Patent Description:
<CIT>, <CIT>, <CIT> and <CIT> all disclose methods of producing a blended fuel.

The method of the invention is defined in the appended claims.

Various embodiments are described hereinafter. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and can be practiced with any other embodiment(s).

As used herein, "about" will mean up to plus or minus <NUM>% of the particular term. For example, "about <NUM> vol. %" would mean "<NUM> vol. % to <NUM> vol.

The use of the terms "a" and "an" and "the" and similar referents in the context of describing the elements (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the embodiments and does not pose a limitation on the scope of the claims unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential.

As used herein, "alkyl" groups include straight chain and branched alkyl groups. Examples of straight chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, sec-butyl, t-butyl, neopentyl, and isopentyl groups. It will be understood that the phrase "Cx-Cy alkyl," such as C<NUM>-C<NUM> alkyl, means an alkyl group with a carbon number falling in the range from x to y.

The term "aromatics" as used herein is synonymous with "aromates" and means both cyclic aromatic hydrocarbons that do not contain heteroatoms as well as heterocyclic aromatic compounds. The term includes monocyclic, bicyclic and polycyclic ring systems (collectively, such bicyclic and polycyclic ring systems are referred to herein as "polycyclic aromatics" or "polycyclic aromates"). The term also includes aromatic species with alkyl groups and cycloalkyl groups. Thus, aromatics include, but are not limited to, benzene, azulene, heptalene, phenylbenzene, indacene, fluorene, phenanthrene, triphenylene, pyrene, naphthacene, chrysene, anthracene, indene, indane, pentalene, and naphthalene, as well as alkyl and cycloalkyl substituted variants of these compounds. In some embodiments, aromatic species contains <NUM>-<NUM> carbons, and in others from <NUM> to <NUM> or even <NUM>-<NUM> carbon atoms in the ring portions of the groups. The phrase includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indane, tetrahydronaphthene, and the like).

"Oxygenates" as used herein means carbon-containing compounds containing at least one covalent bond to oxygen. Examples of functional groups encompassed by the term include, but are not limited to, carboxylic acids, carboxylates, acid anhydrides, aldehydes, esters, ethers, ketones, and alcohols, as well as heteroatom esters and anhydrides such as phosphate esters and phosphate anhydrides. Oxygenates may also be oxygen containing variants of aromatics, cycloparaffins, and paraffins as described herein.

The term "paraffins" as used herein means non-cyclic, branched or unbranched alkanes. An unbranched paraffin is an n-paraffin; a branched paraffin is an isoparaffin. "Cycloparaffins" are cyclic, branched or unbranched alkanes.

The term "paraffinic" as used herein means both paraffins and cycloparaffins as defined above as well as predominantly hydrocarbon chains possessing regions that are alkane, either branched or unbranched, with mono- or di-unsaturation (i.e., one or two double bonds).

Hydroprocessing as used herein describes the various types of catalytic reactions that occur in the presence of hydrogen without limitation. Examples of the most common hydroprocessing reactions include, but are not limited to, hydrogenation, hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrotreating (HT), hydrocracking (HC), aromatic saturation or hydrodearomatization (HDA), hydrodeoxygenation (HDO), decarboxylation (DCO), hydroisomerization (HI), hydrodewaxing (HDW), hydrodemetallization (HDM), decarbonylation, methanation, and reforming. Depending upon the type of catalyst, reactor configuration, reactor conditions, and feedstock composition, multiple reactions can take place that range from purely thermal (i.e., do not require catalyst) to catalytic. In the case of describing the main function of a particular hydroprocessing unit, for example an HDO reaction system, it is understood that the HDO reaction is merely one of the predominant reactions that are taking place and that other reactions may also take place.

Decarboxylation (DCO) is understood to mean hydroprocessing of an organic molecule such that a carboxyl group is removed from the organic molecule to produce CO<NUM>, as well as decarbonylation which results in the formation of CO.

Pyrolysis is understood to mean thermochemical decomposition of carbonaceous material with little to no diatomic oxygen or diatomic hydrogen present during the thermochemical reaction. The optional use of a catalyst in pyrolysis is typically referred to as catalytic cracking, which is encompassed by the term as pyrolysis, and is not be confused with hydrocracking.

Hydrotreating (HT) involves the removal of elements from groups <NUM>, <NUM>, <NUM>, and/or <NUM> of the Periodic Table from organic compounds. Hydrotreating may also include hydrodemetallization (HDM) reactions. Hydrotreating thus involves removal of heteroatoms such as oxygen, nitrogen, sulfur, and combinations of any two more thereof through hydroprocessing. For example, hydrodeoxygenation (HDO) is understood to mean removal of oxygen by a catalytic hydroprocessing reaction to produce water as a by-product; similarly, hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) describe the respective removal of the indicated elements through hydroprocessing.

Hydrogenation involves the addition of hydrogen to an organic molecule without breaking the molecule into subunits. Addition of hydrogen to a carbon-carbon or carbon-oxygen double bond to produce single bonds are two nonlimiting examples of hydrogenation. Partial hydrogenation and selective hydrogenation are terms used to refer to hydrogenation reactions that result in partial saturation of an unsaturated feedstock. For example, vegetable oils with a high percentage of polyunsaturated fatty acids (e.g., linoleic acid) may undergo partial hydrogenation to provide a hydroprocessed product wherein the polyunsaturated fatty acids are converted to mono-unsaturated fatty acids (e.g., oleic acid) without increasing the percentage of undesired saturated fatty acids (e.g., stearic acid). While hydrogenation is distinct from hydrotreatment, hydroisomerization, and hydrocracking, hydrogenation may occur amidst these other reactions.

Hydrocracking (HC) is understood to mean the breaking of a molecule's carbon-carbon bond to form at least two molecules in the presence of hydrogen. Such reactions typically undergo subsequent hydrogenation of the resulting double bond.

Hydroisomerization (HI) is defined as the skeletal rearrangement of carbon-carbon bonds in the presence of hydrogen to form an isomer. Hydrocracking is a competing reaction for most HI catalytic reactions and it is understood that the HC reaction pathway, as a minor reaction, is included in the use of the term HI. Hydrodewaxing (HDW) is a specific form of hydrocracking and hydroisomerization designed to improve the low temperature characteristics of a hydrocarbon fluid.

It will be understood that if a composition is stated to include "Cx-Cy hydrocarbons," such as C<NUM>-C<NUM> n-paraffins, this means the composition includes one or more paraffins with a carbon number falling in the range from x to y.

A "diesel fuel" in general refers to a fuel with boiling point that falls in the range from about <NUM> to about <NUM> (the "diesel boiling range").

A "biodiesel" as used herein refers to fatty acid C<NUM>-C<NUM> alkyl esters produced by esterification and/or transesterification reactions between a C<NUM>-C<NUM> alkyl alcohol and free fatty acids and/or fatty acid glycerides, such as described in <CIT>,.

A "synthetic paraffinic diesel" as used throughout herein refers to diesel boiling range paraffinic hydrocarbons (<NUM>) generated by a process that includes hydrodeoxygenation (HDO) of one or more biorenewable feedstocks to produce a HDO product, optionally followed by hydroisomerization of the HDO product; or (<NUM>) a combination of (<NUM>) and a fuel generated by a process that includes a Fischer-Tropsch process.

A "petroleum diesel" as used herein refers to diesel fuel produced from crude oil, such as in a crude oil refining facility and includes hydrotreated straight-run diesel, hydrotreated fluidized catalytic cracker light cycle oil, hydrotreated coker light gasoil, hydrocracked FCC heavy cycle oil, and combinations thereof.

It is to be understood that a "volume percent" or "vol. %" of a component in a composition or a volume ratio of different components in a composition is determined at <NUM> (<NUM>°F) based on the initial volume of each individual component, not the final volume of combined components.

The higher fuel efficiency of the diesel engine compared to gasoline engine results in significantly lower CO<NUM> emissions per miles traveled. However, from an emissions standpoint, it is the non-CO<NUM> emissions that have presented the challenge with diesel engines/fuels. A particular challenge relates to emissions of nitrogen oxides (NOx) and particulate matter (PM).

Generally, NOx is formed by the high temperature reaction of N<NUM> and O<NUM> in air, whereas PM is formed by incomplete combustion of fuel. While modification of both fuel composition (e.g., in the form of additives such as di-tert-butyl peroxide, <NUM>-ethylhexyl nitrate, other organic peroxides, and/or cetane improvers) and engine operation have been attempted to reduce NOx or PM to some extent, there is a trade-off between the two and a decrease in one is typically accompanied by an increase in the other. This has been referred to in the art as the "diesel dilemma" or the "NOx/PM trade-off.

Another type of undesirable emission that affects both diesel and gasoline fuels is carbon monoxide (CO) and hydrocarbons, both of which are byproducts of incomplete fuel combustion. Although these emissions can be partially addressed by after-treatment systems, such as a diesel particulate filter (DPF) and/or direct oxidation catalyst system, there is a need for diesel fuels that emit lower levels of these components in engines without after-treatment systems and that reduce the load on the after-treatment systems in engines that have them. While a DPF allows equipped engines to reduce tailpipe emissions a majority of the time, the DPF requires periodic regeneration by combusting fuel to burn off the soot/PM it collects - a "non-useful" consumption of fuel. This non-useful fuel consumption can be reduced by reducing the engine-out emissions, such as by in-cylinder reductions of these pollutants via more complete combustion, which provides for improved fuel efficiency due to both the improved combustion on a continuous basis and less frequent or less intensive DPF regenerations. Despite this important benefit, the intractable challenge has been to achieve reduction in PM, CO, and hydrocarbon emissions without simultaneously increasing NOx emissions.

Lower PM emissions for a given NOx emission level has been achieved by reducing sulfur and aromatics in petroleum diesel, where CARB (California Air Resource Board guidelines) and Swedish Diesel are examples. CARB diesel has an aromatics specification of <NUM> vol. % max (CCR <NUM>) while Swedish Diesel (<NUM> Mk1 Diesel Specifications) sets the upper limit of aromatics and sulfur at <NUM> vol. % and <NUM> wppm respectively. These diesel attributes are typically met via severe hydrodesulfurization and hydrodearomatization processes at petroleum refineries. However, such low-sulfur/low aromatic fuels have generated issues associated with elastomer compatibility.

Traditionally, nitrile rubber elastomers (the standard gasket material used in legacy fleets) are used in fuel system components because they swell when exposed to typical fuels (commonly regarded as due to the presence of aromatics) and thereby provide a tight seal for fuel system components. However, in low-sulfur/low aromatic petroleum fuels, leakage has been observed; this problem is particularly acute with synthetic paraffinic diesels with undetectable to very low concentrations of aromatics and sulfur, such as those meeting European Standard EN15940 (<NUM>) for diesel fuels which sets the upper limit for sulfur and aromatics as <NUM> wppm and <NUM> wt% respectively.

Although air emission standards for marine applications are not as stringent as they are for on-road diesel, fuels with better biodegradability and marine eco-toxicity are becoming highly desirable. Biodiesel has excellent biodegradability and is considered an essentially non-toxic fuel.

One of the challenges in developing diesel fuels with good biodegradability is that these have relatively poor thermo-oxidative stability. Low thermo-oxidative stability generally correlates to poor storage stability and higher likelihood of engine deposits. Along with its excellent biodegradability, biodiesel typically exhibits lower oxidative stability than petroleum fuels - a concern for some potential users of renewable fuels. Fuels providing a combination of better biodegradability and lower toxicity than petroleum diesel and better thermo-oxidative stability than biodiesel would be highly valued by multiple markets and regulatory jurisdictions.

In addition, fuels with lower "carbon intensity" are also becoming increasingly desirable in many fuel markets. In general, lower carbon intensity fuels are produced from renewable sources rather than exclusively petroleum sources. An example is biodiesel.

There is therefore a need for diesel fuels that provide a better balance of emission properties and a less significant trade-off between biodegradability and stability while ensuring that the fuel is compatible with vehicles using conventional elastomers and concomitantly ensuring such fuels provide lower carbon intensity than conventional petroleum fuels.

Attempts to provide such a balance have typically focused on blending petroleum diesel with biodiesel, where various studies on the effect of biodiesel content on properties of D2/ULSD/CARB diesel (petroleum) fuels have been published. These generally report an improvement in particulate matter, CO, and HC emissions with increasing levels of biodiesel inclusion, however, this tends to be accompanied by an increase in NOx emissions. Other published studies have looked at additives to reduce NOx emissions in petroleum diesel/biodiesel blends.

Guidance on advantageous two component blends of synthetic paraffinic diesel and biodiesel or on advantageous three component blends of petroleum diesel, biodiesel, and synthetic paraffinic diesel is needed in terms of providing blends with a broad set of performance properties, including emissions (e.g., engine emissions), biodegradability, and cold flow properties, and elastomer compatibility. In fact, commercial producers of synthetic paraffinic fuel production have stated that synthetic paraffinic fuels are incompatible with biodiesel at all but low biodiesel concentrations (e.g., "low biodiesel concentrations" being a volume ratio of biodiesel to synthetic paraffinic diesel of less than about <NUM>:<NUM>). For example, the recently published <NPL>) states, "a maximum <NUM>% of high quality FAME [a biodiesel]. can be mixed with Neste Renewable Diesel. Precipitation risk of FAME's impurities increase if more or low quality FAME is used.

In contrast to this, the present technology provides blended fuel compositions including both biodiesel and synthetic paraffinic diesel that are not only viable but surprisingly and unexpectedly offer advantageous fuel and emission properties. The present technology also provides an unprecedented solution to any precipitation risk.

In any embodiment herein, it may be that when the blended fuel composition does not include petroleum diesel (i.e., <NUM> vol. % petroleum diesel), at least about <NUM> vol. % biodiesel is included. In any embodiment herein, it may be that when the blended fuel composition does not include petroleum diesel (i.e., <NUM> vol. % petroleum diesel), at least about <NUM> vol. % biodiesel is included. Exemplary blended fuel compositions are also illustrated in the ternary blend diagram of <FIG>. Such compositions surprisingly and unexpectedly offer advantageous fuel and emission properties. As an example, the present disclosure illustrates synergistic advantages provided by such blended fuel compositions. In addition, the blended fuel compositions of the present technology have a surprisingly better balance of other physical and chemical properties such as improved biodegradability with very little change in oxidative stability as well as surprisingly improved elastomer compatibility as compared to synthetic paraffinic diesel alone or ultra-low sulfur diesel (ULSD) alone. The blended fuel composition may be suitable as a diesel fuel, a diesel fuel additive, a diesel fuel blendstock, or a combination of any two or more thereof.

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Hydrotreatment is a process typically conducted in the presence of hydrogen over sulfided forms of hydrogenation metals from Group VIB and Group VIII of the periodic table. Examples of suitable mono-metallic, bi-metallic, and tri-metallic catalysts include Mo, Ni, Co, W, CoMo, NiMo, NiW, NiCoMo. These catalysts may be supported on alumina, or alumina modified with oxides of silicon and/or phosphorus. These catalysts may be purchased in the reduced sulfide form, or more commonly purchased as metal oxides and sulfided during startup. Hydrotreatment may be performed at a temperature falling in the range from about <NUM> °F (<NUM>) to about <NUM> °F (<NUM>) and at a pressure from about <NUM> psig (<NUM> barg) to about <NUM>,<NUM> psig (<NUM> barg). A weighted average bed temperature (WABT) is commonly used in fixed bed, adiabatic reactors to express the "average" temperature of the reactor which accounts for the nonlinear temperature profile between the inlet and outlet of the reactor. <MAT> <MAT>.

In the equation above, <MAT> and <MAT>refer to the temperature at the inlet and outlet, respectively, of catalyst bed i. As shown, the WABT of a reactor system with N different catalyst beds may be calculated using the WABT of each bed (WABTi) and the weight of catalyst in each bed (Wci). Hydroisomerization is typically conducted in the presence of hydrogen over a bifunctional catalyst at temperatures in the range of about <NUM> to about <NUM>. Bifunctional catalysts are those having a hydrogenation-dehydrogenation activity from a Group VIB and/or Group VIII metal, and acidic activity from an amorphous or crystalline support such as amorphous silica-alumina (ASA), silicon-aluminum-phosphate (SAPO) molecular sieve, or aluminum silicate zeolite (ZSM). Exemplary hydroisomerization catalysts include Pt/Pd-on-ASA, and Pt-on-SAPO-<NUM>.

Exemplary biorenewable feedstocks include, but are not limited to, an animal fat, animal oil, microbial oil, plant fat, plant oil, vegetable fat, vegetable oil, grease, or a mixture of any two or more thereof. Plant and/or vegetable oils and/or microbial oils include, but are not limited to, corn oil, distiller's corn oil, babassu oil, carinata oil, soybean oil, canola oil, coconut oil, rapeseed oil, tall oil, tall oil fatty acid, palm oil, palm oil fatty acid distillate, jatropha oil, palm kernel oil, sunflower oil, castor oil, camelina oil, archaeal oil, bacterial oil, fungal oil, protozoal oil, algal oil, seaweed oil, oils from halophiles, and mixtures of any two or more thereof. These may be classified as crude, degummed, refined, and RBD (refined, bleached, and deodorized) grade, depending on level of pretreatment and residual phosphorus and metals content. However, any of these grades may be used in the present technology. Animal fats and/or oils as used above includes, but is not limited to, inedible tallow, edible tallow, technical tallow, floatation tallow, lard, poultry fat, poultry oils, fish fat, fish oils, and mixtures of any two or more thereof. Greases may include, but are not limited to, yellow grease, brown grease, waste vegetable oils, restaurant greases, trap grease from municipalities such as water treatment facilities, and spent oils from industrial packaged food operations, and mixtures of any two or more thereof. Exemplary biorenewable feedstocks additionally include fractions of the above feeds which have been prepared by pyrolysis or thermal cracking. Depending on level of pretreatment, such biorenewable feedstocks may contain between about <NUM> wppm and about <NUM>,<NUM> wppm phosphorus, and between about <NUM> wppm and about <NUM>,<NUM> wppm total metals (mainly sodium, potassium, magnesium, calcium, iron, and copper).

Thus, the hydroprocessed biorenewable feedstock of any embodiment herein may include a hydroprocessed product of corn oil, inedible corn oil (also known as distiller's corn oil), babassu oil, carinata oil, soybean oil, canola oil, coconut oil, rapeseed oil, tall oil, tall oil fatty acid, palm oil, palm oil fatty acid distillate, jatropha oil, palm kernel oil, sunflower oil, castor oil, camelina oil, archaeal oil, bacterial oil, fungal oil, protozoal oil, algal oil, seaweed oil, oils from halophiles, rendered fats, inedible tallow, edible tallow, technical tallow, floatation tallow, lard, poultry fat, poultry oils, fish fat, fish oils, frying oils, yellow grease, brown grease, waste vegetable oils, restaurant greases, trap grease from municipalities such as water treatment facilities, and spent oils from industrial packaged food operations, or a mixture of any two or more thereof.

The hydroprocessed biorenewable feedstock may include at least about <NUM> wt% of two or more different carbon number paraffins that fall within the C<NUM> to C<NUM> range. The composition may contain paraffins in the amount of about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, and any range including and/or in between any two of these values or above any one of these values. The paraffins may include C<NUM> and C<NUM> paraffins, such as at least about <NUM>% wt% C<NUM> and C<NUM> paraffins (i.e., the total weight percent combined for C<NUM> and C<NUM> paraffins), at least about <NUM>% wt% C<NUM> and C<NUM> paraffins, or at least about <NUM> wt% C<NUM> and Cis paraffins. The hydroprocessed biorenewable feedstock may include at least about <NUM> wt% even carbon number paraffins. Thus, the hydroprocessed biorenewable feedstock may include even carbon number paraffins in an amount of about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, or any range including and in-between any two of these values.

In any embodiment herein, the hydroprocessed biorenewable feedstock may include iso-paraffins (such as from hydroisomerization) in addition to n-paraffins (such as from hydrotreatment of a biorenewable feedstock. Thus, the paraffins in the hydroprocessed biorenewable feestock may include iso-paraffins and n-paraffins. A ratio of iso-paraffins to n-paraffins may be at about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, and ranges including and/or in between any two of these values or above any one of these values. Where the hydroprocessed biorenewable feedstock includes iso-paraffins, it may be that at least <NUM> wt % of the iso-paraffins in the hydroprocessed biorenewable feedstock are mono-methyl branched paraffins. The mono-methyl branched paraffins may be about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt %, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, and any range including and/or in between any two of these values or above any one of these values. Of the mono-methyl branched iso-paraffins, less than <NUM> wt% are terminal branched (i.e., <NUM>-methyl branched), such as less than <NUM> wt%, less than <NUM> wt%, less than <NUM> wt% , or less than <NUM> wt% of the mono-methyl branched iso-paraffins are terminal branched.

The hydroprocessed biorenewable feedstock typically has about <NUM> wt% or less of cycloparaffins. The hydroprocessed biorenewable feedstock may have cycloparaffins in the amount of about <NUM> wt% about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, or any range including and/or in between any two of these values or below any one of these values.

In any embodiment herein, the hydroprocessed biorenewable feedstock may contains less than about <NUM> wt% aromatics, and may contain from about <NUM> wt% to about <NUM> wt% aromatics. The hydroprocessed biorenewable feedstock may contain aromatics in the amount of about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, and ranges including and between any two of these values or below any one of these values. In some embodiments, the hydroprocessed biorenewable feedstock contains less than about <NUM> wt % total aromatics. In any embodiment herein, the hydroprocessed biorenewable feedstock may contain less than about <NUM> wt% benzene. The hydroprocessed biorenewable feedstock may contain benzene in the amount of about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt% and ranges including and between any two of these values or less than any one of these values. Such low values of benzene may be determined through appropriate analytical techniques, including but not limited to two-dimensional gas chromatography of the composition. In any embodiment herein, the hydroprocessed biorenewable feedstock may have less than about <NUM> wt% of benzene. In any embodiment herein, the hydroprocessed biorenewable feedstock may contain less than about <NUM> wt% polyaromatic hydrocarbons. The hydroprocessed biorenewable feedstock may contain polyaromatic hydrocarbons in the amount of about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt% and ranges including and between any two of these values or less than any one of these values. In any embodiment herein, the hydroprocessed biorenewable feedstock may have less than about <NUM> wt% of benzenepolyaromatic hydrocarbons.

The hydroprocessed biorenewable feedstock of any embodiment herein may have a sulfur content less than about <NUM> wppm. The hydroprocessed biorenewable feedstock may have a sulfur content of about <NUM> wppm, about <NUM> wppm, about <NUM> wppm, about <NUM> wppm, about <NUM> wppm, about <NUM> wppm, about <NUM> wppm, about <NUM> wppm, about <NUM> wppm, about <NUM> wppm, about <NUM> wppm, about <NUM> wppm, about <NUM> wppm, and ranges including and between any two of these values or less than any one of these values.

The hydroprocessed biorenewable feedstock of any embodiment herein, prior to inclusion of any diesel additives such as anti-oxidants, may have less than about <NUM> wt% oxygenates calculated as elemental oxygen (i.e., less than about <NUM> wt% elemental oxygen). The hydroprocessed biorenewable feedstock may have oxygenates in the amount of about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, about <NUM> wt%, and ranges including and between any two of these values or below any one of these values. Such low values of elemental oxygen may be detected through appropriate analytical techniques, including but not limited to Neutron Activation Analysis.

The hydroprocessed biorenewable feedstock of any embodiment herein may include one or more added anti-oxidants. Exemplary anti-oxidants include monophenols (e.g., alkylated hindered phenols such as <NUM>,<NUM>-di-tert-butyl-<NUM>-methylphenol or BHT), bisphenol/thiobisphenols (e.g., <NUM>,<NUM>'-methylene-bis-(<NUM>-methyl-<NUM>-tert-butyl phenol)), polyphenols (e.g., butylated reaction product of p-cresol and dicyclopentadiene), hydroquinones (e.g., <NUM>,<NUM>-di-tert-amyl hydroquinone), phosphites (e.g., tris (p-nonylphenyl) phosphite), and thioesters (e.g.,dilauryl-<NUM>,<NUM>'-thio-dipropionate). The total amount of anti-oxidants added may be from about <NUM> wppm to about <NUM> wppm.

They hydroprocessed biorenewable feedstock typically has a density less than about <NUM>/L at a temperature of <NUM> °F, and may have a density of about <NUM>/L, about <NUM>/L, about <NUM>/L, about <NUM>/L, about <NUM>/L, about <NUM>/L, about <NUM>/L, about <NUM>/L, about <NUM>/L, about <NUM>/L, about <NUM>/L, about <NUM>/L, about <NUM>/L, or any range including and/or in between any two of these values or less than any one of these values.

The synthetic paraffinic diesel (e.g., a hydroprocessed biorenewable feedstock) in any embodiment herein may have a high thermal and oxidative stability (i.e., having a total insoluble content of <NUM>/<NUM> or less according to the ASTM D2274 accelerated oxidative aging method when about <NUM> wppm antioxidant is added to the synthetic paraffinic diesel), low aquatic toxicity and ecotoxicity (i.e., having an LC<NUM> value of <NUM>/L or higher where LC<NUM> is the concentration at which half a population of the organism dies of ingesting the fluid, and is typically the average of <NUM> hour, <NUM> hour, and <NUM> hour exposure tests on Daphia magna, Pimephales promelas, or Rainbow Trout), and a biodegradability greater than about <NUM>% according to ASTM D5864-<NUM>. ASTM D2274 and ASTM D5864-<NUM> are each incorporated herein by reference. ASTM D5864-<NUM> measures how much of a material breaks down into CO<NUM> by microorganisms capable of degrading hydrocarbons over a period of <NUM> days. Organic compounds with low biodegradability (i.e., less than about <NUM>% biodegradability) are said to bioaccumulate. Bioaccumulation tends to magnify the toxic effect of chemicals on the environment.

The amount of biodiesel in the blended fuel composition may be about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, about <NUM> vol. %, or any range including and/or in between any two of these values. The biodiesel of any embodiment herein may conform to ASTM D6751-<NUM>.

The biodiesel may include a fatty acid C<NUM>-C<NUM> alkyl ester produced from an animal fat, animal oil, microbial oil, plant fat, plant oil, vegetable fat, vegetable oil, grease, or a mixture of any two or more thereof. For example, the biodiesel may include a fatty acid C<NUM>-C<NUM> alkyl ester produced from corn oil, inedible corn oil, babassu oil, carinata oil, soybean oil, canola oil, coconut oil, rapeseed oil, tall oil, tall oil fatty acid, palm oil, palm oil fatty acid distillate, jatropha oil, palm kernel oil, sunflower oil, castor oil, camelina oil, archaeal oil, bacterial oil, fungal oil, protozoal oil, algal oil, seaweed oil, oils from halophiles, rendered fats, inedible tallow, edible tallow, technical tallow, floatation tallow, lard, poultry fat, poultry oils, fish fat, fish oils, frying oils, yellow grease, brown grease, waste vegetable oils, restaurant greases, trap grease from municipalities such as water treatment facilities, and spent oils from industrial packaged food operations, or a mixture of any two or more thereof. In any embodiment herein, the biodiesel may include a fatty acid methyl ester, a fatty acid ethyl ester, a fatty acid propyl ester, a fatty acid butyl ester, or a mixture of any two or more thereof.

The biodiesel may or may not include a cold-filtered biodiesel that is not distilled, such as described in <CIT> and <CIT>. Cold-filtered biodiesels include, but are not limited to, filtration with diatomaceous earth, cellulose, bleaching clay, filtration with magnesium sulfate, filtration with silica gel, as well as filtration with other sorbent media. Such filtration is typically conducted at a temperature lower than the temperature at which the biodiesel is stripped of e.g., residual methanol and/or water. Thus, in any embodiment herein, such filtration may occur at a temperature between about <NUM> °F and about <NUM> °F, between about <NUM> °F and about <NUM> °F, or between about <NUM> °F and about <NUM> °F. In any embodiment herein, the biodiesel may include a distilled biodiesel, such as a biodiesel where about <NUM> wt% to about <NUM> wt. % of the initial amount of biodiesel that is distilled is recovered as distillate. Such distillation includes, but is not limited to, atmospheric distillation in a trayed or packed column as well as vacuum distillation in a trayed or packed column. For example, the biodiesel may include a biodiesel distilled in a wiped film evaporator at a temperature of about <NUM> and at a pressure of about <NUM> mbar (a "<NUM> distilled biodiesel"). Where the biodiesel includes both a cold-filtered biodiesel and a distilled biodiesel, it may be a volume ratio of cold-filtered biodiesel to distilled biodiesel is about <NUM>:<NUM> to about <NUM>:<NUM>; thus, the volume ratio may be about <NUM>:<NUM> about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, or any range including and/or in between any two of these values. Note that °C = (°F - <NUM>) × <NUM>/<NUM>.

In any embodiment herein, the biodiesel may include a biodiesel with a Modified Cold Soak Filter Blocking Tendency Test Procedure score ("Modified CSFBT Test Procedure score") of less than about <NUM>. The Modified CSFBT Test Procedure score is described infra. Thus, the biodiesel may have a Modified CSFBT Test Procedure score of about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, or any range including and/or in between any two of these values. In any embodiment herein, the biodiesel may or may not include an additive that reduces a Modified CSFBT Test Procedure score as compared to the biodiesel without such an additive.

In any embodiment herein, the blended fuel composition may include a volume ratio of synthetic paraffinic diesel (e.g., a hydroprocessed biorenewable feedstock) to biodiesel of about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>; about <NUM>:<NUM>; about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, about <NUM>:<NUM>, or any range including and/or in between any two of these values.

The petroleum diesel may be a hydrotreated straight-run diesel, hydrotreated fluidized catalytic cracker light cycle oil, hydrotreated coker light gasoil, hydrocracked FCC heavy cycle oil, and combinations thereof. The petroleum diesel of any embodiment herein may conform to ASTM D975-<NUM> prior to blending with the biodiesel and the synthetic paraffinic diesel; the petroleum diesel of any embodiment herein may include a blendstock that requires upgrading to achieve conventional diesel quality. The petroleum diesel may exhibit a cetane number from about <NUM> to about <NUM>. The petroleum diesel may have an aromatics content of about <NUM> vol. % to about <NUM> vol. Such aromatics may include monocyclic aromatics, polycyclic aromatics, or both. Exemplary polycyclic aromatics include, but are not limited to, diphenyl alkanes (e.g., <NUM>,<NUM>-diphenyl ethane) and polynuclear aromatics (PNA) (e.g., <NUM>-methylnaphthalene). Thus, the petroleum diesel may have a polycyclic aromatics content of about <NUM> vol. % to about <NUM> vol. The petroleum diesel may have an olefin content of about <NUM> vol. % to about <NUM> vol. The petroleum diesel may have a paraffin content of about <NUM> vol. % to about <NUM> vol. The petroleum diesel may exhibit a cloud point from about <NUM> to about -<NUM>. The petroleum diesel may have a sulfur content of about <NUM> ppm or less (such as about <NUM> ppm to about <NUM> ppm). The petroleum diesel may have a nitrogen content of about <NUM> ppm to about <NUM> ppm. The petroleum diesel may exhibit a kinematic viscosity at <NUM> from about <NUM> cSt to about <NUM> cSt. The petroleum diesel may exhibit a flash point from about <NUM> to about <NUM>.

The blended fuel composition in any embodiment herein may have an oxidative stability according to the ASTM D2274 of less than about <NUM>/<NUM>, such as from about <NUM>/<NUM> to about <NUM>/<NUM>, a low aquatic toxicity and ecotoxicity (i.e., having an LC<NUM> value of <NUM>/L or higher where LC<NUM> is the concentration at which half a population of the organism dies of ingesting the fluid, and is typically the average of <NUM> hour, <NUM> hour, and <NUM> hour exposure tests on Daphia magna, Pimephales promelas, or Rainbow Trout), and/or a biodegradability greater than about <NUM>% according to ASTM D5864-<NUM>.

The blended fuel composition in any embodiment herein may include one or more added anti-oxidants, such as the exemplary anti-oxidants discussed previously. The total amount of anti-oxidants added may be from about <NUM> ppm to about <NUM> ppm (w/v of the blended fuel composition in any embodiment herein).

The blended fuel composition of any embodiment herein may include a cloud point from about <NUM> to about -<NUM>, or less. The cloud point of the composition may be about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about - <NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, or any range including and/or in between any two of these values or less than any one of these values.

The blended fuel composition of any embodiment herein may include a Freezing Point as determined according to ASTM D5972 from about <NUM> to about -<NUM>, or less. While Freezing Point according to ASTM D5972 may be considered an unconventional test for diesel fuel, it is a requirement for jet fuel because it provides an estimate of the temperature at which a fuel will first start to form solid particles that could interfere with fuel filter or engine operation. Thus, Freezing Point is a more conservative indication of safe fuel temperature limits than Cloud Point or Cold Filter Plugging Point (CFPP), which therefore makes Freezing Point particularly useful when evaluating non-conventional fuels and fuel blends such as the blended fuel compositions of the present technology. Thus, in any embodiment herein, the blended fuel composition may include a Freezing Point of about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, about -<NUM>, or any range including and/or in between any two of these values or less than any one of these values.

The method may include combining the synthetic paraffinic diesel and the biodiesel to form an initial blend, and subsequently combining the initial blend with the petroleum diesel to produce the blended fuel composition (when petroleum diesel is included in the blended fuel composition). In an alternative when petroleum diesel is included in the blended fuel composition, the method may include combining the synthetic paraffinic diesel and the petroleum diesel to form an initial blend, and subsequently combining the initial blend with the biodiesel to produce the blended fuel composition. In yet another alternative when petroleum diesel is included in the blended fuel composition, the method may include combining the biodiesel and the petroleum diesel to form an initial blend, and subsequently combining the initial blend with the synthetic paraffinic diesel to produce the blended fuel composition.

The method of producing the blended fuel comprises selecting the components such that the resulting blend is more likely to perform successfully in the field. The testing required for proper selection of the blending components necessary for successful performance of these novel fuels include test methods that are not conventional tests for diesel fuels, which could explain why production of these fuel blends has historically been discouraged. Appropriate non-conventional tests for the blended fuel compositions and methods of the present technology may include a Modified CSFBT Test Procedure and/or a Freezing Point test. A low Modified CSFBT Test Procedure score indicates a biodiesel for which biodiesel-SPD blends can be allowed to reach their Freezing Points with minimal concern for filter-plugging precipitation. The higher the Modified CSFBT Test Procedure score, the greater the potential for blends of that biodiesel with SPD to form filter-plugging precipitates above their Freezing Points, particularly for biodiesel-SPD blends with lower and higher biodiesel contents.

Generally speaking, Cold Soak Filter Blocking Tendency tests involve applying a Filter Blocking Tendency (FBT) test procedure to a sample that has experienced an extended period of cold exposure (a "cold soak") prior to the FBT test procedure. Common FBT test methods include ASTM D2068: Standard Test Method for Determining Filter Blocking Tendency and IP <NUM>: Determination of Filter Blocking Tendency. The specific Cold Soak Filter Blocking Tendency test method considered under the present technology is a recently established biodiesel test method that was developed by the Canadian General Standards Board (CGSB) to assess biodiesel for cold weather performance in blends with conventional petroleum diesel: CAN/CGSB-<NUM> No. <NUM>: Cold soak filter blocking tendency of biodiesel (B100), referred to herein as the "CSFBT Test". The CSFBT Test uses a <NUM> vol% blend of the test biodiesel in an isoparaffinic diesel-surrogate solvent to evaluate the potential of the biodiesel to contribute to filter blocking precipitates after blending with hydrocarbon diesel in field use ("hydrocarbon diesel" refering to diesel fuels comprised primarily of hydrocarbons, such as petroleum diesel and synthetic paraffinic diesel). As such, the CSFBT Test provides direct information about how biodiesel will perform in blends with hydrocarbon diesels. The CSFBT Test testing procedure may be adapted to provide useful information about a test biodiesel in blends with hydrocarbon diesel fuels by replacing the prescribed isoparaffinic diesel-surrogate solvent with a diesel fuel of interest, such as a petroleum diesel or a synthetic paraffinic diesel ("SPD"). As described below, the inventors have discovered that the CSFBT Test procedure may also be performed with different blend levels of biodiesel to give surprisingly useful results.

The conventional test for cold weather performance suitability of a biodiesel is commonly referred to as the Cold Soak Filtration test [ASTM D7501: Test Method for Determination of Fuel Filter Blocking Potential of Biodiesel (B100) Blend Stock by Cold Soak Filtration Test (CSFT)]. This test is included in the current ASTM specification for biodiesel [ASTM D6751-<NUM>: Standard Specification for Biodiesel Fuel Blend Stock (B100) for Middle Distillate Fuels] and has been regarded as very useful over the past decade for biodiesel quality assurance. However, there are concerns among some in the industry that the current ASTM biodiesel specification is not adequately stringent to ensure trouble-free operation in the field for blends of biodiesel. The present technology provides a means to addresses this concern directly. Example <NUM> provides data correlating the cold sediment quantities produced in biodiesel-SPD blends with the Cold Soak Filtration test (ASTM D7501) and the <NUM>/<NUM> CSFBT Test (described herein). Sediment formation (aka precipitation) tendency can be evaluated using a cold precipitation test on blends of biodiesel and SPD. For this cold precipitation test of Example <NUM>, neat biodiesel is added to SPD at <NUM> vol% and the blended sample is chilled for <NUM> hours at <NUM>. The sample is then returned to <NUM> and centrifuged in a clear graduated centrifuge tube. Sediment may then be quantified volumetrically using the gradations on the centrifuge tube. These data indicate that the Cold Soak Filtration test does not correlate well with sediment formation in biodiesel-SPD blends, particularly for biodiesels that demonstrate high precipitation tendency. On the other hand, the cold sediment test results correspond much more closely to the results for the CSFBT Test, confirming that the CSFBT Test is generally better able to predict potential filter-plugging precipitation issues in biodiesel-SPD blends than the Cold Soak Filtration test. The present technology provides an effective method for diminishing the likelihood of filter plugging problems that cannot be predicted by the tests provided in the U. biodiesel blendstock specification, ASTM D6751 (The European Union biodiesel specification "EN <NUM>:<NUM>, Liquid petroleum products - Fatty acid methyl esters (FAME) for use in diesel engines and heating applications - Requirements and test methods," which does not include a test to evaluate sediment formation tendency or potential filtration issues, is even less helpful than the ASTM biodiesel specification for predicting precipitation in biodiesel-SPD blends).

Two modifications to the current revision of the standard CGSB CSFBT Test method [CAN/CGSB-<NUM> No. <NUM>-<NUM>: Cold soak filter blocking tendency of biodiesel (B100)] have been applied to provide a "Modified CSFBT Test Procedure" that can effectively evaluate the suitability of a particular biodiesel specifically for successful performance when included in blends with SPD.

The first modification to the CSFBT Test method is a requirement that the suction tube of the apparatus must be configured such that the test sample is drawn from a position within <NUM> of the bottom of the sample container. For example, a Seta Multi Filtration Tester from Stanhope-Seta required the attachment of a length of flexible plastic tubing to the original suction tube to extend the suction point into the appropriate suction zone (i.e. within <NUM> of the bottom of the sample container) for this modification requirement. The tubing had an inner diameter of about <NUM> to match the original suction tube diameter, was about <NUM> long to allow sufficient length to be attached to the original suction tube, and was clamped to the suction tube with a small tubing clamp to ensure a tight seal. This apparatus requirement greatly diminishes the tendency to leave precipitates and/or gelled material in the sample container at the end of the test, which consequently greatly improves the consistency of the test results and allows the collection of actionable information about the suitability of different biodiesels for blending with SPD.

Without this new apparatus requirement (the first modification), the CSFBT Test may be susceptible to providing falsely favorable test results, which are particularly undesirable when blending biodiesel with SPD. Any FBT apparatus that conforms to this suction point position requirement is considered herein to be a Modified FBT Apparatus (or MFA), whether or not the apparatus required a modification to conform. The term <NUM>/<NUM> CSFBT Test will refer herein to the CSFBT Test when performed with an MFA and the <NUM>% biodiesel blend with the isoparaffinic diesel-surrogate solvent prescribed in CAN/CGSB-<NUM> No. <NUM>.

The second modification to the CSFBT Test method arose from recent evaluations of the CSFBT Test method with a MFA that demonstrated that test results for blends with greater than <NUM> vol% biodiesel (a "majority biodiesel blend") in the isoparaffinic diesel-surrogate solvent and in SPD can diverge from test results for the <NUM>/<NUM> CSFBT Test. See, e.g., Example <NUM> herein. Some samples that produced favorable test results in the <NUM>/<NUM> CSFBT Test performed poorly when the CSFBT procedure was applied to samples with more than <NUM>% biodiesel content in the isoparaffinic diesel-surrogate solvent. It has therefore been concluded that a thorough assessment of the suitability of a biodiesel for blending with SPD requires CSFBT results for both majority and minority biodiesel blends. Example <NUM> provides an overview of CSFBT results for the full range of blends for multiple biodiesels. Based on these and other test results, <NUM>% biodiesel was selected as the preferred majority blend level for biodiesel. The term <NUM>/<NUM> CSFBT Test is therefore designated herein to refer to applying the CSFBT procedure with a Modified FBT Apparatus and an <NUM>% blend of biodiesel in the isoparaffinic diesel-surrogate solvent prescribed by the CSFBT Test. Thus, the second modification to the CSFBT Test requires performing both the <NUM>/<NUM> CSFBT Test and the <NUM>/<NUM> CSFBT Test and then assigning the less favorable (i.e., higher) result of the two tests as the Modified CSFBT Test Procedure score.

The Modified CSFBT Test Procedure score may be used to make decisions about suitable storage and usage conditions for biodiesel-SPD blends. Table <NUM> below provides non-limiting guidance for minimum fuel temperature limits for the relevant range of blends of biodiesel and synthetic paraffinic diesel. The recommended fuel temperature limits are relative to fuel Freezing Point values and are assigned according to a combination of the less favorable (i.e., higher) of the <NUM>/<NUM> CSFBT and <NUM>/<NUM> CSFBT scores for the biodiesel component and the biodiesel blend level of the blended fuel. Biodiesel should have <NUM>/<NUM> and <NUM>/<NUM> CSFBT scores less than <NUM> to ensure the blended fuel will perform successfully down to its Freezing Point, and a maximum CSFBT score of <NUM> should be considered the limit for blending minority blends of biodiesel with synthetic paraffinic diesel at any temperature. In general, the better (i.e., lower) the CSFBT score, the lower the acceptable minimum temperature for the blended fuel relative to its Freezing Point. Interestingly, majority blends of certain biodiesels in SPD have been observed to avoid particulate formation at temperatures around the blended fuel Freezing Points better than minority blends, particularly when the biodiesel has an intermediate modified-CSFBT score (i.e., between <NUM> and <NUM>). Also, approximately equal blends of biodiesel and isoparaffinic solvent (i.e., <NUM> - <NUM>% biodiesel) were the least likely to produce an unexpectedly unfavorable CSFBT test score compared to other blends. This supports the surprising observation that approximately equal blends of biodiesel and SPD can produce unexpected Freezing Point reductions relative to the neat Freezing Points of the two blending components.

In addition to the criteria in Table <NUM>, for fuel blends including petroleum diesel or another non-SPD hydrocarbon diesel, such components should also individually have a Freezing Point below the minimum temperature the blended fuel is expected to reach when being dispensed or while in use.

The present technology, thus generally described, will be understood more readily by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present technology.

Experiments were run on various blends using a <NUM> Detroit Diesel Corporation Series <NUM> diesel test engine. The engine was connected to an electrical dynamometer and redundant water brake to ensure constant load. The engine was fully mapped prior to data collection to ensure peak performance. All tests were conducted in hot-start triplicates.

The synthetic paraffinic diesel ("SPD") used in these examples was produced by a two-step hydroprocessing method. In the first step, a blend of various low value fats and oils, including beef tallow and used cooking oil, was hydrotreated at <NUM>-<NUM> °F and <NUM> bar (<NUM> psi) hydrogen partial pressure over a sulfided base metal catalyst system comprising commercially available NiMo catalysts. The catalysts contained <NUM>-<NUM> wt % Ni and <NUM>-<NUM> wt% Mo, impregnated onto shaped alumina extrudates supports. The catalyst size (equivalent diameter) was in the <NUM> to <NUM> range. The hydrotreated product was a mainly C<NUM>-C<NUM> paraffinic composition with a cloud point of <NUM>. The fat/oil blend was pretreated to reduce total metals and phosphorus to less than <NUM> ppm prior to hydrotreating. In the second step, the paraffinic product was stripped of dissolved hydrotreating byproducts (e.g., H<NUM>S, NH<NUM>, water), and hydroisomerized over a bifunctional catalyst (noble metal hydrogenation-dehydrogenation functionality plus silica-alumina acidic support functionality) at <NUM>-<NUM> °F at <NUM> bar (<NUM> psi) H<NUM> partial pressure. The hydroisomerizate was then fractionated to yield a diesel fuel with flash point > <NUM> per ASTM D93-<NUM>, a cloud point of -<NUM> per ASTM D5773-<NUM>, a Freezing Point of -<NUM> per ASTM D5972-<NUM>, and a cetane number > <NUM> per ASTM D613-<NUM>.

The biodiesel used was a blend of fatty acid methyl esters produced by transesterification of soybean oil, used cooking oil, and inedible corn oil with methanol in the presence of a sodium methoxide catalyst. Prior to transesterification the oil feedstocks were acid degummed and free fatty acids were stripped out as necessary to achieve a suitable phosphorus and FFA, respectively, entering the transesterification reaction. Following transesterification and glycerin separation the crude methyl esters were stripped of residual moisture and methanol. The biodiesel used was a combination of two components from this process: <NUM> vol. % that was distilled in a wiped film evaporator at approximately <NUM> and <NUM> mbar, and <NUM> vol. % that was instead cold filtered with diatomaceous earth at <NUM>-<NUM>. The finished biodiesel had a cloud point of -<NUM> per ASTM D5773-<NUM> and a Freezing Point of <NUM> per ASTM D5972-<NUM>.

The petroleum diesel was a reference ULSD fuel characterized by relatively low aromatics and polynuclear aromatics at <NUM> and <NUM> wt. %, respectively. Sulfur content was about <NUM> ppm and cloud point was -<NUM>.

The NOx, PM, CO, and total hydrocarbon emissions were measured on a brake specific basis according to the EPA Federal Test Procedure detailed in <NUM> CFR, Part <NUM>, Subpart N. For each of the blends, the NOx-vs-PM data points were plotted. As observed in <FIG>, there is a surprising dampening of the response curve for biodiesel/SPD blends in the <NUM>/<NUM> to <NUM>/<NUM> range. The PM and NOx emissions are respectively presented in <FIG> and <FIG> for the blends with reference ULSD petroleum fuel.

The experiment in Example <NUM> was also used to measure carbon monoxide emissions for the same biodiesel/SPD blends. The results are plotted in <FIG>, wherein the error bars represent the standard deviation of triplicates.

Carbon monoxide is a measure of incomplete combustion. With its high H-to-C ratio and high cetane, SPD is considered to be a diesel fuel with superior combustion characteristics. Nevertheless, blending with biodiesel resulted in a surprising and unexpected improvement in CO emissions, particularly around the a SPD:biodiesel ratio of about <NUM>:<NUM> to about <NUM>:<NUM> where a significant and unexpected synergistic effect is observed.

Multiple blended fuel compositions according to the present technology will be prepared and subjected to the ASTM D5864 method for measuring biodegradability. As a non-limiting example, the biodegradability of a reference petroleum diesel fuel will be compared with a blended fuel composition of <NUM> vol. % distilled biodiesel, <NUM> vol. % SPD from HDO and HI of a biorenewable feedstock (such as the SPD from Example <NUM>) and <NUM> vol. % the reference petroleum diesel. The blended fuel composition, containing <NUM>/L BHT anti-oxidant, is expected to exhibit greater than <NUM>+% biodegradability over <NUM> days, whereas the reference fuel is expected to exhibit substantially less biodegradability.

The ASTM D2274 oxidative stability test will be performed on both samples, where it is expected that the results will be about the same for both samples (~<NUM>/<NUM>).

Blends of (<NUM>) the biodiesel described in Example <NUM> (herein referred to as "BD") and (<NUM>) the synthetic paraffinic diesel described in Example <NUM> (herein referred to as "SPD") were prepared as outlined in Table <NUM> for evaluation with common fuel system elastomers. The petroleum diesel described in Example <NUM> (herein referred to as "PetD1") was used as a reference for elastomer behavior expected with petroleum diesels.

A nitrile butadiene rubber (NBR) and a fluorinated synthetic rubber (FKM) were selected to represent legacy and modern fuel system elastomers, respectively. Size <NUM> o-rings were purchased from ESP International, an industrial seals distributor, to evaluate the volume change of these elastomers after exposure to the blends listed in Table <NUM>. In accordance with ASTM D471-16a, the elastomers were submersed in each fuel blend and held at <NUM> for <NUM>. O-ring volume was measured after exposure to each fuel blend and compared to a control o-ring which was suspended in air at <NUM> for <NUM>. The change in volume for the o-rings is reported below in Table <NUM>.

The change in volume for each of the elastomers exposed to blends of biodiesel and synthetic paraffinic diesel was compared to that of the elastomers exposed to the petroleum diesel reference (PetD1) to calculate a relative change in volume. The relative change in elastomer volume data is shown in <FIG>. These results show a linear relationship between the relative change in elastomer volume and the percent biodiesel in the blend. For the purposes of this study, a relative change in volume within ± <NUM>% of the reference fuel is considered to be approximately equal to that of the reference diesel. NBR demonstrated elastomer swell approximately equal to that caused by the reference diesel when the diesel fuel blend comprised between <NUM> vol. % and <NUM> vol. % biodiesel. FKM demonstrated elastomer swell approximately equal to that caused by the reference diesel when the diesel fuel blend comprised between <NUM> and <NUM> vol. % biodiesel. These results indicate the surprising benefit of biodiesel when blended with synthetic paraffinic diesel wherein the biodiesel content of the blended fuel composition enables elastomer swell approximately equal to that of petroleum diesel fuels.

Additional elastomer swell studies were conducted to expand upon the work presented in Example <NUM>. A second petroleum diesel ("PetD2") was included in addition to the fuels presented in Example <NUM>, where PetD2 was an ULSD characterized by aromatics and polynuclear aromatics at <NUM> and <NUM> wt%, respectively, as measured according to ASTM D5186-<NUM>. Blends of the biodiesel (BD), the synthetic paraffinic diesel (SPD), and the two petroleum diesels (PetD1 and PetD2) were prepared according to Table <NUM>. Elastomer swell was evaluated for the nitrile butadiene rubber (NBR) as described above in Example <NUM>. Similarly, the methods and procedures used for this study were also identical to those disclosed in Example <NUM>.

This study provides a comparison of the effect of aromatics in hydrocarbon diesel blends on NBR swell to that of biodiesel in blends with synthetic paraffinic diesel. This is best illustrated by comparing the trends shown in <FIG> and <FIG>. In <FIG>, the impact of total aromatics on NBR swell is compared to that of biodiesel, and demonstrates a poor correlation. In contrast, <FIG> shows the impact of polynuclear aromatics on NBR swell with a much better correlation with the impact of biodiesel on NBR swell. This data indicates that polynuclear aromatics, rather than total aromatics, are more strongly correlated with the impact of biodiesel on blends with synthetic paraffinic diesel.

Blends of (<NUM>) the SPD described in Example <NUM> and (<NUM>) the biodiesel described in Example <NUM> were prepared and subjected to the ASTM <NUM>-<NUM> method for measuring Freezing Point. The blended fuels of the present technology demonstrated an improvement over predicted values from the individual components when the components were blended in all proportions, as shown in <FIG>. Furthermore, blends with <NUM> vol. % or less biodiesel exhibited an improvement even over each of the individual components alone. This demonstrates an unexpected improvement in cold flow properties achieved from blends of biodiesel and SPD according to the present technology.

These fuels were also subjected to the ASTM D6371-<NUM> method for measuring the cold filter plugging point (CFPP). Blends of <NUM> vol% biodiesel or greater are shown in <FIG> to offer an improvement over the predicted results from the individual components. Blends between <NUM> and <NUM> vol% biodiesel offered the most surprising benefit. This also represents an unexpected cold flow benefit of blending biodiesel with a synthetic paraffinic diesel according to the present technology.

Three biodiesel samples were prepared wherein each sample was a mixture of fatty acid methyl esters produced by transesterification (with methanol in the presence of a sodium methoxide catalyst) of, respectively, soybean oil (Sample <NUM>), used cooking oil and inedible corn oil (Sample <NUM>), and inedible corn oil and rendered animal fats (Sample <NUM>). Prior to transesterification the oil feedstocks were acid degummed and free fatty acids were stripped out as necessary to achieve a suitable phosphorus and FFA, respectively, entering the reaction. Following transesterification and glycerin separation the crude methyl esters were stripped of residual moisture and methanol. The soybean oil methyl ester sample was cold-filtered with diatomaceous earth at <NUM>-<NUM> and had a cloud point of -<NUM> according to ASTM D5773-<NUM>, where Sample <NUM> is also herein referred to as "undistilled soy". Samples <NUM> and <NUM> were distilled in wiped film evaporators at approximately <NUM> and <NUM> mbar, and had a cloud point of <NUM> and <NUM>, respectively, according to ASTM D5773-<NUM>. Samples <NUM> and (<NUM>) are also herein referred to as Distilled REG-<NUM>/<NUM> (or REG Distilled <NUM>) and Distilled REG-<NUM>/<NUM> (or REG Distilled <NUM>), respectively.

These biodiesel fuels were subjected to the CAN/CGSB-<NUM> No. <NUM> method for measuring cold soak filter blocking tendency (the CSFBT Test). The CSFBT Test is a predictive indicator of the cold weather suitability of biodiesel fuels as blend components with hydrocarbon fuels, including both petroleum diesels and synthetic paraffinic diesels. A "perfect" CSFBT Test score is <NUM>. Samples <NUM> and <NUM> demonstrated a CSFBT Test score of less than <NUM> as shown in <FIG>. This is in contrast to the cold weather suitability indicated by cloud point alone, and illustrates the benefits of distilled biodiesel in cold conditions.

Three biodiesel samples (<NUM>) produced from a blend consisting of predominantly Distiller's Corn Oil, Used Cooking Oil, and Choice White Grease, (<NUM>) produced from a blend consisting of predominantly Used Cooking Oil, Yellow Grease, and Bleachable Fancy Tallow, and (<NUM>) produced from a blend consisting of predominantly Choice White Grease, Used Cooking Oil, Distiller's Corn Oil, and Bleachable Fancy Tallow were blended with a SPD similar to the SPD of Example <NUM> with the exception of a -<NUM> cloud point. Each biodiesel sample was blended with the SPD across the entire range from <NUM> to <NUM> vol% biodiesel in SPD. The three biodiesels met all of the requirements for the ASTM D6751-<NUM> biodiesel specification, including having Cold Soak Filtration test times less than <NUM> seconds.

Biodiesels number <NUM> and <NUM> were distilled and Biodiesel number <NUM> was cold filtered. The test results in <FIG> demonstrate the potential for filter plugging potential to be detected at different points in the blend range. This supports that the Modified CSFBT Test Procedure provides the better analysis of the potential for a biodiesel blend with SPD to contribute to filter plugging issues. The data also support that approximately equal ratios of biodiesel and SPD are less likely, in general, to contribute to filter plugging concerns than minority and majority biodiesel blends.

A cold precipitation test was performed on <NUM> blends of biodiesel and a synthetic paraffinic diesel sample. Each biodiesel sample was blended to a B20 level, chilled for <NUM> hours at <NUM> and then centrifuged after being returned to <NUM>. Sediment was quantified volumetrically using the gradations on the centrifuge tube, and test results were compared to results for the B100 Cold Soak Filtration test (a B100 test) and the CSFBT Test performed using a Modified FBT Apparatus (i.e., the <NUM>/<NUM> CSFBT Test). <FIG> provides averaged results for both the Cold Soak Filtration test and the <NUM>/<NUM> CSFBT Test for each of six levels of precipitate formation, from zero to greater than <NUM> vol%. This data set confirms that the Cold Soak Filtration test is not an adequate predictor of the tendency for filter plugging precipitate formation in blends of biodiesel and SPD and that the <NUM>/<NUM> CSFBT provides more prescriptive results across the full range of potential precipitation quantity.

While certain embodiments have been illustrated and described, it should be understood that changes and modifications can be made therein in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.

The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms "comprising," "including," "containing," etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase "consisting essentially of" will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase "consisting of" excludes any element not specified.

Claim 1:
A method of producing a blended fuel composition comprising combining:
about <NUM> vol.% to about <NUM> vol.% of synthetic paraffinic diesel that is a hydroprocessed biorenewable feedstock comprising a hydrotreated and hydroisomerized biorenewable feedstock;
about <NUM> vol.% to about <NUM> vol.% of a biodiesel that comprises a distilled biodiesel, a biodiesel with a Modified CSFBT Test Procedure score of less than about <NUM>, or both, wherein a volume ratio of synthetic paraffinic diesel to biodiesel in the blended fuel composition is about <NUM>:<NUM> to about <NUM>:<NUM>; and
about <NUM> vol.% to about <NUM> vol.% of a petroleum diesel, provided that at least about <NUM> vol.% biodiesel is included when the blended fuel composition does not include the petroleum diesel;
to produce the blended fuel composition,
wherein the "biodiesel" consists of fatty acid C<NUM>-C<NUM> alkyl esters produced by esterification and/or transesterification reactions between a C1-C4 alkyl alcohol and free fatty acids and/or fatty acid glycerides;
"petroleum diesel" is a diesel fuel produced from crude oil; and
wherein the Modified CSFBT Test Procedure is as defined in the description;
wherein "about" provides an error margin of up to plus or minus <NUM>%.