present in the formulation from about 1 to about 3%. object.   14. The fuel oil composition according to claim 13, further comprising or obtained by mixing the additive with a carrier or diluent.   14. The fuel oil composition of claim 13, wherein the carrier and diluent are selected from the group consisting of aromatics, aliphatic hydrocarbons, alcohols, and carbonyl-containing materials (eg, aldehydes, ketones, esters, and amides). object. A method for increasing the storage stability of renewable fuels, comprising:
A method of increasing the storage stability of a renewable fuel by weighing and adding a multifunctional stabilizer package up to 3% by volume of the renewable fuel into the renewable fuel. A method for increasing the storage stability of a fuel composition comprising:
A method of increasing the storage stability of a fuel composition by weighing and adding up to 3% by volume of a multifunctional stabilizer package in a bio / petroleum fuel blend.   (A) Electrostatic dissipation / conductivity improving additive, (b) Low temperature operability / cold flow additive, (c) Corrosion inhibitor, (d) Lubricant improving agent, (e) Cetane number improving agent, (f) The fuel oil composition of claim 1, in combination with a detergent and (g) an additive selected from the group consisting of a dye and a marker.   A method of operating an internal combustion engine, such as a compression ignition engine, using the fuel oil composition of claim 1 as fuel.   35. The method of claim 34, wherein the selected fuel oil has a composition that is about 1% to about 30% biocomponents with the remainder being petroleum components.   35. The method of claim 34, wherein the petroleum component of a bio petroleum blend is a middle distillate fuel containing less than 500 ppm (mass) of sulfur.

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