Process for bio-renewable light paraffinic kerosene and sustainable aviation fuel

Abstract

The present disclosure relates to biofuels, and more specifically to kerosene and aviation turbine fuels derived from biomass. In one aspect, a method for producing light paraffinic kerosene (LPK) is disclosed, comprising the steps of: 14 ~C 24 The method further comprises the steps of: hydrotreating the biorenewable feedstock to obtain a heavy hydrotreater fraction comprising n-paraffins; hydroisomerizing and hydrocrack- ing the heavy hydrotreater fraction with a hydroisomerization catalyst under conditions to obtain a heavy hydroisomerizer fraction and a hydroisomerizer product comprising LPK; and separating the LPK from the hydroisomerizer product. The LPK provided by the method has an actual gums value of 7 mg / 100 mL or less as measured by IP540 air evaporation method and further comprises (a) a weight ratio of isoparaffins to n-paraffins of about 2:1 or greater, or (b) no detectable hydrocarbons having 14 or more carbon atoms as measured by gas chromatography, or (c) a weight ratio of isoparaffins to n-paraffins of about 2:1 or greater and no detectable hydrocarbons having 14 or more carbon atoms as measured by gas chromatography. TIFF2024522114000008.tif83147

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of and priority to U.S. Provisional Patent Application No. 63 / 195,665, filed June 1, 2021, the entirety of which is incorporated herein by reference for all purposes.

[0002] Field This technology relates to synthetic fuels, and more specifically to kerosene and aviation turbine fuels derived from biomass. Summary of the Invention

[0003] overview In one aspect, the present technology provides a method for producing light paraffinic kerosene (LPK), comprising the steps of: 14 ~C 24 To obtain a heavy hydrotreating fraction containing n-paraffins, 14 ~C 24 Hydrotreating a biorenewable feedstock comprising fatty acids, fatty acid esters, and / or fatty acid glycerides; 11 and separating LPK from the hydroisomerization unit product, the LPK having an actual gums value of 7 mg / 100 mL or less as measured by IP540 air evaporation method, and further comprising: (a) a weight ratio of isoparaffins to n-paraffins of about 2:1 or greater, or (b) no detectable hydrocarbons having 14 or more carbon atoms as measured by gas chromatography, or (c) a weight ratio of isoparaffins to n-paraffins of about 2:1 or greater and no detectable hydrocarbons having 14 or more carbon atoms as measured by gas chromatography.

[0004] In a related aspect, C 12 ~C 16A method for producing sustainable aviation fuel (SAF) is provided, comprising blending isoparaffins with LPK produced by any embodiment of the present technology's method for producing LPK. In a further related aspect, the present technology provides SAF produced by the aforementioned method. In one aspect, the present technology provides a method for producing sustainable aviation fuel (SAF) comprising blending isoparaffins with LPK produced by any embodiment of the present technology's method for producing LPK. 12 ~C 16 Provided is an SAF composition comprising isoparaffin and LPK produced by any embodiment of the method of the present technology for producing LPK.

[0005] In one aspect, the present technology provides a method for producing bio-renewable sustainable aviation fuel (SAF), comprising the steps of: 14 ~C 24 To obtain a heavy hydrotreating fraction containing n-paraffins, 14 ~C 24 hydrotreating a biorenewable feedstock comprising fatty acids, fatty acid esters, and / or fatty acid glycerides; 11hydroisomerizing and hydrocracking a heavy hydrotreater fraction with a hydroisomerization catalyst under conditions to yield a hydroisomerization unit product comprising a light paraffinic kerosene (LPK) containing hydrocarbons and having a ratio of isoparaffins to n-paraffins of about 2:1 or greater; and separating a sustainable aviation fuel (SAF) from the hydroisomerization unit product, wherein the SAF comprises at least a portion of the LPK; the LPK has an actual gums value of 7 mg / 100 mL or less as measured in accordance with the IP540 air evaporation method and further comprises (a) a weight ratio of isoparaffins to n-paraffins of about 2:1 or greater, or (b) no detectable hydrocarbons having 14 or more carbon atoms as measured by gas chromatography, or (c) a weight ratio of isoparaffins to n-paraffins of about 2:1 or greater and no detectable hydrocarbons having 14 or more carbon atoms as measured by gas chromatography; and the SAF has an actual gums value of 7 mg / 100 mL or less as measured in accordance with the IP540 air evaporation method. In a related aspect, the present technology provides biorenewable SAF produced according to any embodiment of the method of the present technology for producing biorenewable SAF. [Brief description of the drawings]

[0006] [Figure 1] 1 provides a schematic diagram of an exemplary process for producing LPK, according to an embodiment. [Diagram 2] FIG. 1 is a reproduction of the GC peaks of a "gum" residue that shows no peaks in the high molecular weight region, according to an embodiment. [Diagram 3] FIG. 1 is a reproduction of an overlay chromatogram of seven "gum" residues representing various C14-C22 paraffinic hydrocarbons as discussed in the Examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] Detailed Description Various embodiments are described below. Please note that specific embodiments are not intended as exhaustive descriptions or limitations to the broader aspects discussed herein. An aspect described through a specific embodiment is not necessarily limited to that embodiment and can be implemented in any other embodiment.

[0008] As used herein, "about" will be understood by those skilled in the art and will vary to some extent depending on the context in which it is used. If the use of the term is not clear to those skilled in the art, taking into account the context in which it is used, "about" will be understood to mean up to plus or minus 10% of the particular term, for example, "about 10% by weight" will mean "9% to 11% by weight". When "about" precedes a term, the term will be interpreted as disclosing "about" the term as well as the term not modified by "about", for example, "about 10% by weight" will be understood as "10% by weight" as well as disclosing "9% to 11% by weight".

[0009] The term "and / or" as used in this disclosure means any one of the listed members individually or any two or more of them in combination; for example, "A, B, and / or C" is understood to mean "A, B, C, A and B, A and C, B and C, or A, B, and C."

[0010] As used herein and in the appended claims, singular articles such as "a," "an," and "the" and similar referents in the context of describing elements (particularly in the context of the claims below) should be construed to include both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The recitation of ranges of values ​​herein is intended only to serve as a shorthand method of individually referring to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually set forth herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. Any examples provided herein, or the use of exemplary language (e.g., "such as"), are intended only to better illustrate the embodiments and do not pose a limitation on the scope of the claims unless otherwise indicated. No language in the specification should be construed as indicating that any element not recited in a claim is essential.

[0011] As used herein, "alkyl" groups include straight chain and branched alkyl groups, such as those having 1 to 25 carbon atoms. 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. "C alkyl" groups, such as C1-C4 alkyl, are also used. x ~C y The term "alkyl" will be understood to mean an alkyl group having a carbon number falling within the range of x to y.

[0012] Cycloalkyl groups include monocyclic, bicyclic, or tricyclic alkyl groups having 3 to 12 carbon atoms in the ring. Cycloalkyl groups may be substituted or unsubstituted with one or more alkyl groups. Exemplary monocyclic cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, cycloalkyl groups have 3 to 8 ring members, while in other embodiments the number of ring carbon atoms ranges from 3 to 5, 3 to 6, or 3 to 7. Bi- and tricyclic ring systems include both bridged cycloalkyl groups and fused rings, including, but not limited to, bicyclo[2.1.1]hexane, adamantyl, decalinyl, and the like. Representative substituted cycloalkyl groups may be mono-substituted or substituted more than once, including, but not limited to, 2,2-, 2,3-, 2,4-, 2,5-, or 2,6-disubstituted cyclohexyl groups.

[0013] Alkenyl groups include straight and branched chain alkyl groups as defined above, except that there is at least one double bond between two carbon atoms. Alkenyl groups have 2 to 25 carbon atoms. The alkenyl groups of any embodiment herein may have 1, 2, 3, or 4 carbon-carbon double bonds. Examples of alkenyl groups include, but are not limited to, vinyl, allyl, -CH=CH(CH3), -CH=C(CH3)2, -C(CH3)=CH2, -C(CH3)=CH(CH3), -C(CH2CH3)=CH2, among others.

[0014] Cycloalkenyl groups include cycloalkyl groups as defined above having at least one double bond between two carbon atoms. Cycloalkenyl groups may be unsubstituted or substituted with one or more alkyl groups. Cycloalkenyl groups may have one, two, or three double bonds, but do not include aromatic compounds. Cycloalkenyl groups may have 4 to 14 carbon atoms, 5 to 14 carbon atoms, 5 to 10 carbon atoms, or even 5, 6, 7, or 8 carbon atoms. Examples of cycloalkenyl groups include cyclohexenyl, cyclopentenyl, cyclohexadienyl, cyclobutadienyl, and cyclopentadienyl.

[0015] The term "aromatics" as used herein is synonymous with "aromates" and refers to both cyclic aromatic hydrocarbons and heterocyclic aromatic compounds that do not contain heteroatoms. 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 aromatic materials"). The term also includes aromatic species having alkyl 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 contain 6-14 carbons in the ring portion of the group, and in other embodiments 6-12 or even 6-10 carbon atoms. The phrase includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (eg, indane, tetrahydronaphthene, etc.).

[0016] As used herein, "oxygenate" refers to a carbon-containing compound that contains 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 can also be oxygen-containing variants of the aromatics, cycloparaffins, and paraffins described herein.

[0017] The term "paraffin" as used herein means acyclic branched or unbranched alkanes. Unbranched paraffins are n-paraffins and branched paraffins are iso-paraffins (also called "isoparaffins"). "Cycloparaffins" are cyclic branched or unbranched alkanes.

[0018] The term "paraffinic" as used herein refers to predominantly hydrocarbon chains having regions that are both paraffins and cycloparaffins as defined above, as well as mono- or di-unsaturated (i.e., with one or two double bonds) alkanes, either branched or unbranched.

[0019] Hydroprocessing as used herein describes, without limitation, various types of catalytic reactions that occur in the presence of hydrogen. Examples of the most common hydroprocessing reactions include, without limitation, hydrogenation, hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrotreating (HT), hydrocracking (HC), aromatic saturation or hydrodearomatization (HDA), hydrodeoxygenation (HDO), decarbonation (DCO), hydroisomerization (HI), hydrodewaxing (HDW), hydrodemetallization (HDM), decarbonylation, methanation, and reforming. Depending on the type of catalyst, reactor configuration, reactor conditions, and feed composition, a variety of reactions can be performed, ranging from purely thermal (i.e., no catalyst required) to catalytic. When describing the main functions of a particular hydroprocessing unit, such as an HDO reaction system, it is understood that the HDO reaction is only one of the main reactions taking place, and other reactions may also take place.

[0020] Pyrolysis is understood to mean the thermochemical decomposition of carbonaceous materials in which little or no diatomic oxygen or diatomic hydrogen is present during the thermochemical reaction. Any use of a catalyst in pyrolysis is usually called catalytic cracking, which is encompassed by the term pyrolysis and should not be confused with hydrocracking.

[0021] Hydrotreating (HT) involves the removal of elements of groups 3, 5, 6, and / or 7 of the periodic table from organic compounds. Hydrotreating may also include hydrodemetallization (HDM) reactions. Thus, hydrotreating involves the removal of heteroatoms such as oxygen, nitrogen, sulfur, and any combination of two or more thereof through hydroprocessing. For example, hydrodeoxygenation (HDO) is understood to mean the removal of oxygen by a catalytic hydroprocessing reaction that produces water as a by-product, similarly hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) describe the removal of each of the indicated elements through hydroprocessing.

[0022] Hydrogenation involves the addition of hydrogen to organic molecules without breaking the molecule down to subunits. The addition of hydrogen to a carbon-carbon or carbon-oxygen double bond to produce a single bond are two non-limiting 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) can be subjected to partial hydrogenation to result in a hydrogenated processing product in which the polyunsaturated fatty acids are converted to monounsaturated fatty acids (e.g., oleic acid) without increasing the percentage of undesirable saturated fatty acids (e.g., stearic acid). While hydrogenation is distinct from hydrotreating, hydroisomerization, and hydrocracking, hydrogenation can occur during these other reactions.

[0023] Hydrogenolysis (HC) is understood to mean the cleavage of a carbon-carbon bond of a molecule in the presence of hydrogen to form at least two molecules. Such a reaction usually involves subsequent hydrogenation of the resulting double bond.

[0024] Hydroisomerization (HI) is defined as the skeletal rearrangement of carbon-carbon bonds in the presence of hydrogen to form isomers. Hydrocracking is a competing reaction to most HI catalyzed reactions, and the HC reaction pathway is understood to be included in the use of the term HI as a minor reaction. Hydrodewaxing (HDW) is a specific form of hydrocracking and hydroisomerization designed to improve the low temperature properties of hydrocarbon fluids.

[0025] Composition is C7~C 12 n-paraffin etc. x ~C y When a composition is described as containing "hydrocarbons," this will be understood to mean that the composition contains one or more paraffins having a carbon number in the range of x to y. z +" or "C z The term "C plus" is understood to include compounds having z or more carbon atoms, and similarly, the term "C w -" or "C wThe term "minus" is understood to include compounds having w or fewer carbon atoms.

[0026] The phrase "at least a portion of" with respect to a composition means from about 1% to about 100% by weight of the composition.

[0027] "Diesel fuel" generally refers to fuels having a boiling point in the range of about 150° C. to about 360° C. (the "diesel boiling range").

[0028] "Gasoline" generally refers to a fuel for spark-ignition engines with a boiling point in the range of about 30°C to about 200°C.

[0029] As used herein, "biodiesel" refers to fatty acid C1-C4 alkyl esters produced by esterification and / or transesterification reactions between C1-C4 alkyl alcohols and free fatty acids and / or fatty acid glycerides, such as those described in U.S. Patent Application Publication No. 2016 / 0145536, which is incorporated herein by reference.

[0030] As used herein, "petroleum diesel" refers to diesel fuel produced from crude oil, such as in a crude oil refinery, and includes hydrotreated straight run diesel, hydrotreated fluid catalytic cracked light cycle oil, hydrotreated coker light gas oil, hydrocracked FCC heavy cycle oil, and combinations thereof. Similarly, a "petroleum-derived" compound or composition (e.g., a petroleum-based feedstock) refers to a compound or composition produced directly from crude oil or from components and / or feedstocks ultimately produced from crude oil and non-bio-renewable feedstocks (bio-renewable feedstocks are described in more detail below).

[0031] It should be understood that the "volume percent" or "vol. %" of a component in a composition or the volume ratios of different components in a composition are determined at 60° F. based on the initial volume of each individual component, not the final volume of the components combined.

[0032] Throughout this disclosure, various publications, patents, patent applications, and published patent specifications are referenced with an identified citation, the disclosures of which are incorporated by reference into this disclosure.

[0033] This technology Hydroprocessing of fats, oils, and greases (FOG) for the production of hydrocarbons, including renewable diesel and jet fuel, has been described in the prior art, e.g., U.S. Patents 8,026,401, 7,968,757, and 7,846,323. Renewable jet fuel produced by hydroprocessing of FOG is also called HEFA (hydroprocessed esters and fatty acids), the specifications of which are described in Annex A2 of ASTM D7566-17a. With respect to HEFA, hydroprocessing involves hydrotreating for conversion of fatty acids / esters to hydrocarbons composed primarily of normal paraffins, followed by hydroisomerization / hydrocracking of n-paraffins to a mixture of isoparaffins and n-paraffins.

[0034] ASTM D7566-17a also provides specifications for other synthetic / renewable jet fuels, broadly referred to as sustainable aviation fuels (SAF). These include Fischer-Tropsch hydroprocessed synthetic paraffinic kerosene (Annex A1), hydroprocessed synthetic isoparaffin from fermented sugars (Annex A3), and alcohol-to-jet synthetic paraffinic kerosene (Annex A5). All of these synthetic hydrocarbons are paraffins (alkanes) with virtually no aromatic hydrocarbon content. As a result, SAF produces significantly less particulate matter or soot emissions than conventional jet fuels.

[0035] In a 2018 webinar hosted by the Civil Aviation Alternative Fuels Initiative (CAAFI), the National Jet Fuel Combustion Program (NJFCP) reported on several important hydrocarbon fuel properties that affect lean blowout (LBO). LBO is a measure of the minimum fuel supply to the turbine before the flame goes out. A good fuel will keep a jet turbine engine running, even at low supply (or low air-fuel ratio). The NJFCP team has determined that LBO correlates well with the estimated cetane number (DCN). The best LBO performance has been observed with fuels with DCN values ​​above 55, preferably above 60. DCN is a cetane number estimated by measuring ignition delay using the equipment and methodology described in the ASTM D6890 test method. DCN requires less sample to determine cetane number than the older D613 test method, which relies on actual test diesel engines. Cetane number is an important fuel property for diesel engines, but is not thought to have a direct effect on jet engine performance. Therefore, DCN can be considered as an indirect indicator of fuel chemistry that mitigates LBO.

[0036] The NJFCP also highlighted results showing that lighter paraffinic jet fuels exhibit better ignition characteristics (e.g., easier to ignite at very low temperatures) than conventional, i.e., heavier, jet fuels. In addition to a lower boiling point range, lighter fuels generally have lower viscosities and surface tensions. These properties appear to aid in low-temperature ignition. The NJFCP found a strong correlation between this jet engine performance parameter and the fuels' T10, T20, T50 (i.e., 10%, 20%, and 50% volumetric distillation temperatures in ASTM D86) and low-temperature viscosity values. The most ignitable fuels tested were those that boiled in the range of 150-180C. The final boiling point (FBP) value of 180C is significantly lower than the FBP of 300C specified for SAF in ASTM D7566.

[0037] To comply with the ASTM D7566 specification, jet fuel must have a gum present value of 7 mg / 100 mL or less. Gum present value is a measure of the thermo-oxidative stability of the fuel and may be measured according to the ASTM D381 test method (steam is used as the stripping medium for jet fuel vaporization) or the IP540 test method (air may be used instead of steam). For example, peroxides formed from oxidation reactions may initiate polymerization resulting in a gummy residue. Thus, gum present is an indication of oxidation products (typically polymers) formed within the fuel. The gum present test also indicates heavy contaminants or particulate matter present within the fuel. It is understood in the art that the ASTM D381 and IP540 test methods are similar and therefore would be expected to produce the same results from test to test within the indicated repeatability and reproducibility.

[0038] However, when the inventors of the present technology produced light paraffinic kerosene (LPK) from bio-renewable feedstocks with a boiling range of 180°C or less and a DCN of about 55 or more, the produced LPK generally complied with ASTM D7566 HEFA specifications (including density and flash point), but did not always meet the required real gum specifications. In particular, for LPK, ASTM D381 and IP540 produced different results, and the IP540 air evaporation method generally produced values ​​above 7mg / 100mL. Thus, the inventors found a need to produce LPK from a process that includes bio-renewable feedstocks, and to produce SAFs that include such LPK, to ensure compliance with the real gum specifications tested according to IP540.

[0039] Thus, in one aspect, the present technology provides a method for producing light paraffinic kerosene (LPK), comprising: 14 ~C 24 To obtain a heavy hydrotreating fraction containing n-paraffins, 14 ~C 24Hydrotreating a biorenewable feedstock comprising fatty acids, fatty acid esters, and / or fatty acid glycerides; 11 and separating LPK from the hydroisomerization unit product, the LPK having an actual gums value of 7 mg / 100 mL or less as measured by IP540 air evaporation method, and further comprising (a) a weight ratio of isoparaffins to n-paraffins of about 2:1 or greater, or (b) no detectable hydrocarbons having 14 or more carbon atoms as measured by gas chromatography, or (c) a weight ratio of isoparaffins to n-paraffins of about 2:1 or greater and no detectable hydrocarbons having 14 or more carbon atoms as measured by gas chromatography.

[0040] In a related aspect, C 12 ~C 16 A method for producing sustainable aviation fuel (SAF) is provided, comprising blending isoparaffins with LPK produced by any embodiment of the present technology's method for producing LPK. In a further related aspect, the present technology provides SAF produced by the aforementioned method. In one aspect, the present technology provides a method for producing sustainable aviation fuel (SAF) comprising blending isoparaffins with LPK produced by any embodiment of the present technology's method for producing LPK. 12 ~C 16 Provided is an SAF composition comprising isoparaffin and LPK produced by any embodiment of the method of the present technology for producing LPK.

[0041] In one aspect, the present technology provides a method for producing bio-renewable sustainable aviation fuel (SAF), comprising the steps of: 14 ~C 24 To obtain a heavy hydrotreating fraction containing n-paraffins, 14 ~C 24 hydrotreating a biorenewable feedstock comprising fatty acids, fatty acid esters, and / or fatty acid glycerides; 11hydroisomerizing and hydrocracking a heavy hydrotreater fraction with a hydroisomerization catalyst under conditions to yield a hydroisomerization unit product comprising a light paraffinic kerosene (LPK) containing hydrocarbons and having a ratio of isoparaffins to n-paraffins of about 2:1 or greater; and separating a sustainable aviation fuel (SAF) from the hydroisomerization unit product, wherein the SAF comprises at least a portion of the LPK; the LPK has an actual gums value of 7 mg / 100 mL or less as measured in accordance with the IP540 air evaporation method and further comprises (a) a weight ratio of isoparaffins to n-paraffins of about 2:1 or greater, or (b) no detectable hydrocarbons having 14 or more carbon atoms as measured by gas chromatography, or (c) a weight ratio of isoparaffins to n-paraffins of about 2:1 or greater and no detectable hydrocarbons having 14 or more carbon atoms as measured by gas chromatography; and the SAF has an actual gums value of 7 mg / 100 mL or less as measured in accordance with the IP540 air evaporation method. In a related aspect, the present technology provides biorenewable SAF produced according to any embodiment of the method of the present technology for producing biorenewable SAF.

[0042] The biorenewable feedstock of any aspect and any embodiment disclosed herein includes free fatty acids, fatty acid esters (including mono-, di-, and triglycerides), or any two or more combinations thereof. For example, the free fatty acids may include free fatty acids obtained by stripping free fatty acids from a triglyceride transesterification feedstock. The biorenewable feedstock may include animal fats, animal oils, plant fats, plant oils, vegetable fats, vegetable oils, greases, or any two or more mixtures thereof. The fatty acid esters may include fatty acid methyl esters, fatty acid ethyl esters, fatty acid propyl esters, fatty acid butyl esters, or any two or more mixtures thereof. The biorenewable feedstock may include fatty acid distillates from vegetable oil deodorizers. Depending on the degree of pretreatment, fats, oils, and greases may contain from about 1 wppm to about 1,000 wppm phosphorus, and from about 1 wppm to about 500 wppm of total metals (primarily sodium, potassium, magnesium, calcium, iron, and copper). Plant and / or vegetable oils and / or microbial oils include, but are not limited to, corn oil, distilled corn oil, non-edible corn oil, babassu oil, carinata oil, soybean oil, canola oil, coconut oil, rapeseed oil, tall oil, tall oil fatty acid, palm oil, palm fatty acid distillate, palm sludge oil, jatropha oil, palm kernel oil, sunflower oil, castor oil, camelina oil, archaeal oil, bacterial oil, fungal oil, protozoan oil, algae oil, seaweed oil, halophilic bacteria derived oil, shepherd's purse derived oil (e.g., seed oil), other flowering plant derived oil (e.g., seed oil), and mixtures of any two or more thereof. These can be classified into crude, degummed, and RBD (refined, bleached, and deodorized) grades depending on the degree of pretreatment and the residual phosphorus and metal content. However, any of these grades can be used in the present technology.Animal fats and / or oils as used above include, but are not limited to, inedible tallow, edible tallow, industrial tallow, floating tallow, bleachable fancy tallow, lard, industrial lard, choice white grease, poultry fat, poultry oil, fish fat, fish oil, and mixtures of any two or more thereof. Grease includes, but is not limited to, yellow grease, brown grease, waste vegetable oil, restaurant grease, trap grease from municipalities such as water treatment plants, used oil from industrial packaged food operations, and mixtures of any two or more thereof. The biorenewable feedstock may include animal fats, poultry oils, soybean oils, canola oils, carinata oils, rapeseed oils, palm oils, jatropha oils, castor oils, camelina oils, seaweed oils, halophilic oils, rendered fats, restaurant greases, brown greases, yellow greases, waste industrial frying oils, fish oils, tall oils, tall oil fatty acids, or mixtures of any two or more thereof. The biorenewable feedstock may include animal fats, restaurant greases, brown greases, yellow greases, waste industrial frying oils, or mixtures of any two or more thereof. In any embodiment herein, the biorenewable feedstock may be a branched C8, C. 12 and / or C. 16 Olefins (e.g., formed by oligomerization of bioisobutylene), branched C 15 It may include olefins (eg, produced via fermentation of sugars).

[0043] As described in the previous paragraph, the biorenewable feedstock may be pretreated. For example, in any aspect and embodiment, the biorenewable feedstock may be pretreated to remove phosphorus and metal contaminants to less than 10 wppm total, as described in U.S. Pat. No. 9,404,064. Such pretreatment includes, but is not limited to, degumming, neutralization, bleaching, deodorization, or any two or more combinations thereof. One type of degumming is acid degumming, which involves contacting the fat / oil with a concentrated aqueous acidic solution. Exemplary acids are phosphoric acid, citric acid, and maleic acid. This pretreatment step removes metals such as calcium and magnesium in addition to phosphorus. Neutralization is typically performed by adding caustic (referring to any base, such as aqueous NaOH) to the acid-degummed fats and oils. Processing equipment used for acid degumming and / or neutralization may include high shear mixers and disc stack centrifuges. Bleaching typically involves contacting the degummed fat / oil with an adsorbent clay and filtering the spent clay through a pressure leaf filter. It has been reported that using synthetic silica instead of clay improves adsorption. The bleaching step removes chlorophyll as well as most residual metals and phosphorus. Any soaps that may have formed during the caustic neutralization step (i.e., by reaction with free fatty acids) are also removed during the bleaching step. The aforementioned treatment processes are known in the art and are described in the patent literature, including, but not limited to, U.S. Patents 4,049,686, 4,698,185, 4,734,226, and 5,239,096.

[0044] Bleaching, as used herein, is a common filtration process for the processing of glyceride oils. Many types of processing configurations and filtration media are known to those skilled in the art, such as diatomaceous earth, perlite, silica hydrogel, cellulose media, clay, bleaching earth, carbon, bauxite, silica aluminate, natural fibers and flakes, synthetic fibers and mixtures thereof. Bleaching may also be referred to by other names, such as clay processing, which is a common industrial process for petroleum, synthetic and biological feeds and products.

[0045] Further types of filtration may be performed before and / or after and / or instead of degumming and / or bleaching to remove suspended solids from the biorenewable feedstock. In some embodiments, rotoscreen filtration is used to remove solids greater than about 1 mm from the biorenewable feedstock. Rotoscreen filtration is a mechanically vibrating wire mesh screen with openings of about 1 mm or greater that continuously removes a large amount of solids. Other wire mesh filters of about 1 mm or greater housed in various types of filters, including self-cleaning and backwashing filters, may also be employed, so long as they provide a large amount of separation of solids greater than 1 mm, e.g., from about 1 mm to about 20 mm. In embodiments where clay-coated pressure leaf filter bleaching is not used, cartridge or bag filters of about 0.1 to about 100 micron grade may be used to ensure that only solubilized and / or finely suspended (e.g., colloidal phase) admixtures are present in the feed stream. Filtration is typically performed at a temperature high enough to ensure that the feed stream is a liquid with a viscosity of about 0.1 to 100 cP. This will generally be in the temperature range of 20° C. to 90° C. (about 70° F. to about 195° F.).

[0046] In any embodiment disclosed herein, the free fatty acids of the mixture may include fatty acids generated from hydrolysis of fatty acid esters of fats, oils, and / or greases. In any embodiment disclosed herein, the free fatty acids may include fatty acids from tall oil and / or generated from hydrolysis of tall oil esters. In any embodiment disclosed herein, the free fatty acids may include fatty acids from palm fatty acid distillates. In any embodiment disclosed herein, the free fatty acids may include fatty acids distilled from fats, oils, and / or greases, such as those containing at least about 10 wt% free fatty acids. In any embodiment disclosed herein, the free fatty acids may include fatty acids distilled from palm sludge oil and / or used cooking oil. In any embodiment disclosed herein, the free fatty acids may include oleic acid, linoleic acid, stearic acid, palmitic acid, or any combination of two or more thereof. In any of the aspects disclosed herein, the free fatty acids can include soap forms of the free fatty acids (e.g., sodium soaps and / or potassium soaps), and in such aspects including soap forms, the free fatty acids have an alkalinity of at least 200 mg / kg, at least 500 mg / kg, or at least 1000 mg / kg.

[0047] In any embodiment disclosed herein, the biorenewable feedstock may comprise about 5 wt% to about 90 wt% free fatty acids (FFA). Thus, in any aspect and embodiment disclosed herein, the biorenewable feedstock may comprise free fatty acids in an amount of about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, or any range inclusive of and / or between any two of these values.

[0048] Suitable hydrotreating catalysts for hydrotreating biorenewable feedstocks of any aspect or embodiment of the present technology include Co, Mo, Ni, Pt, Pd, Ru, W, NiMo, NiW, CoMo, or any combination of two or more thereof. Hydrotreating catalysts can include NiMo, NiW, CoMo, and any combination of two or more thereof. Supports for hydrotreating catalysts include alumina, and alumina with silicon oxide and / or phosphorus oxide. It should be noted that a person skilled in the art can select a suitable hydrotreating catalyst that will produce a particular result and still be consistent with the present technology.

[0049] In any aspect or embodiment of the present technology, the step of hydrotreating the biorenewable feedstock may include contacting a feedstream (a feedstream comprising a biorenewable feedstock) with a hydrotreating catalyst in a fixed bed hydrotreating reactor to produce a heavy hydrotreater fraction. In any aspect or embodiment herein, the feedstream may further comprise a petroleum-based feedstock or may be free of a petroleum-based feedstock. The fixed bed hydrotreating reactor may have a temperature of less than about 750°F (400°C) and a pressure of about 200 psig (13.8 barg) to about 4,000 psig (275 barg). The fixed bed hydrotreating reactor may be a continuous fixed bed hydrotreating reactor. In any aspect or embodiment, the feedstream further comprises a diluent. The diluent may include recycled hydroprocessing products (e.g., at least a portion of a heavy hydrotreater fraction), a distilled fraction of a heavy hydrotreater fraction, a petroleum-based hydrocarbon fluid, a synthetic hydrocarbon product stream from a Fischer-Tropsch process, a hydrocarbon product stream produced by fermentation of sugars (e.g., farnesene), natural hydrocarbons such as limonene and terpenes, natural gas liquids, or a mixture of any two or more thereof. The volume ratio of diluent to bio-renewable feedstock can be from about 0.5:1 to about 20:1, and thus the volume ratio of diluent to bio-renewable feedstock can be about 1:1, about 2:1, about 3:1, about 4:1, about 5:1, about 6:1, about 7:1, about 8:1, about 9:1, about 10:1, about 11:1, about 12:1, about 13:1, about 14:1, about 15:1, about 16:1, about 17:1, about 18:1, about 19:1, about 20:1, or any range inclusive of and / or between any two of these values.

[0050] In any aspect or embodiment of the present technology involving a fixed bed reactor in hydroprocessing a biorenewable feedstock, the fixed bed reactor may be at a temperature in the range of about 480° F. (250° C.) to about 750° F. (400° C.). The fixed bed reactor may be operated at a temperature of about 450° F. (230° C.), about 500° F. (260° C.), about 540° F. (280° C.), about 570° F. (300° C.), about 610° F. (320° C.), about 645° F. (340° C.), about 680° F. (360° C.), about 720° F. (380° C.), about 750° F. (400° C.), or any range inclusive of and / or between any two of these values. Weighted average bed temperature (WABT) is commonly used in fixed-bed adiabatic reactors to represent the "average" temperature of the reactor taking into account the non-linear temperature profile between the inlet and outlet of the reactor. In the formula above, T i in and T i out and WABT of a reactor system having N different catalyst beds are calculated by multiplying the WABT of each bed (WABT i ) and the weight of catalyst in each bed (Wc i ) can be used to calculate it.

[0051] Although most biorenewable feedstocks have traces of organic sulfur, in order to maintain active metal sulfide functionality of the hydroprocessing catalyst, in any aspect or embodiment of the present technology, the biorenewable feedstock and / or feedstream may be supplemented with sulfur compounds that decompose to hydrogen sulfide when heated and / or contacted with the catalyst. The sulfur compounds may include methyl mercaptan, ethyl mercaptan, n-butyl mercaptan, dimethyl sulfide (DMS), dimethyl disulfide (DMDS), dimethyl sulfoxide (DMSO), diethyl sulfide, di-tert-butyl polysulfide (TBPS), dioctyl polysulfide, di-tert-nonyl polysulfide (TNPS), carbon disulfide, thiophene, or a mixture of any two or more thereof. The concentration of sulfur compounds (e.g., in the feedstream) may be from about 50 ppm to about 2,000 ppm by weight of sulfur. In any aspect or embodiment of the present technology, the step of hydrotreating the biorenewable feedstock may include hydrotreating the biorenewable feedstock with a petroleum-based feedstock - for example, the feedstream may include a petroleum-based feedstock in addition to the biorenewable feedstock - where the petroleum-based feedstock provides sulfur either in combination with or in the absence of the sulfur compounds described above.

[0052] In any aspect or embodiment of the present technology, the step of hydrotreating the biorenewable feedstock can include a pressure of about 200 psig (about 13.8 barg) to about 4,000 psig (e.g., hydrotreating in a fixed bed hydrotreating reactor at a pressure of about 200 psig (about 13.8 barg) to about 4,000 psig (about 275 barg). The pressure may be about 300 psig (21 barg), about 400 psig (28 barg), about 500 psig (34 barg), about 600 psig (41 barg), about 700 psig (48 barg), about 800 psig (55 barg), about 900 psig (62 barg), about 1,000 psig (69 barg), about 1,100 psig (76 barg), about 1,200 psig (83 barg), about 1,300 psig (90 barg), about 1,400 psig (97 barg), about 1,500 psig (103 barg), about 1,600 psig (110 barg), about 1,700 psig (117 barg), about 1,800 psig (124 barg). ), about 1,900 psig (131 barg), about 2,000 psig (138 barg), about 2,200 psig (152 barg), about 2,400 psig (165 barg), about 2,600 psig (179 barg), about 2,800 psig (193 barg), about 3,000 psig (207 barg), about 3,200 psig (221 barg), about 3,400 psig (234 barg), about 3,600 psig (248 barg), about 3,800 psig (262 barg), about 3,900 psig (269 barg), or any range including and / or between any two of these values. For example, the pressure can be from about 1,000 psig (69 barg) to about 2,000 psig (138 barg).

[0053] In any aspect or embodiment of the present technology that includes a fixed bed reactor for hydrotreating a biorenewable feedstock, the liquid hourly space velocity (LHSV) of the biorenewable feedstock through the fixed bed hydrotreating reactor is about 0.2 h -1 ~about 10.0h -1 Therefore, the LHSV is about 0.3h -1 , about 0.4h-1 、about 0.5 h -1 、about 0.6 h -1 、about 0.7 h -1 、about 0.8 h -1 、about 0.9 h -1 、about 1.0 h -1 、about 1.2 h -1 、about 1.4 h -1 、about 1.6 h -1 、about 1.8 h -1 、about 2.0 h -1 、about 2.2 h -1 、about 2.4 h -1 、about 2.6 h -1 、about 2.8 h -1 、about 3.0 h -1 、about 3.2 h -1 、about 3.4 h -1 、about 3.6 h -1 、about 3.8 h -1 、about 4.0 h -1 、about 4.2 h -1 、about 4.4 h -1 、about 4.6 h -1 、about 4.8 h -1 、about 5.0 h -1 、about 5.2 h -1 、about 5.4 h -1 、about 5.6 h -1 、about 5.8 h -1 、about 6.0 h -1 、about 6.2 h -1 、about 6.4 h -1 、about 6.6 h -1 、about 6.8 h -1 、about 7.0 h -1 、about 7.2 h -1 、about 7.4 h -1 、about 7.6 h -1 、about 7.8 h -1 、about 8.0 h -1 、about 8.2 h -1 、about 8.4 h -1 、about 8.6 h -1 、about 8.8 h -1 、about 9.0 h -1 、about 9.2 h -1 、about 9.4 h -1 、about 9.6 h -1 、about 9.8 h -1or any range including and / or between any two of these values.

[0054] In any aspect or embodiment of the present technology, hydrotreating the biorenewable feedstock can include mixing the biorenewable feedstock (and / or a feedstream containing the biorenewable feedstock) with a hydrogen-rich process gas. The ratio of hydrogen-rich process gas to biorenewable feedstock can range from about 2,000 to about 10,000 SCF / bbl (in normal liters of gas per liter of liquid (Nl / l), about 355 Nl / l to about 1780 Nl / l). The ratio of hydrogen-rich process gas to biorenewable feedstock is approximately 2,500 SCF / bbl (approx. 445 Nl / l), approximately 3,000 SCF / bbl (approx. 535 Nl / l), approximately 3,500 SCF / bbl (approx. 625 Nl / l), approximately 4,000 SCF / bbl (approx. 710 Nl / l), approximately 4,500 SCF / bbl (approx. 800 Nl / l), approximately 5,000 SCF / bbl (approx. 890 Nl / l), approximately 5,500 SCF / bbl (approx. 980 Nl / l), approximately 6,000 SCF / bbl (approx. 1070 Nl / l), approximately 6,500 SCF / bbl (approx. 1100 Nl / l), approximately 7,000 SCF / bbl (approx. 1200 Nl / l), approximately 8,000 SCF / bbl (approx. 1300 Nl / l), approximately 9,000 SCF / bbl (approx. 1400 Nl / l), approximately 15,000 SCF / bbl (approx. 1600 Nl / l), approximately 17,000 SCF / bbl (approx. 1800 Nl / l), approximately 19,000 SCF / bbl (approx. 1900 Nl / l), approximately 20,000 SCF / bbl (approx. 2100 Nl / l), approximately 22,000 SCF / bbl (approx. 2300 Nl / l), approximately 24,000 SCF / bbl (approx. 2500 Nl / l), approximately 25,000 SCF / bbl (approx. 2600 Nl / l), approximately 26,000 SCF / bbl (approx. 270 SCF / bbl (about 1160 Nl / l), about 7,000 SCF / bbl (about 1250 Nl / l), about 7,500 SCF / bbl (about 1335 Nl / l), about 8,000 SCF / bbl (about 1425 Nl / l), about 8,500 SCF / bbl (about 1515 Nl / l), about 9,000 SCF / bbl (about 1600 Nl / l), about 9,500 SCF / bbl (about 1690 Nl / l), or any range including and / or between any two of these values. The hydrogen-rich process gas may contain about 70 mol% to about 100 mol% hydrogen. In terms of mass ratio, the ratio of the feed stream to the hydrogen-rich process gas is about 5:1 to 25:1. The ratio of the feed stream to the hydrogen-rich treat gas can be about 6:1, about 7:1, about 8:1, about 9:1, about 10:1, about 11:1, about 12:1, about 13:1, about 14:1, about 15:1, about 16:1, about 17:1, about 18:1, about 19:1, about 20:1, about 22:1, about 23:1, about 24:1,), or any range including and / or between any two of these values.

[0055] As discussed above, each aspect of the process includes hydroisomerizing and hydrocracking a heavy hydrotreater fraction with a hydroisomerization catalyst under conditions to obtain a hydroisomerized product, the hydroisomerization product comprising a heavy hydroisomerization fraction and LPK, where the ratio of isoparaffins to n-paraffins in the LPK (in any aspect or embodiment) can be about 2:1 or greater. In any aspect or embodiment disclosed herein, the hydroisomerization catalyst can be a bifunctional catalyst having hydrogenation-dehydrogenation activity from Group VIB and / or Group VIII metals 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). In any aspect or embodiment disclosed herein, the hydroisomerization catalyst may comprise platinum, palladium, or a combination thereof on a crystalline silica-alumina support with zeolite. In any aspect or embodiment disclosed herein, the hydroisomerization catalyst may comprise tungsten (particularly useful for, e.g., "sour service", when sulfur species are present in the heavy hydrotreater fraction). In any aspect or embodiment disclosed herein, the hydroisomerization catalyst may comprise Pt / Pd-on-ASA and / or Pt-on-SAPO-11. In any aspect or embodiment, the conditions may include a temperature of about 200° C. to about 500° C.; thus, the hydroisomerization and hydrocracking steps may be carried out at a temperature of about 220° C., about 240° C., about 260° C., about 280° C., about 300° C., about 304° C., about 320° C., about 330° C., about 335° C., about 340° C., about 350° C., about 360° C., about 370° C., about 380° C., about 390° C., about 400° C., about 420° C., about 440° C., about 460° C., about 480° C., or any range inclusive and / or between any two of these values. Temperatures of about 580° F. (about 304° C.) to about 750° F. (about 400° C.) are particularly useful to ensure that the LPK has an isoparaffin to n-paraffin ratio of about 2:1 or greater.In any aspect or embodiment, the conditions can include a pressure of about 250 psig to about 3,000 psig; thus, the pressure can be about 250 psig, about 300 psig, about 400 psig, about 500 psig, about 600 psig, about 700 psig, about 800 psig, about 900 psig, about 1,000 psig, about 1,100 psig, about 1,200 psig, about 1,300 psig, about 1,400 psig, about 1,500 psig, about 1,600 psig, about 1,700 psig, about 1,800 psig, about 1,900 psig, about 2,100 psig, about 2,200 psig, about 2,300 psig, about 2,400 psig, about 2,500 psig, about 2,600 psig, about 2,700 psig, about 2,800 psig, about 2,900 psig, about 3,000 psig, about 3,100 psig, about 3,200 psig, about 3,300 psig, about 3,400 psig, about 3,500 psig, about 3,600 psig, about 3,700 psig, about 3,800 psig, about 3,900 psig, about 4,0 ... The pressure may be about 700 psig, about 1,800 psig, about 1,900 psig, about 2,000 psig, 2,100 psig, about 2,200 psig, about 2,300 psig, 2,400 psig, about 2,500 psig, about 2,600 psig, about 2,700 psig, about 2,800 psig, about 2,900 psig, about 3,000 psig, or any range including and / or between any two of these values.

[0056] In any aspect or embodiment of the present technology, the step of hydroisomerizing and hydrocracking the heavy hydrotreater fraction may include mixing the heavy hydrotreater fraction (and / or a feedstream comprising the heavy hydrotreater fraction) with a hydrogen-rich treat gas. The ratio of hydrogen-rich treat gas to heavy hydrotreater fraction can range from about 1,000 to about 5,000 SCF / bbl; thus, the ratio of hydrogen-rich treat gas to heavy hydrotreater fraction can be about 1,000 SCF / bbl, about 1,500 SCF / bbl, about 2,000 SCF / bbl, about 2,500 SCF / bbl, about 3,000 SCF / bbl, about 3,500 SCF / bbl, about 4,000 SCF / bbl, about 4,500 SCF / bbl, about 5,000 SCF / bbl, or any range inclusive of and / or between any two of these values. The hydrogen-rich treat gas can contain from about 70 mol% to about 100 mol% hydrogen.

[0057] In any aspect or embodiment, the hydroisomerization and hydrocracking steps may be carried out in a continuous fixed bed reactor (e.g., both hydroisomerization and hydrocracking occur in a single fixed bed reactor). When carried out in a continuous fixed bed reactor, the liquid hourly space velocity (LHSV) of the heavy hydrotreater fraction passing through the continuous fixed bed reactor is about 0.1 h -1 ~about 4.0h -1 Therefore, the LHSV is about 0.1h -1 , about 0.2h -1 , about 0.3h -1 , about 0.4h -1 , about 0.5h -1 , about 0.6h -1 , about 0.7h -1 , about 0.8h -1 , about 0.9h -1 , about 1.0h -1 , about 1.2h -1 , about 1.4h -1 , about 1.6h -1 , about 1.8h -1 , about 2.0h -1 , about 2.2h -1 , about 2.4h -1 , about 2.6h -1 , about 2.8h -1 , about 3.0h -1 , about 3.2h -1 , about 3.4h -1 , about 3.6h -1 , about 3.8h -1 , about 4.0h -1 or any range including and / or between any two of these values.

[0058] In any aspect or embodiment, the step of separating LPK from the hydroisomerization unit product and / or the step of separating SAF from the hydroisomerization unit product may include fractionation. The fractionation of any aspect or embodiment may be carried out in a distillation column with a reboiler or stripping steam at the bottom of the column and a condenser at the top. In such an embodiment, the reboiler or stripping steam provides thermal energy to vaporize the heavier fraction of the hydrocarbons while the condenser cools the lighter hydrocarbon gases and returns the hydrocarbon liquid to the top of the column. The distillation column includes multiple mechanisms (e.g., plates, ridges, and / or packing beds) for countercurrent contact of the ascending gases with the descending liquids. The temperature profile of the column from the bottom to the top depends on the composition of the hydrocarbon feed and the column pressure. In some embodiments, the column pressure ranges from about 200 psig (about 13.8 barg) to about -14.5 psig (about -1 barg). The column includes one or more feed nozzles. A portion of the condenser liquid (typically 10-90 vol%) is withdrawn as an overhead product and the remainder is refluxed to the column. Some embodiments utilize multiple withdrawal nozzles to fractionate the feed into multiple cuts in the same column, while other embodiments achieve this separation using multiple columns in series, each of which separates the feed into an overhead and bottoms fraction. In any aspect or embodiment, the separating step may be carried out such that the LPK contains no detectable hydrocarbons having 14 or more carbon atoms as determined by gas chromatography.

[0059] In any aspect or embodiment where the LPK does not contain detectable hydrocarbons having 14 or more carbon atoms as measured by gas chromatography, the LPK may have a weight ratio of isoparaffins to n-paraffins of about 1:1 to about 5:1 (or more); thus, the LPK of any aspect or embodiment of the present technology (wherein the LPK does not contain detectable hydrocarbons having 14 or more carbon atoms as measured by gas chromatography) may have a weight ratio of isoparaffins to n-paraffins of about 1:1, about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, or more. , about 1.5:1, about 1.6:1, about 1.7:1, about 1.8:1, about 1.9:1, about 2.0:1, about 2.1:1, about 2.2:1, about 2.3:1, about 2.4:1, about 2.5:1, about 2.6:1, about 2.7:1, about 2.8:1, about 2.9:1, about 3.0:1, about 3.2:1, about 3.4:1, about 3.6:1, about 3.8:1, about 4.0:1, about 4.2:1, about 4.4:1, about 4.6:1, about 4.8:1, about 5.0:1, or any range including and / or between any two of these values.

[0060] In any aspect or embodiment in which the LPK comprises detectable hydrocarbons having 14 or more carbon atoms as determined by gas chromatography, the LPK may have a weight ratio of isoparaffins to n-paraffins of about 2:1 to about 5:1 (or more), e.g., about 2.0:1, about 2.1:1, about 2.2:1, about 2.3:1, about 2.4:1, about 2.5:1, about 2.6:1, about 2.7:1, about 2.8:1, about 2.9:1, about 3.0:1, about 3.2:1, about 3.4:1, about 3.6:1, about 3.8:1, about 4.0:1, about 4.2:1, about 4.4:1, about 4.6:1, about 4.8:1, about 5.0:1, or any range inclusive of and / or between any two of these values. As discussed above, such isoparaffin to n-paraffin weight ratios are effected by the hydroisomerization and hydrocracking conditions of the heavy hydrotreater fraction.

[0061] In any aspect or embodiment of the present technology, the LPK may have a flash point of about 38° C. or greater, e.g., about 38° C. to about 42° C.; thus, the flash point of the LPK may be about 38° C. (about 100° F.), about 39° C. (about 102° F.), about 40° C. (about 104° F.), about 41° C. (about 106° F.), about 42° C. (about 108° F.), or any range inclusive of and / or between any two of these values. In any aspect or embodiment of the present technology, the LPK may have a cetane number (i.e., predicted cetane number; "DCN") of about 55 or greater, e.g., about 55, about 60, about 65, about 70, about 75, about 80, or any range inclusive of and / or between any two of these values. In any aspect or embodiment of the present technology, the LPK may have a freezing point (determined according to ASTM D5972) of less than about -40°C; thus, the LPK may have a freezing point determined according to ASTM D5972 of less than about -40°C, about -42°C, about -44°C, about -46°C, about -48°C, about -50°C, about -52°C, about -54°C, about -56°C, about -58°C, about -60°C, about -62°C, about -64°C, about -66°C, about -68°C, about -70°C, or any range including and / or between any two of these values, or any one of these values. In any aspect or embodiment of the present technology, the LPK may exhibit at least 80 vol% boiling in the range of 150-180°C based on the ASTM D86 test method.

[0062] In any aspect or embodiment of the present technology, the LPK may comprise about 99.7 wt% or more of hydrocarbons with less than 14 carbon atoms. In any aspect or embodiment of the present technology, the LPK may comprise about 99.8 wt% or more of hydrocarbons with less than 14 carbon atoms. In any aspect or embodiment of the present technology, the LPK may comprise about 99.9 wt% or more of hydrocarbons with less than 14 carbon atoms. The LPK may have less than about 0.1 wt% oxygenates, about 0.09 wt%, about 0.08 wt%, about 0.07 wt%, about 0.05 wt%, about 0.04 wt%, about 0.03 wt%, about 0.02 wt%, about 0.01 wt%, or any range inclusive of and / or between any two of these values ​​or less than any one of these values. Such low levels of oxygenates may be detected through appropriate analytical techniques, including but not limited to instrumental neutron activation analysis.

[0063] The LPK of any aspect or embodiment of the present technology may have less than about 0.1 wt% aromatics. Thus, the LPK may contain an amount of aromatics of about 0.09 wt%, about 0.08 wt%, about 0.07 wt%, about 0.06 wt%, about 0.05 wt%, about 0.04 wt%, about 0.03 wt%, about 0.02 wt%, about 0.01 wt%, about 0.009 wt%, about 0.008 wt%, about 0.007 wt%, about 0.006 wt%, about 0.005 wt%, about 0.004 wt%, about 0.003 wt%, about 0.002 wt%, about 0.001 wt%, or any range inclusive of and / or between any two of these values ​​or less than any one of these values. In any aspect or embodiment of the present technology, the LPK may contain no detectable aromatic substances as measured by gas chromatography. The LPK may contain less than about 0.01 wt% benzene, and may contain an amount of benzene of about 0.008 wt%, about 0.006 wt%, about 0.004 wt%, about 0.002 wt%, about 0.001 wt%, about 0.0008 wt%, about 0.0006 wt%, about 0.0004 wt%, about 0.0002 wt%, about 0.0001 wt%, about 0.00008 wt%, about 0.00006 wt%, about 0.00004 wt%, about 0.00002 wt%, about 0.00001 wt%, or any range including and / or between any two of these values ​​or less than any one of these values. Such low levels of benzene may be determined through appropriate analytical techniques, including but not limited to, two-dimensional gas chromatography of the LPK. In any aspect or embodiment of the present technology, the LPK may contain no detectable benzene.

[0064] The LPK of any aspect or embodiment of the present technology may have a sulfur content of less than about 5 wppm. Thus, in any aspect or embodiment of the present technology, the LPK may have a sulfur content of about 4 wppm, about 3 wppm, about 2 wppm, about 1 wppm, about 0.9 wppm, about 0.8 wppm, about 0.7 wppm, about 0.6 wppm, about 0.5 wppm, about 0.4 wppm, about 0.3 wppm, about 0.2 wppm, about 0.1 wppm, or any range including and / or between any two of these values ​​or less than any one of these values.

[0065] In any aspect or embodiment of the present technology, the SAF may comprise LPK of any aspect or embodiment disclosed herein in an amount of about 30 wt% or more. Thus, in any aspect or embodiment of the present technology, the SAF may comprise LPK in an amount of about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 70 wt%, about 80 wt%, about 90 wt%, about 95 wt%, or any range including and / or between any two of these values ​​or any range exceeding any one of these values. In any aspect or embodiment of the present technology, the SAF may comprise C 200 from a heavy hydroisomerization unit fraction. 12 ~C 16 Isoparaffin and / or petroleum C 12 ~C 16 Isoparaffin, etc. 12 ~C 16 It may further comprise isoparaffin.

[0066] In any aspect or embodiment, separating the LPK from the hydroisomerization unit product and / or separating the SAF from the hydroisomerization unit product can include separating a renewable diesel from the hydroisomerization unit product, the renewable diesel comprising at least a portion of the heavy hydroisomerization unit fraction. The renewable diesel can have less than about 0.1 wt% oxygenates in any aspect or embodiment, and can have an amount of oxygenates of about 0.09 wt%, about 0.08 wt%, about 0.07 wt%, about 0.05 wt%, about 0.04 wt%, about 0.03 wt%, about 0.02 wt%, about 0.01 wt%, or any range inclusive of and / or between any two of these values ​​or less than any one of these values. The renewable diesel in any aspect or embodiment can have less than about 0.1 wt% aromatics. Thus, the renewable diesel may contain an amount of aromatics of about 0.09 wt%, about 0.08 wt%, about 0.07 wt%, about 0.06 wt%, about 0.05 wt%, about 0.04 wt%, about 0.03 wt%, about 0.02 wt%, about 0.01 wt%, about 0.009 wt%, about 0.008 wt%, about 0.007 wt%, about 0.006 wt%, about 0.005 wt%, about 0.004 wt%, about 0.003 wt%, about 0.002 wt%, about 0.001 wt%, or any range including and / or between any two of these values ​​or less than any one of these values. In any aspect or embodiment, the renewable diesel may be free of detectable aromatics as measured by gas chromatography. Renewable diesel may contain less than about 0.01 wt% benzene, and may contain an amount of benzene of about 0.008 wt%, about 0.006 wt%, about 0.004 wt%, about 0.002 wt%, about 0.001 wt%, about 0.0008 wt%, about 0.0006 wt%, about 0.0004 wt%, about 0.0002 wt%, about 0.0001 wt%, about 0.00008 wt%, about 0.00006 wt%, about 0.00004 wt%, about 0.00002 wt%, about 0.00001 wt%, or any range including and / or between any two of these values ​​or less than any one of these values.Renewable diesel may have a sulfur content of less than about 5 wppm; thus, renewable diesel may have a sulfur content of about 4 wppm, about 3 wppm, about 2 wppm, about 1 wppm, about 0.9 wppm, about 0.8 wppm, about 0.7 wppm, about 0.6 wppm, about 0.5 wppm, about 0.4 wppm, about 0.3 wppm, about 0.2 wppm, about 0.1 wppm, or any range including and / or between any two of these values ​​or less than any one of these values.

[0067] The renewable diesel in any aspect or embodiment of the present technology may have a cloud point below about 0° C. and may further have a cetane number of 60 or greater. Thus, in any embodiment herein, the renewable diesel may include a cloud point of about 0°C, about -2°C, about -4°C, about -6°C, about -8°C, about -10°C, about -12°C, about -14°C, about -16°C, about -18°C, about -20°C, about -22°C, about -24°C, about -26°C, about -28°C, about -30°C, about -32°C, about -34°C, about -36°C, about -38°C, about -40°C, about -42°C, about -44°C, about -46°C, about -48°C, about -50°C, about -52°C, about -54°C, about -56°C, about -58°C, about -60°C, or any range between and / or including any two of these values ​​or any range less than any one of these values.

[0068] Referring now to the drawings, Figure 1 provides a non-limiting, exemplary embodiment of the present technology. In Figure 1, a renewable feed 101 having naturally occurring fatty acids and fatty acid esters / glycerides is transferred to a hydrotreater 102 where it is reacted with hydrogen under a pressure of about 300 psig to about 3,000 psig (e.g., about 500 psig to about 2,000 psig). As previously mentioned, the hydrotreater 102 can include a packed bed of a sulfided catalyst such as nickel-molybdenum (NiMo), nickel-tungsten (NiW), or cobalt-molybdenum (CoMo) on a gamma-alumina support.

[0069] Feed 101 may be preheated prior to entering hydrotreater 102, where hydrotreater 102 may operate at about 300° F. to about 900° F. (e.g., about 550° F. to about 650° F.). Many methods known in the art may be used to reduce the adiabatic temperature rise from the exothermic hydrotreating reactions and maintain hydrotreater 102 within the preferred operating temperature range. These methods include, but are not limited to, dilution of the feed with a solvent or other diluent, recirculation of liquid products or solvents, and the use of a quench zone in the fixed bed reactor where hydrogen is introduced.

[0070] The liquid hourly space velocity of the feed 101 through the hydrotreater 102 is about 0.2 h -1 ~about 10h -1 (For example, about 0.5 h -1 ~about 5.0h -1 The ratio of hydrogen-rich treat gas 110 to renewable feed 101 can be from about 2,000 to about 15,000 SCF / bbl (e.g., from about 4,000 to about 12,000 SCF / bbl). The hydrogen-rich treat gas 110 can contain from about 70 mol% to about 100 mol% hydrogen.

[0071] The hydrotreater effluent 103 comprises a deoxygenated heavy hydrotreater fraction and a gaseous fraction containing unreacted hydrogen. The deoxygenated heavy hydrotreater fraction comprises a C 24 Mainly C with up to 2% of heavier compounds 13 ~C 24 The hydrogen-rich gas contains n-paraffins in the range of C1-C3 hydrocarbons, water, carbon oxides, ammonia, and / or hydrogen sulfide in addition to hydrogen. The heavy hydrotreater fraction in the liquid phase may be separated from the gas phase components in separator 104.

[0072] Separator 104 may use a high pressure drum operating at hydrotreater discharge pressure (e.g., from about 50 psig to about 3,000 psig; from about 500 psig to about 2,000 psig) and the heavy hydrotreater fraction may be separated from hydrogen and gas phase hydrotreater by-products such as water, carbon dioxide, ammonia, hydrogen sulfide, and / or propane. Depending on the temperature, the water by-product may be in the gas or liquid phase. The high pressure drum may operate at a temperature of from about 350°F to about 500°F, whereby water, carbon oxides, ammonia, hydrogen sulfide, and / or propane are separated from the heavy hydrocarbon fraction in the liquid phase along with hydrogen in the gas phase. Separator 104 may further include a high pressure drum operating at a lower temperature (e.g., from about 60°F to about 250°F) to condense aqueous solution stream 111. The aqueous solution stream 111 may contain dissolved ammonia and / or carbon dioxide and may be separated from the hydrogen-rich gas phase 105 which is then recycled to the hydrotreater 102 .

[0073] The heavy hydrotreater fraction 112 from separator 104 may then be processed through hydroisomerization unit 114. The heavy hydrotreater fraction 112 may optionally be combined with hydroisomerization unit heavy fraction 125. The hydroisomerization unit 114 may operate at a hydrogen pressure of about 250 psig to about 3,000 psig (e.g., about 1,000 psig to about 2,000 psig), which may be provided by the hydrogen-rich gas 110a. The temperature of the hydroisomerization unit 114 may be about 400°F to about 900°F (e.g., about 580°F to about 750°F).

[0074] In the hydroisomerization and hydrocracking of the present technology, hydrocracking converts at least a portion of the heavy hydrocarbon feed into liquefied petroleum gas ("LPG") containing C3-C4 hydrocarbons, light naphtha (C5-C8 hydrocarbons), and LPK (C8-C10 hydrocarbons). 11For a given hydroisomerization catalyst, higher temperatures and lower LHSVs result in increased hydrocracking. Increased hydrocracking, in turn, increases the iso-to-n-paraffin ratio of the LPK. To produce the desired LPK that avoids incompatibility with real gums while minimizing yield losses from excessive cracking, the hydrocracking side reaction should result in an LPK with an iso / n ratio of about 2.0 to about 5.0. When the iso / n ratio is less than about 3.0, e.g., about 1.0 to 2.8, trace concentrations of heavier hydrocarbons, especially C 14 These hydrocarbons must be removed from the LPK in fractionator 124 (described below with respect to FIG. 1).

[0075] The effluent stream 115 exits the hydroisomerization unit 114. The effluent stream 115 is a two-phase fluid from which hydrogen-rich gas 117 is separated from the hydroisomerization unit product in separator 116. Separator 116 may include a high pressure separation drum (not shown) operating at hydroisomerization unit discharge pressure (e.g., about 500 psig to about 2,000 psig) where the liquid hydrocarbons are separated from the hydrogen, gaseous hydrocarbons, and / or any other gas phase products. The hydrogen-rich gas 117 from separator 116 is mixed with the hydrogen-rich gas 105 from separator 104 and optionally processed through an absorption column and / or scrubber 108 to remove ammonia, carbon oxides, and / or hydrogen sulfide before being compressed for recycle to the hydrotreater 102 and / or hydroisomerization unit 114. Depending on the contaminants to be removed, scrubber 108 may use various solvents such as amines and caustic solutions. Those skilled in the art will appreciate that other gas purification techniques may be used in place of, or in addition to, the scrubber 108 to remove contaminants that affect the catalytic activity and selectivity of the hydrotreater 102 and hydroisomerization unit 114. Examples of alternative gas purification techniques include membrane systems and adsorption beds.

[0076] Bleed gas 107 may be removed from the recycle gas 106 to prevent the accumulation of gas phase contaminants that are not effectively removed in the scrubber 108. The purified hydrogen-rich gas 108a from the scrubber 108 may be mixed with make-up hydrogen 109 to form a hydrogen-rich stream 110 for the hydrotreater 102 and hydroisomerization unit 114.

[0077] The liquid hydrocarbon phase 123 from separator 116 is directed to fractionator 124 to fractionate the hydroisomerizer product into a crude naphtha stream 127, an LPK fraction 126, and a heavy hydroisomerizer fraction 125. The heavy hydroisomerizer fraction 125 may optionally be recycled to the hydroisomerizer 114. Fractionator 124 may be a single distillation column in which the LPK fraction 126 is recovered as a side draw, or it may be two different distillation columns configured such that after separation of the crude naphtha in the first column, the LPK fraction 126 is recovered as an overhead fraction in the second column. In embodiments where hydroisomerization unit 114 is operated to provide LPK with an i / n ratio of less than about 2.0, e.g., an i / n ratio between 1.0 and 1.8, fractionator 124 can be configured and operated to ensure that no detectable (by gas chromatography) hydrocarbons having 14 or more carbon atoms are entrained in the LPK. In embodiments where fractionator 124 has two columns, the C 14 LPKs may be recovered as an overhead fraction from the second column under conditions that achieve the above separation of heavy hydrocarbons. Such conditions are known to those skilled in the art and include increasing the column reflux ratio and additional theoretical trays, as further described below.

[0078] Regardless of the configuration, the distillation column may include a reboiler or conduit for a superheated steam supply to provide heat of vaporization to move the gas up the column, and a condenser to provide a cooling function to condense the gas and produce reflux to flow down the column. Each distillation column includes equipment to facilitate contact of the gas with the liquid. Trays or packing within the column are used for this purpose, various types of which are well known to those skilled in the art. The number of trays or packing height required is often expressed as the theoretical trays (or theoretical stages) of the column. In an embodiment with two columns, the second distillation column, in which the LPK 126 (or SAF stream containing LPK) is separated as the overhead fraction and the hydroisomerization unit heavy fraction 125 as the bottoms, may be a vacuum tower with about 10 to about 40 theoretical trays. In either embodiment, the vacuum tower may be operated at an absolute pressure of about 50 mmHg to about 350 mmHg to reduce the temperature requirements for vaporization. In either embodiment, the hydroisomerization unit heavy fraction 125 may be used as renewable diesel fuel. In either embodiment, the crude naphtha stream 127 may be processed through a debutanizer (not shown) to separate the stream into C3-C4 LPG and C5-C8 light naphtha. Those skilled in the art will appreciate that any configuration of distillation columns and fractionation schemes or arrangements may be used so long as the system functions according to the present technology. The LPG 126 exiting the fractionator 124 is a mixture of C8-C8 LPG and C5-C8 light naphtha. 11 It is a hydrocarbon fraction.

[0079] From the above description, it is clear that the present technology is well adapted to accomplish the objects and achieve the advantages described herein and inherent in the invention. Although presently preferred embodiments have been described for purposes of this disclosure, it will be understood that many modifications may be made that are readily understood by those skilled in the art and are accomplished within the spirit of the disclosed and claimed technology. The present technology thus far generally described will be more readily understood by reference to the following examples, which are provided by way of illustration and are not intended to limit the present technology. EXAMPLES

[0080] Example 1. A FOG feedstock containing used commercial cooking oil was subjected to hydrotreating in an adiabatic fixed bed reactor operating under a hydrogen partial pressure of approximately 1700 psia at a temperature range of 540-680°F throughout the reactor system. The hydrotreater was loaded with a catalyst system comprising a sulfided NiMo catalyst. The hydrotreater effluent (a two-phase stream containing hydrogen and water in the gas phase) was processed through a high temperature separator to separate the gas / vapor from the liquid product stream. The latter was stripped with nitrogen at a pressure lower than the high temperature separator pressure. The stripping step was performed to remove the gas phase by-products of hydrotreating (i.e., solubilized water, CO, CO2, H2S, and NH3). The stripped liquid was sampled to determine C, C-C, C-H, C-H-O ... 14 ~C 18 Liquid hydrocarbons containing primarily n-paraffins were found. The liquid hydrocarbons were subsequently subjected to hydroisomerization (HI) in another fixed bed reactor operating under a H2 partial pressure of approximately 900 psia and an average catalyst temperature ranging from 600 to 620°F. The HI reactor was loaded with a bifunctional catalyst containing platinum. The HI reactor effluent was fractionated into three cuts: (1) diesel, (2) broad boiling range naphtha, and (3) LPG and non-condensable components. Analysis of the broad boiling range naphtha via GC revealed C5-C 14 + isoparaffinic hydrocarbon composition. The results of the GC analysis are shown in Table 1.

[0081] (Table 1) Hydrocarbon composition of naphtha with a wide boiling range TIFF2024522114000003.tif83128

[0082] Next, light hydrocarbons were stripped from naphtha, which has a wide boiling range, to obtain light paraffinic kerosene (LPK) with a flash point in the range of 38 to 42°C. This was achieved by distilling light naphtha hydrocarbons (light components of C8 or less) as the overhead fraction and by separating C8 to C8 with an iso / normal ratio of about 1. 11The LPK was recovered as a bottoms fraction containing mostly hydrocarbons (approximately 98 wt% or more). Several samples were taken for fuel property measurements, and the results are summarized in Table 2.

[0083] (Table 2) Volatility characteristics of LPK compared to HEFA fuel specifications TIFF2024522114000004.tif24979

[0084] As shown in Table 2, at least 90 vol.% of the LPK boils within the target 150-180°C associated with excellent low temperature jet engine ignition properties. The LPK fraction is at the lighter end of the volatility specification limits but meets the specifications. In fact, the LPK fraction was found to meet all of the ASTM D7566 HEFA SAF specifications except for the actual gums (discussed in Example 2 below).

[0085] Example 2. Investigation of "gum" residues from real gum tests After stripping the LPK of Example 1 according to the standard test method IP540 air evaporation method, the residues remaining in the seven test tubes were analyzed via GC-MS (GC with mass spectrometer detector) to identify the composition of the "gum" residues. Technically, these are polymeric materials (molecular weight > C 24 However, tests did not show any "heavies" or polymeric materials in these gum residues (Figure 2), but instead showed mainly tetradecane (C 14 ), hexadecane (C 16 ), and octadecane (C 18 ), and other C 14 ~C 22 Figure 3 shows the GC overlays from all seven "gum" residues recovered from the LPK real gum test.

[0086] Example 3. Cetane number A sample of the LPK produced according to the procedure described in Example 1 was subjected to cetane number testing according to ASTM D613 test method. The cetane number of the LPK was found to be 65.1, well above the target minimum cetane number (55) for mitigating lean blowout (LBO).

[0087] Example 4. Effect of LPK iso / normal ratio on real gum test results The diesel and LPK fractions prepared according to the conditions described in Example 1 were combined to give a broader boiling range HI product. In a first trial (Trial 1), the HI reactor was operated at the lower end of the 600-620°F temperature range of Example 1 to minimize hydrocracking side reactions. The diesel and LPK fractions were combined to give a broader boiling range HI product. The cloud point of this first HI product was found to be -11C.

[0088] In the second trial (Trial 2), the HI reactor was operated at the higher end of the temperature range of 600-620°F to increase the hydrocracking side reaction. The corresponding diesel and LPK fractions were combined. The cloud point of this second HI product was found to be -21°C.

[0089] The diesel fractions from both trials were tested for traces of heteroatoms. Sulfur and nitrogen were not detected (i.e., <0.5 ppm detection limit). Acid number was also below detection limit (<0.02 mg KOH / g).

[0090] The HI products from trial 1 and trial 2 were distilled to obtain SAF distillates containing LPK. A 12 liter laboratory spinning band distillation system (Model 9600) from BR Instruments was used. The distillation system consisted of a perforated spiral Teflon band designed to create approximately 50 theoretical trays. The apparatus was operated at a vacuum of approximately 100 mmHg. The reflux ratio was set at 5:1 for these experiments. Two distillates were obtained from each HI product and analyzed for n-paraffin and isoparaffin concentrations by carbon number by GC simulated distillation (using GC area counts). Each SAF distillate sample was also analyzed for freezing point and subjected to real gum analysis by both ASTM D381 (steam evaporation) and IP540 (air evaporation) methods. The results are summarized in Table 3.

[0091] Table 3. Distillation of HI products and properties of corresponding SAF distillates TIFF2024522114000005.tif24371

[0092] As seen in Table 3, the LPK fractions (C8–C 11 ) had an iso / normal ratio of 1.1. These SAF distillates showed variation between the actual gum values ​​measured by the two standard test methods, with one of the two distillates failing the gum test using the IP540 air evaporation method. Note that the actual gum value of 9 mg / 100 mL for SAF distillate 2 exceeds the specified maximum of 7 mg / 100 mL.

[0093] On the other hand, the LPK fractions of SAF distillates 3 and 4 had an i / n ratio of 3.6. They showed consistent compliance with the actual gum specification of 7 mg / 100 mL maximum according to both test methods (ASTM D381 steam evaporation and IP540 air evaporation). All SAF products with freezing point values ​​below -40C had an LPK content of at least 30 wt%.

[0094] Example 5. Effect of residual C14+ paraffin on LPK real gum test results The LPK sample was analyzed via GC and found to be 99.7% C13 The following light hydrocarbons were found to have an iso / normal ratio of 1.3: C 14 + (i.e., C 14 Heavy hydrocarbons (heavier than C 14 ~C 16 Paraffin at 0.2% and C 17 ~C 18 It contained 0.1% paraffin. The actual gum content of the LPK sample was measured according to the IP540 air method and found to be 13 mg / 100 mL.

[0095] The LPK was subjected to distillation through a spinning band distillation apparatus as described in Example 4. The operating pressure for this series of distillation experiments was 50 mmHg. The fractions obtained, their compositions by GC analysis, and the corresponding real gum test results are summarized in Table 4.

[0096] Table 4: Actual gum test results of LPK cuts in Example 5 and combinations of cuts TIFF2024522114000006.tif192113

[0097] Example 6 LPK was produced according to the methods and conditions described in Example 1, except that a higher HI reactor temperature in the range of 626°F to 635°F (about 330°C to about 335°C) was utilized to provide more hydrocracking and increase the i / n ratio from about 1 to about 2. Three different LPK samples with different fractionation conditions were collected. The results are summarized in Table 5 below. In particular, "C 14 The presence of "plus" affects the actual gum test results of LPK products according to the ASTM D381 steam method.

[0098] (Table 5) TIFF2024522114000007.tif62163

[0099] While particular embodiments have been illustrated and described, it is to be understood that changes and modifications can be made in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims. Each aspect and embodiment described above can also include or incorporate such variations or aspects disclosed with respect to any or all of the other aspects and embodiments.

[0100] The present technology should also not be limited in relation to the specific aspects and / or embodiments described herein, which are intended as merely illustrative of individual aspects and / or embodiments of the present technology. As will be apparent to those skilled in the art, many modifications and variations can be made without departing from the spirit and scope thereof. In addition to those enumerated herein, functionally equivalent methods and compositions within the scope of the disclosure will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to be within the scope of the appended claims. The present disclosure should be limited only by the language of the appended claims together with the full scope of equivalents to which such claims apply. It should be understood that the present disclosure is not limited to specific methods, reagents, compounds compositions or biological systems, which may of course be modified. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0101] The embodiments illustratively described herein may suitably be practiced in the absence of any element or elements, limitations or limitations not specifically disclosed herein. Thus, for example, terms such as "comprising", "including", "containing" and the like are to be read broadly and without limitation. In addition, the terms and expressions employed herein are used as terms of description and not of limitation, and in the use of such terms and expressions, there is no intention to exclude any equivalents of the shown and described features or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Furthermore, the term "consisting essentially of" will be understood to include the elements specifically described, as well as additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The term "consisting of" excludes any elements not specified.

[0102] Additionally, when features or aspects of the disclosure are described in terms of a Markush group, those skilled in the art will recognize that the disclosure is also described in terms of any individual members or subgroups of members of the Markush group.

[0103] As will be understood by those skilled in the art, for all purposes, particularly in terms of providing a written description, all ranges disclosed herein encompass all possible subranges and combinations of subranges. Any described range can be readily recognized as fully described and operable, with the same range being divided into at least one half, one third, one quarter, one fifth, one tenth, etc. As a non-limiting example, each range discussed herein can be readily divided into a lower third, a middle third, an upper third, etc. As will also be understood by those skilled in the art, phrases such as "up to," "at least," "greater than," "less than," etc., all refer to ranges that are inclusive of the number described and can be subsequently broken down into subranges as discussed above. Finally, as will be understood by those skilled in the art, ranges include individual members.

[0104] All publications, patent applications, issued patents, and other documents referred to herein are incorporated by reference in their entirety to the same extent as if each individual publication, patent application, issued patent, and other reference was specifically and individually indicated to be incorporated by reference. Definitions contained in documents incorporated by reference are excluded if they conflict with definitions in this disclosure.

[0105] It is understood that the present technology may include, but is not limited to, the features and combinations of features set forth in the lettered paragraphs below, and that the following paragraphs should not be construed as limiting the scope of the claims appended hereto or as mandating that all such features must necessarily be included in such claims. A. 1. A process for producing light paraffinic kerosene (LPK), comprising: C 14 ~C 24 To obtain a heavy hydrotreating fraction containing n-paraffins, 14 ~C 24 hydrotreating a bio-renewable feedstock comprising fatty acids, fatty acid esters, and / or fatty acid glycerides; Heavy hydroisomerization unit fraction and C8-C 11 hydroisomerizing and hydrocracking the heavy hydrotreater fraction using a hydroisomerization catalyst under conditions to provide a hydroisomerization unit product comprising LPK and hydrocarbons; and Separating LPK from the hydroisomerization unit product. Including, The LPK has an actual gum value of 7 mg / 100 mL or less as measured according to the IP540 air evaporation method, and The weight ratio of isoparaffins to n-paraffins is greater than or equal to about 2:1, or No hydrocarbons with 14 or more carbon atoms are detected by gas chromatography, or The weight ratio of isoparaffins to n-paraffins is approximately 2:1 or more, and no hydrocarbons with 14 or more carbon atoms are detected by gas chromatography. Including, method. B. The process of paragraph A comprising hydroisomerizing and hydrocracking the heavy hydrotreater fraction at a temperature from about 580°F to about 750°F, optionally from about 626°F to about 635°F. C. The process of paragraph A or paragraph B, wherein the ratio of isoparaffins to n-paraffins in the LPK is from about 2:1 to about 5:1. D. The method of any one of paragraphs A to C, wherein the ratio of isoparaffins to n-paraffins in the LPK is from about 3:1 to about 4:1. E. The method of any one of paragraphs A-D, further comprising separating a renewable diesel comprising a heavy hydroisomerizer fraction from the hydroisomerizer product. F. The method of any one of paragraphs A-E, wherein the bio-renewable feedstock comprises used cooking oil, rendered fat, or a combination thereof. G. The method of any one of paragraphs A-F, wherein the bio-renewable feedstock comprises carinata oil, shepherd's purse oil, flowering plant oil, or a combination of any two or more thereof. H. The method of any one of paragraphs A-G, wherein the LPK has a flash point of about 38° C. to about 42° C. I. The method of any one of paragraphs AH, wherein the LPK has a cetane number from about 55 to about 80. J. The method of any one of paragraphs AI, wherein the LPK contains at least about 99.9 wt% hydrocarbons having less than 14 carbon atoms. K. 1. A method for producing bio-renewable sustainable aviation fuel (SAF), comprising: C 14 ~C 24 To obtain a heavy hydrotreating fraction containing n-paraffins, 14 ~C 24 hydrotreating a bio-renewable feedstock comprising fatty acids, fatty acid esters, and / or fatty acid glycerides; Heavy hydroisomerization unit fraction and C8-C 11 hydroisomerizing and hydrocracking the heavy hydrotreater fraction using a hydroisomerization catalyst under conditions to provide a hydroisomerization unit product comprising: Separating sustainable aviation fuel (SAF) from hydroisomerization unit product Including, the SAF comprises at least a portion of the LPK; The LPK has an actual gum value of 7 mg / 100 mL or less as measured according to the IP540 air evaporation method, and The weight ratio of isoparaffins to n-paraffins is greater than or equal to about 2:1, or No hydrocarbons with 14 or more carbon atoms are detected by gas chromatography, or The weight ratio of isoparaffins to n-paraffins is approximately 2:1 or more, and no hydrocarbons with 14 or more carbon atoms are detected by gas chromatography. and The SAF has an actual gum value of 7 mg / 100 mL or less as measured according to the IP540 air evaporation method; method. L. The method of paragraph K, wherein the separating step is performed to result in a SAF containing at least about 30 wt% LPK. M. The method of paragraph K or paragraph L, wherein the SAF comprises about 30 wt% to about 90 wt% LPK. N. SAF, C 12 ~C 16 The method of any one of paragraphs KM, further comprising isoparaffin. O. The method of any one of paragraphs K-N comprising hydroisomerizing and hydrocracking the heavy hydrotreater fraction at a temperature from about 580°F to about 750°F. P. The method of any one of paragraphs K-O, wherein the ratio of isoparaffins to n-paraffins in the LPK is from about 2:1 to about 5:1. Q. The method of any one of paragraphs KP, wherein the ratio of isoparaffins to n-paraffins in the LPK is from about 3:1 to about 4:1. R. The method of any one of paragraphs K-Q, further comprising separating a renewable diesel comprising a heavy hydroisomerizer fraction from the hydroisomerizer product. S. The method of any one of paragraphs K-R, wherein the bio-renewable feedstock comprises used cooking oil, refined fat, or a combination thereof. T. The method of any one of paragraphs K-S, wherein the bio-renewable feedstock comprises carinata oil, shepherd's purse oil, flowering plant oil, or a combination of any two or more thereof. U. The method of any one of paragraphs KT, wherein the LPK has a flash point of from about 38° C. to about 42° C. V. The method of any one of paragraphs K-U, wherein the LPK has a cetane number from about 55 to about 80. W. The method of any one of paragraphs K-V, wherein the LPK contains at least about 99.9 wt% hydrocarbons having less than 14 carbon atoms. X. C 12 ~C 16 A method for producing sustainable aviation fuel (SAF), comprising the step of blending isoparaffin with LPK produced by the method of any one of paragraphs A-J. Y. A sustainable aviation fuel (SAF) produced according to the method described in paragraph X. Z. C 12 ~C 16 Isoparaffins; and Light paraffinic kerosene (LPK) produced according to the method of any one of paragraphs A to J. and sustainable aviation fuel (SAF). A.A. A bio-renewable sustainable aviation fuel (SAF) produced according to the method of any one of paragraphs K-W.

[0106] Other aspects are set forth in the following claims.

Claims

1. 1. A process for producing light paraffinic kerosene (LPK), comprising: C 14 ~C 24 To obtain a heavy hydrotreating fraction containing n-paraffins, 14 ~C 24 hydrotreating a bio-renewable feedstock comprising fatty acids, fatty acid esters, and / or fatty acid glycerides; Heavy hydroisomerization unit fraction and C 8 ~C 11 hydroisomerizing and hydrocracking the heavy hydrotreater fraction using a hydroisomerization catalyst under conditions to provide a hydroisomerization unit product comprising LPK and hydrocarbons; and Separating LPK from the hydroisomerization unit product. Including, The LPK has an actual gum value of 7 mg / 100 mL or less as measured according to the IP540 air evaporation method, and The weight ratio of isoparaffins to n-paraffins is greater than or equal to about 2:1, or No hydrocarbons with 14 or more carbon atoms are detected by gas chromatography, or The weight ratio of isoparaffins to n-paraffins is approximately 2:1 or more, and no hydrocarbons with 14 or more carbon atoms are detected by gas chromatography. Including, method.

2. 10. The process of claim 1, comprising hydroisomerizing and hydrocracking the heavy hydrotreater fraction at a temperature of from about 580°F to about 750°F.

3. 2. The method of claim 1, wherein the ratio of isoparaffins to n-paraffins in the LPK is from about 2:1 to about 5:

1.

4. 2. The method of claim 1, wherein the ratio of isoparaffins to n-paraffins in the LPK is from about 3:1 to about 4:

1.

5. 10. The method of claim 1, further comprising separating a renewable diesel comprising a heavy hydroisomerizer fraction from the hydroisomerizer product.

6. 2. The method of claim 1, wherein the bio-renewable feedstock comprises used cooking oil, rendered fat, or a combination thereof.

7. 2. The method of claim 1, wherein the bio-renewable feedstock comprises carinata oil, shepherd's purse oil, flowering plant oil, or a combination of any two or more thereof.

8. 10. The method of claim 1, wherein the LPK has a flash point of about 38°C to about 42°C.

9. 10. The method of claim 1, wherein the LPK has a cetane number of about 55 to about 80.

10. 2. The method of claim 1, wherein the LPK comprises about 99.9 wt% hydrocarbons having less than 14 carbon atoms.

11. 1. A method for producing bio-renewable sustainable aviation fuel (SAF), comprising: C 14 ~C 24 To obtain a heavy hydrotreating fraction containing n-paraffins, 14 ~C 24 hydrotreating a bio-renewable feedstock comprising fatty acids, fatty acid esters, and / or fatty acid glycerides; Heavy hydroisomerization unit fraction and C 8 ~C 11 hydroisomerizing and hydrocracking the heavy hydrotreater fraction using a hydroisomerization catalyst under conditions to provide a hydroisomerization unit product comprising: Separating sustainable aviation fuel (SAF) from hydroisomerization unit product Including, the SAF comprises at least a portion of the LPK; The LPK has an actual gum value of 7 mg / 100 mL or less as measured according to the IP540 air evaporation method, and The weight ratio of isoparaffins to n-paraffins is greater than or equal to about 2:1, or No hydrocarbons with 14 or more carbon atoms are detected by gas chromatography, or The weight ratio of isoparaffins to n-paraffins is approximately 2:1 or more, and no hydrocarbons with 14 or more carbon atoms are detected by gas chromatography. and The SAF has an actual gum value of 7 mg / 100 mL or less as measured according to the IP540 air evaporation method; method.

12. 12. The method of claim 11, wherein the separating step is carried out to result in a SAF containing about 30 wt% or more LPK.

13. 12. The method of claim 11, wherein the SAF comprises about 30 wt% to about 90 wt% LPK.

14. SAF, C 12 ~C 16 12. The method of claim 11, further comprising isoparaffin.

15. 12. The process of claim 11, comprising hydroisomerizing and hydrocracking the heavy hydrotreater fraction at a temperature of from about 580°F to about 750°F.

16. 12. The method of claim 11, wherein the ratio of isoparaffins to n-paraffins in the LPK is from about 2:1 to about 5:

1.

17. 12. The method of claim 11, wherein the ratio of isoparaffins to n-paraffins in the LPK is from about 3:1 to about 4:

1.

18. 12. The method of claim 11, further comprising separating a renewable diesel comprising a heavy hydroisomerizer fraction from the hydroisomerizer product.

19. 12. The method of claim 11, wherein the bio-renewable feedstock comprises used cooking oil, refined fat, or a combination thereof.

20. 12. The method of claim 11, wherein the bio-renewable feedstock comprises Carinata oil, Shepherd's purse oil, flowering plant oil, or a combination of any two or more thereof.

21. 12. The method of claim 11, wherein the LPK has a flash point of about 38°C to about 42°C.

22. 12. The method of claim 11, wherein the LPK has a cetane number of about 55 to about 80.

23. 12. The method of claim 11, wherein the LPK comprises at least about 99.9 wt% hydrocarbons having less than 14 carbon atoms.

24. C 12 ~C 16 11. A method for producing sustainable aviation fuel (SAF), comprising the step of mixing isoparaffin with LPK produced by the method of any one of claims 1 to 10.

25. 25. A sustainable aviation fuel (SAF) produced according to the method of claim 24.

26. C 12 ~C 16 Isoparaffins; and Light paraffinic kerosene (LPK) produced according to the method of any one of claims 1 to 10. and sustainable aviation fuel (SAF).

27. A bio-renewable sustainable aviation fuel (SAF) produced according to the method of any one of claims 11 to 23.

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