Sustainable aviation fuel composition

Abstract

A sustainable aviation fuel composition is disclosed. The sustainable aviation fuel composition comprises a T10 of more than about 110°C and a final boiling point of no more than about 300°C, about 5 to about 25 wt% aromatics, no more than about 15 wt% hydrogen, no more than about 1 wt% oxygen, and has a flash point of at least about 38°C. Further, a process of producing sustainable aviation fuel is disclosed. The sustainable aviation fuel can be used as fuel stream or a blend stock for blending with a fuel stream or both.

Description

SUSTAINABLE AVIATION FUEL COMPOSITIONFIELD

[0001] The field is related to an aviation fuel composition. Particularly, the field relates to a sustainable aviation fuel composition produced from bio-oil .BACKGROUND

[0002] Bio-oils are obtained by thermochemical processes including liquefaction, or pyrolysis. Notably biomass pyrolysis includes several classes of processes such as flash, fast, slow or catalytic pyrolysis. Pyrolysis is a thermal decomposition process in the absence of oxygen with thermal cracking of the feedstocks to gas, liquid and solid products. A catalyst can be added to enhance the conversion in catalytic pyrolysis. Various technologies have been deployed for large scale biomass pyrolysis. They include bubbling fluidized beds, circulating fluidizing beds, ablative pyrolysis, vacuum pyrolysis, and rotating cone pyrolysis reactors.Catalytic pyrolysis generally leads to bio-oil having a lower oxygen content than bio-oil obtained by thermal decomposition. The selectivity between gas, liquid and solid is well related to the reaction temperature and vapor residence time. Lower temperature, for example, around 400°C and longer residence time, for example, a few minutes to a few hours, obtained by slow pyrolysis, favors the production of solid product, also called char or char coal, with typically 35 wt% gas, 30 wt% liquid, and 35 wt% char. Very high temperature of above 800°C used in the gasification processes favors gas production, typically more than 85 wt%. Intermediate reaction temperature, typically about 450°C to about 550°C, and short vapor residence time, typically about 10 to about 20 seconds, for the pyrolysis, favor the liquid yield: typically 30 wt% gas, 50 wt% liquid, and 20 wt% char. Intermediate reaction temperature, typically about 450°C to about 550°C, and very short vapor residence time, typically about 1 to about 2 seconds, for the flash pyrolysis or fast pyrolysis, favor even more the liquid yield: typically 10 to about 20 wt% gas, about 60 to about 75 wt% liquid, about 10 to about 20 wt% char. The highest liquid yields may be obtained by the flash pyrolysis processes, with up to 75 wt%.

[0003] Bio-oils can be processed to provide low-cost renewable liquid fuels; indeed, they can be used as fuel for boilers, as well as for stationary gas turbines and diesel engines. Furthermore,fast pyrolysis has been demonstrated at fairly large scales, of the order of several hundred tons per day. Nevertheless, there has not been any significant commercial uptake of this technology. The reasons may relate mostly to the poor physical and chemical properties of bio-oils in general and fast pyrolysis bio-oils in particular. For example, some of the undesirable properties of pyrolysis bio-oils may include: (1) corrosivity on account of their high water and acidic contents; (2) relatively low specific calorific value on account of the high oxygen content, which typically is around 40% or more by mass; (3) chemical instability on account of the abundance of reactive functional groups like carboxyl groups and phenolic groups that can lead to polymerization on storage and consequent phase separation; (4) relatively high viscosity and susceptibility to phase separation under high shear conditions, for instance in a nozzle; (5) incompatibility with, on account of insolubility in, conventional hydrocarbon based fuels; (6) blockage in nozzles and pipes caused by adventitious char particles, which will always be present in unfiltered bio-oil to a greater or lesser degree. All these aspects combine to render bio-oil handling, shipping storage and usage difficult and expensive.

[0004] The economic viability of bio-oil production for fuel or energy applications therefore depends on finding appropriate methods to upgrade it to a higher quality liquid fuel at a sufficiently low cost.

[0005] Sustainable aviation fuel (SAF) is a high value product in a growing market driven by government climate mandates in various parts of the world. The predominance of currently available technologies produce sustainable paraffinic kerosene (SPK) from triglyceride feedstocks. These feedstocks have a limited supply. Technologies are needed to process more diverse and available renewable feedstocks such as lignocellulosic biomass. Moreover, the SPK produced from these technologies and similar paraffinic distillates for producing the SAF have viscosity on the higher end of jet fuel specification. Therefore, the fossil distillates that can be used to blend these SPKs for a blend-stock may need to have low viscosity. Further, these blendstocks are limited and can necessitate blenders to reduce the amount of SPK blended into SAF or would require them to procure fossil fuel stocks at a premium, and require severe processing conditions in hydroisomerization reactors in order to meet jet fuel freeze point specifications. These severe processing conditions reduce overall product yield. Renewable SAF blend stocks with low viscosity and low freeze point are needed to alleviate this problem. By extension, iffully renewable jet fuels are to be realized, a less viscous renewable blend-stock with low freeze point will be needed. A small amount of aromatics will also be needed in such a blend-stock.SUMMARY

[0006] The present disclosure provides a sustainable aviation fuel composition. The sustainable aviation fuel composition comprises a T10 of at least about 110°C and a final boiling point of no more than about 300°C, about 5 to about 25 wt% aromatics, no more than about 15 wt% hydrogen, no more than about 1 wt% oxygen, and has a flash point of at least about 38°C. The sustainable aviation fuel of the present disclosure comprises no detectable level of oxygen.

[0007] A process of producing sustainable aviation fuel is disclosed. The process of producing the sustainable aviation fuel avoids full deoxygenation of a bio-oil feed in upstream processing, such as a liquid phase hydrotreating reactor which allows operating the reactor at a lower severity as compared to operating upstream processing at the full deoxygenation of the feed. The sustainable aviation fuel of the present disclosure can be used as a fuel stream or a blend stock for blending with a fuel stream such as a bio-derived fuel stream and a petroleum-derived fuel stream or both.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] FIG. 1 illustrates a schematic diagram of a process of producing a sustainable aviation fuel in accordance with an embodiment of the present disclosure.

[0009] FIG. 2 illustrates a schematic diagram of a process of producing a sustainable aviation fuel in accordance with another embodiment of the present disclosure.DEFINITIONS

[0010] As used herein the terms “reactor”, “process equipment,” “process units,” or “reactor components” shall include any and all process equipment and process units that are utilized in biomass, bio-oil, or hydrocarbon conversion processes including any upstream and / or downstream equipment from the particular unit and / or ancillaries, such as furnace tubes, associated piping, heat exchangers, heater tubes, and the like.

[0011] As used herein, the term “predominant” or “predominate” or “predominance” means greater than 50%, suitably greater than 75% and preferably greater than 90%.

[0012] As used herein, the term “carbon number” refers to the number of carbon atoms per molecule.

[0013] As used herein, “petroleum stream” or “petroleum feedstock” may refer to crude oil, crude oil refinery distillates, crude oil refinery residue, cracked products or hydrocarbons from a crude oil refinery, liquefied coal, bitumen, typically extracted from the ground or sea floor.

[0014] As used herein, the term “True Boiling Point” (TBP) means a test method for determining the boiling point of a material which corresponds to ASTM D-2892 for the production of a liquefied gas, distillate fractions, and residuum of standardized quality on which analytical data can be obtained, and the determination of yields of the above fractions by both mass and volume from which a graph of temperature versus mass % distilled is produced using fifteen theoretical plates in a column with a 5: 1 reflux ratio.

[0015] As used herein, the term “T5”, “T10” or “T90” means the temperature at which 5 mass percent or 10 mass percent or 90 mass percent, as the case may be, respectively, of the sample boils using ASTM D-86 or TBP. In examples herein, the T5, T10, T90 and other distillation properties of a laboratory or pilot plant sample may at times be accurately estimated by simulated distillation, methods such as ASTM D2887, ASTM D2713, ASTM D632 or ASTM D7169, which utilize calibrated gas chromatographic analyses to simulate the boiling distribution of a sample.

[0016] As used herein, the term “vacuum gas oil” (VGO) includes hydrocarbons having an initial boiling point above approximately 343 °C (650°F), with a T10 boiling point temperature using ASTM DI 160 of approximately 370°C (698°F) and a T90 boiling point temperature using ASTM DI 160 of approximately 500°C (932°F).

[0017] As used herein, the terms “mol% H” and “mol% C” refer to the percentage of moles of hydrogen or carbon atoms, respectively, of the total moles of hydrogen or carbon atoms in oil. For example, if the bio-oil composition contains 5 moles of hydrogen atoms and 10 moles of carbon atoms and it is said that the bio-oil contains 10 mol% H of aldehydes and 20 mol % C of carboxylic acids and esters it means that 0.5 moles of hydrogen atoms in the bio-oil correspond to H atoms of molecules within an aldehyde functional group and 2 moles of carbon atoms in the bio-oil correspond to C atoms of molecules within either a carboxylic acid or ester functional group.

[0018] As used herein, the term “bioderived” or “biogenic” material means a material that comes from or made of, but not limited to, plants, animals, microorganisms, algae, or biopolymers.

[0019] As used herein, the term “recycle ratio” or “recycle rate” means the ratio of the recycle flow rate to the fresh feed flow rate.DETAILED DESCRIPTION

[0020] Biocrude or bio-oil polymerization of bio-oils such as pyrolysis oil during deoxygenation or hydrotreating reactions is a major challenge when attempting to convert bio-oil to fuels. The present disclosure provides a process to upgrade a biomass-based feed such as biooil in the presence of a catalyst and a stable oil to produce an upgraded bio-oil. This upgrading process to produce a stable oil is herein referred to as first stage treating or first stage upgrading. The upgraded bio-oil can be hydroprocessed using methods such as fixed bed hydrotreating to produce a sustainable aviation fuel. This hydroprocessing step may be referred to as a second stage treating. The first stage upgrading process may include various analyses to generate spectroscopy data to identify molecular functional groups that are responsible for bio-oil polymerization. Identification and tracking of functional group evolution as a function of catalyst or process conditions helps in targeting the groups responsible for rapid polymerization and charring providing the potential to selectively eliminate them thereby enhancing the performance of the first stage upgrading process.

[0021] Bio-oil, perhaps derived from lignocellulosic biomass, is a complex mixture of compounds, including oxygenates, that are obtained from the breakdown of biopolymers in biomass. Bio-oils can be derived from plants such as grasses and trees, wood chips, chaff, grains, grasses, com, corn husks, weeds, aquatic plants, hay and other sources of lignocellulosic material, such as derived from municipal waste, food processing wastes, forestry wastes and cuttings, energy crops, or agricultural and industrial wastes (such as sugar cane bagasse, oil palm wastes, sawdust or straws). Bio-oils can also be derived from pulp and paper byproducts (recycled or not). Bio-oils are generally obtained from these biomass feeds by thermochemical liquefaction, notably pyrolysis, such as flash pyrolysis, fast pyrolysis, slow pyrolysis, or catalyticpyrolysis. Hydrothermal liquefaction may also be utilized to generate bio-oil feeds. Several different processes which produce bio-oil can be utilized to produce biocrude feed.

[0022] Bio-oil is a highly oxygenated, polar hydrocarbon product that typically contains at least about 10 mass% oxygen, typically about 10 to 60 mass% oxygen, more typically about 30 to about 50 mass% oxygen on a water-free basis. In general, bio-oil comprises oxygenates that may include alcohols, aldehydes, ketones, acetates, ethers, esters, organic acids and aromatic oxygenates. Oxygen is also present as free water which constitutes at least about 10 mass%, typically about 15 to about 35 mass% of the bio-oil. These properties render bio-oil immiscible with fuel grade hydrocarbons, even with aromatic hydrocarbons, which typically contain little or no oxygen.

[0023] In an aspect of the present disclosure, the bio-derived feed stream may comprise a bio-oil stream obtained by pyrolysis of a biomass feedstock.

[0024] The bio-derived feed stream in the present disclosure may further contain other oxygenates derived from biomass such as vegetable oils or animal fat derived oils. Vegetable oil or animal fat-derived oil comprises fatty matter and therefore correspond to a natural or elaborate substance of animal or vegetable origin, mainly containing triglycerides. This essentially involves oils from renewable resources such as fats and oils from vegetable and animal resources (such as lard, tallow, fowl fat, bone fat, fish oil and fat of dairy origin), as well as the compounds and the mixtures derived therefrom, such as fatty acids or fatty acid alkyl esters. The products resulting from recycling of animal fat and of vegetable oils from the food processing industry can also be used, pure or in admixture with other constituent classes described above. The feeds may comprise vegetable oils from oilseed such as rape, erucic rape, soybean, jatropha, sunflower, palm, copra, palm-nut, arachidic, olive, corn, cocoa butter, nut, linseed oil or oil from any other vegetable. These vegetable oils very predominantly consist of fatty acids in form of triglycerides (generally above 97% by mass) having long alkyl chains ranging from 8 to 24 carbon number, such as butyric fatty acid, caproic, caprylic, capric, lauric, myristic, palmitic, palmitoleic, stearic, oleic, linoleic, linolenic, arachidic, gadoleic, eicosapentaenoic (EP A), behenic, erucic, docosahexaenoic (DHA) and lignoceric acids. The fatty acid salt, fatty acid alkyl ester and free fatty acid derivatives such as fatty alcohols that can be produced by hydrolysis, by fractionation or by transesterification, for example, of triglycerides or of mixtures of these oilsand of their derivatives also come into the definition of the “oil of vegetable or animal origin” feed in the present disclosure. All products or mixtures of products resulting from the thermochemical conversion of algae or products from the hydrothermal conversion of lignocellulosic biomass or algae (in the presence of a catalyst or not) or pyrolytic lignin are also feeds that can be used.

[0025] Moreover, the feed containing bio-oil can be co-processed with petroleum and / or coal derived hydrocarbon feedstocks in the first stage upgrading process or in the second stage treating process. In the first stage upgrading process, the petroleum derived hydrocarbon feed stock can be straight run vacuum distillates, vacuum distillates from a conversion process such as those from coking, from fixed bed hydroconversion or from ebullated bed or slurry hydrocracking heavy fraction hydrotreatment processes, or from solvent deasphalted oils. The feeds can also be formed by mixing those various fractions in any proportions in particular deasphalted oil and vacuum distillate. They can also contain products from the fluid catalytic cracking units, such as light cycle oil (LCO) of various origins, heavy cycle oil (HCO) of various origins and any distillate fraction from fluid catalytic cracking generally having a distillation range of about 150°C to about 370°C. They may also contain aromatic extracts and paraffins obtained from the manufacture of lubricating oils. The coal derived hydrocarbon feedstock can be products from the liquefaction of coal. Aromatics fractions from coal pyrolysis or coal gasification can also be used as bio-mass based feed. In the second stage treating process the petroleum derived hydrocarbon feedstock can be straight run vacuum distillates, vacuum distillates from a conversion process such as those from coking, from fixed bed hydroconversion or from ebullated bed or slurry hydrocracking heavy fraction hydrotreatment processes, or from solvent deasphalted oils, straight run diesel, kerosene or naphtha or cracked stocks such as hydrocracked diesel, kerosene or naphtha or products from a fluid catalytic cracking (FCC) unit, or other hydrocarbon streams.

[0026] FIG. 1 shows an exemplary embodiment of the process 100 of producing a sustainable aviation fuel. A bio-oil stream is taken in line 122 from a source, for example, a biooil storage drum 120. Generally, the bio-oil may be a pyrolysis oil obtained from a process such as pyrolysis of biomass or a product of hydrothermal liquefaction of bio-derived feeds. The biooil stream in line 122 may be passed to a mixer 140. Perhaps, the bio-oil stream in line 122 maybe pumped via a pump 123 and a pumped bio-oil stream in line 124 be passed to the mixer 140. In an aspect, a control valve 125 is provided for maintaining a required flow rate of the bio-oil stream to the mixer 140.

[0027] In accordance with the present disclosure, a non-bio derived feed stream may also be passed to the mixer and mixed with the bio-oil stream. In an embodiment of the present disclosure, a petroleum stream is the non-bio derived feed stream. The petroleum stream is taken in line 132 from a source, for example, a petroleum storage drum 130. The petroleum stream in line 132 may be passed to the mixer 140. Perhaps the petroleum stream in line 132 may be pumped via a pump 133 and a pumped petroleum stream in line 134 is passed to the mixer 140. In an aspect, a control valve 135 is provided for maintaining a required flow rate of the petroleum stream to the mixer 140. In an embodiment, a sulfur source comprising a sulfiding agent in line 131 may be added to the petroleum stream in line 132 or the bio-oil stream in line 122 and passed to the mixer 140. The control valves 125 and 135 can be used to control or adjust the proportions of the bio-oil and the petroleum stream fed to the mixer 140.

[0028] In the mixer 140, the bio-oil stream in line 124 and the petroleum stream in line 134 are mixed and kept well mixed at a ratio perhaps with an excess of the petroleum stream at the startup of the process. In an embodiment, the bio-oil stream in line 124 and the petroleum stream in line 134 are mixed in the mixer 140 at a mass ratio of the bio-oil stream and the petroleum stream of about less than 1 at the start-up to provide a mixed stream. After mixing, a mixed stream in line 142 is taken from the mixer 140. In an aspect, the mixed stream 142 comprises the bio-oil stream and the petroleum stream in a ratio of about 0: 100 to about 80:20 by mass at startup. The ratio of the bio-oil stream to the petroleum stream is adjusted at start-up to be greater than about 50:50, preferably greater than 80:20 during operation in which sustainable aviation fuel precursors are generated. In an exemplary embodiment, the petroleum stream in line 134 is vacuum gas oil (VGO). The mixed stream in line 142 may be reacted with hydrogen in the presence of a catalyst in a reactor to produce an upgraded bio-oil stream.

[0029] In an embodiment, the mixed stream in line 142 is passed to a liquid phase hydrotreating (LPH) reactor 150 in which the reactions of the first stage upgrading process take place. As described later in detail, a recycle stream in line 139 may also be passed to the reactor 150. A hydrogen stream in line 144 may also be charged to the reactor 150. In an embodiment,the hydrogen stream in line 144 may be blended or mixed with the mixed stream in line 142 and passed to the reactor 150. A catalyst stream in line 145 may also be passed to the reactor 150. In an embodiment, the catalyst stream may be blended or mixed with the mixed stream in line 142 to provide a combined stream in line 146 which is passed to the reactor 150. In another embodiment, the catalyst stream 145 may be added to the recycle stream in line 139 to provide a combined recycle stream which is passed to the reactor 150. In the reactor 150, the petroleum stream, the bio-oil stream, the recycle stream, and the hydrogen stream may be reacted over a catalyst in a continuous liquid phase to provide an upgraded bio-oil stream which may comprise sustainable aviation fuel in line 154. At least about 50 wt% of the upgraded bio-oil stream is bioderived. Preferably, about 100 wt% of the upgraded bio-oil stream is bio-derived.

[0030] Liquid phase hydrotreating (LPH) is used for upgrading the heavy hydrocarbon feedstocks to produce distillate products in the first stage upgrading process. The hydrotreating catalyst typically comprises a solid particulate compound of a catalytically active metal, metal sulfide, or a metal in elemental form, either alone or supported on a refractory material such as an inorganic metal oxide (e.g., alumina, silica, titania, zirconia, and mixtures thereof). Other suitable refractory materials include carbon, coal, and clays. Zeolites and non-zeolitic molecular sieves are also useful as solid supports. One advantage of using a solid particulate either alone or supported is its ability to act as a “coke getter” or adsorbent of asphaltene precursors that have a tendency to foul process equipment upon precipitation.

[0031] Catalytically active metals for use in LPH include those from Group IVB, Group VB, Group VIB, Group VIIB, or Group VIII of the Periodic Table, which are incorporated in the heavy hydrocarbon feedstock in amounts effective for catalyzing desired hydrotreating reactions to provide, for example, lower boiling hydrocarbons that may be fractionated from the LPH effluent as naphtha and / or distillate products in the substantial absence of the solid particulate. Representative metals include iron, nickel, molybdenum, vanadium, tungsten, cobalt, ruthenium, and mixtures thereof. The catalytically active metal may be present as a solid particulate in elemental form or as an organic compound or an inorganic compound such as a sulfide (e.g., iron sulfide) or other ionic compound. Metal or metal compound nanoaggregates may also be used to form the solid particulates.

[0032] In some embodiments, the metal compounds can be formed in situ, as solid particulates, from a catalyst precursor such as a metal sulfite (e.g., iron sulfite monohydrate) that decomposes or reacts in the LPH reaction zone environment, or in a pretreatment step, to form a desired, well-dispersed and catalytically active solid particulate (e.g., as iron sulfide). Catalyst precursors also include oil-soluble organometallic compounds containing the catalytically active metal of interest that thermally decompose to form the solid particulate (e.g., iron sulfide) having catalytic activity. Such compounds are generally highly dispersible in the heavy hydrocarbon feedstock and normally convert under pretreatment or LPH reaction conditions to the solid particulate that is contained in the slurry effluent. Catalyst precursors also include oil-soluble organometallic compounds, inorganic molybdenum compounds, or chelated metal compounds containing the catalytically active metal. Molybdenum chelates including molybdenum octoate, molybdenum dithiocarbamate, and molybdenum naphthenate and molybdenum compounds such as ammonium heptamolybdate and phosphomolybdic acid thermally decompose to form the solid particulate through reaction with sulfidation components in the feed or other sulfidation additives such as dimethyl disulfide, di-tert-butyl (poly)sulfide, dibenzyl disulfide, (di)allyl (di)sulfide, ammonium sulfite, dimethyl sulfite, dithiothreitol, elemental sulfur or thiourea to form, for example, molybdenum disulfide having catalytic activity. An exemplary in situ solid particulate preparation, involving pretreating, the heavy hydrocarbon feedstock and precursors of the ultimately desired metal compound, is described, for example, in U.S. Pat. No. 5,474,977.

[0033] In another aspect, a catalyst precursor with the sulfidation component or the sulfidation additive may be provided in a line 131 and added to the petroleum stream in line 132. In another aspect, a catalyst or a catalyst precursor may be added to the feed stream in line 122 or the petroleum stream in line 132.

[0034] Alternatively, such metal sulfides or other active metal compounds can be formed ex-situ or in a separate process step through typical methods for producing metal sulfides. One such method includes hydrothermal synthesis where a molybdenum compound and sulfidation component are added to water with an additional reducing agent such as citric acid, oxalic acid, or hydrochloric acid or gaseous hydrogen. In some cases, the sulfidation component may also act as a reducing agent such as thiourea, ammonium sulfite, dimethyl sulfite, or dithiothreitol. The hydrothermal synthesis solution may be loaded into an autoclave reactor and sealed. If gaseoushydrogen is the reducing agent, the autoclave reactor can be pressurized from about 1378 kPag (200 psig) to about 10342 kPag (1500 psig) with hydrogen gas or the hydrogen gas can flow and bubble through the autoclave reactor. The autoclave reactor is then heated to a synthesis temperature of about 200°C to about 300°C under the foregoing hydrogen or inert gas pressure and held at the synthesis temperature for about 0.5 to about 16 hours. The autoclave reactor is allowed to cool to room temperature before depressurization and unloading. The solid catalyst can be collected such as by centrifugation, filtration, or drying. An example of hydrothermal metal sulfide synthesis is described in J. Espano, Phase Control in the Synthesis of Iron Sulfides, 145 J. Am. Chem. Soc. 18948-18955 (2023).

[0035] Another such method of forming metal sulfides ex situ could be a sulfiding procedure in a fixed bed reactor. Such methods involve loading a fixed bed reactor with a powdered or pelletized molybdenum compound and flowing a sulfiding gas, such as hydrogen sulfide, or a sulfiding liquid, such as oil doped with a sulfiding agent over the catalyst bed. The fixed bed reactor is heated to a sulfiding temperature of about 200°C to about 35O°C, for example, under the flow of sulfiding gas and / or hydrogen gas. The reactor is either pressurized before or after heating to sulfiding temperature to a pressure of about 1378 kPag (200 psig) to about 13790 kPag (2000 psig). The reactor may be heated slowly at, for example, l°C / min, and held at selected temperature setpoints along the way to reach the final sulfiding temperature. The reactor may be held at temperature setpoints for hours to days. Once the sulfiding is complete, the reactor is cooled to room temperature and the catalyst is unloaded from the reactor in its metal sulfide form. The sulfided catalyst may be further reduced in particle size via grinding, milling, or other methods, so that it is a fine powder and highly dispersible.

[0036] Yet another method of forming metal sulfides ex situ could be a sulfiding procedure relying on chemical vapor deposition techniques. Such a method involves molybdenum compounds such as molybdenum trioxide, molybdenum dioxide, molybdenum foil, or dipotassium tetrathiomolybdate and sulfur compounds such as elemental sulfur, alkali sulfates, alkaline earth sulfates, or other metal sulfates or similar metal sulfites. A substrate is also used such as SiOz / Si wafers, graphenes / graphites, or powdered or pelletized substrates commonly used as catalyst supports such as SiCh, AI2O3, or TiCh. Using a typical tube furnace synthesis reactor, the reactants and supports are placed in the reactor tube in a specific order with the sulfursource first (furthest upstream) followed by the molybdenum source downstream followed by the substrate further downstream. All compounds mentioned above are placed in a thermal zone in the tube furnace, typically in ceramic or other thermally and chemically resistant holders, which may be controlled as independent zones or as one zone. The substrate may be placed outside a thermal zone, if desired. This positioning is such that a gas flow through the tube first contacts the sulfur source, followed by the molybdenum source, followed by the substrate. A gas flow could include inert gas, hydrogen, steam, and / or oxygen / air. In typical operation, a gas flow is started, and the tube furnace reactor zones are heated to a temperature that is suitable to vaporize one or more of the compounds mentioned above at ambient pressure, typically equal to or less than 1000°C. The compounds vaporize and flow downstream where they react with each other and deposit on the substrate. The synthesis may run until complete consumption of all reactants or the substrate may be moved in and out of the apparatus so that the deposition time is limited to several minutes. After synthesis completion, the resulting metal sulfide is collected by removal of the substrate holder. The metal sulfide catalyst can be used as-is or, in the case of depositions of flat substrates like silicon wafers, the catalyst powder may be optionally scraped off for use without the silicon wafer. An example of chemical vapor deposition metal sulfide synthesis is described in W. Fu, Toward Edge Engineering of Two-Dimensional Layered Transition-Metal Dichalcogenides by Chemical Vapor Deposition,” 17 (17) ACS Nano 16348-16368 (2023).

[0037] Other suitable precursors include metal oxides that may be converted to catalytically active (or more catalytically active) compounds such as metal sulfides. In a particular embodiment, a metal oxide containing mineral may be used as a precursor of a solid particulate comprising the catalytically active metal (e.g., iron sulfide) on an inorganic refractory metal oxide support (e.g., alumina). Bauxite represents a particular precursor in which conversion of iron oxide crystals contained in this mineral provides an iron sulfide catalyst as a solid particulate, where the iron sulfide after conversion is supported on the alumina that is predominantly present in the bauxite precursor.

[0038] The active metals employed in the hydroprocessing catalysts of the present disclosure as hydrogenation components are the base metals of Group VIII, i.e., iron, cobalt, and nickel. In addition to these metals, other promoters may also be employed in conjunction therewith, including the metals of Group VIB, e.g., molybdenum and tungsten. The amount ofhydrogenating metal in the catalyst can vary within wide ranges. Any amount between about 0.05 wt % and about 80 wt % may be used. In an aspect, molybdenum may be provided as a ground hydrotreating catalyst of particle size typically less than 60 mesh, preferably less than 100 mesh, more preferably less than 200 mesh, and even more preferably less than 400 mesh. The hydrotreating catalyst may be sulfided in situ or ex situ using any method mentioned throughout. In an aspect, molybdenum may be provided as an organic molybdenum such as molybdenum octoate or molybdenum dithiocarbamate which because it is oil or hydrocarbon soluble may be added directly to the hydrocarbon feed separately from or with the carbon particles. The molybdenum may react with sulfur provided in the hydrocarbon feed or an additive to produce molybdenum sulfide in the reactor which is the active form of the molybdenum catalyst.

[0039] Nickel may be provided as a catalyst in the way molybdenum is added.

[0040] In another aspect, the catalyst is a nickel and molybdenum sulfide catalyst where nickel is incorporated into the molybdenum sulfide molecular structure to enhance catalytic activity but may also form separate nickel sulfide phases with their own separate catalytic activity. In syntheses mentioned throughout that involve an aqueous solution, nickel can be added by simply introducing a nickel compound to the aqueous solution before heating to final synthesis temperature. In syntheses that involve a solid and gas or a solid and liquid method, nickel compounds may be physically mixed with the molybdenum compounds. For in situ formation of the nickel and molybdenum sulfide in the LPH, an oil-soluble nickel compound may be added directly to the feed or added from a separate line into the LPH. Nickel compounds that could be used include nickel octoate, nickel nitrate hexahydrate, nickel sulfate, nickel sulfite, nickel acetate tetrahydrate, nickel citrate hydrate, nickel hydroxide, or nickel hydroxide carbonate. The molar ratio of molybdenum to nickel can range from about 1 : 1 to about 5:1, preferably about 2:1 to about 4:1, or preferably about 2.5:1 to about 3.5:1.

[0041] The sulfur can be provided by a solid or liquid sulfiding agent that is added via line 131 into the petroleum stream in line 132 or added into a recycle stream to the reactor or premixed into the feed. Gaseous sulfiding agents like hydrogen sulfide can be added to the hydrogen line 144. Some preferred sulfiding agents are hydrogen sulfide, dimethyl disulfide, di-tert-butyl (poly)sulfide, dibenzyl disulfide, (di)allyl (di)sulfide, ammonium sulfite, dimethyl sulfite, dithiothreitol, elemental sulfur or thiourea.

[0042] An aqueous molybdenum may be derived from reacting MoOs with an aqueous acid or basic solution such as phosphoric acid or ammonium hydroxide, respectively. Molybdenum in aqueous or oil-soluble liquid form in a volume selected to achieve target concentration may be dropped onto carbon particles which may serve as a carrier.

[0043] Without help from other catalysts, the concentration of the molybdenum in the liquid feeds to the LPH reactor 150 may be more than 0 wppm and no more than about 2 wt % in the liquid feed, suitably no more than about 0.5 wt %in the liquid feed, and typically no more than about 2000 wppm in the liquid feed. In some cases, the concentration of molybdenum may be no less than 1000 wppm in the liquid feed, and preferably not less than 500 wppm of the feed.

[0044] In preferred embodiments where the catalyst contains both nickel and molybdenum, the concentration of the molybdenum in the liquid feed to the LPH reactor is the same as specified above. The concentration of the nickel in the liquid feed to the LPH reactor may be more than 0 wppm and no more than about 2 wt % in the liquid feed, suitably no more than about 0.5 wt % in the liquid feed, and typically no more than about 2000 wppm in the liquid feed. In some cases, the concentration of nickel may be no less than 500 wppm in the liquid feed, and preferably not less than 1000 wppm of the feed. By feed, the aggregate of all feed streams to the reactor is meant.

[0045] In preferred embodiments a stream containing catalyst may be recycled to the reactor. Thus, the concentration of molybdenum in the reactor can be controlled at a steady state greater than the concentration of molybdenum in the liquid feed. The concentration of molybdenum in the reactor liquid is typically between 0.1 wt% and 10 wt%, preferably between 0.5 wt% and 7 wt% and more preferably between 2 wt% and 7 wt%, and even more preferably between 0.2 wt% and 3 wt%.

[0046] Conditions in the LPH reactor 150 generally include a temperature from about 315°C (600°F) to about 538°C (1000°F), or about 321°C (610°F) to about 482°C (900°F), or about 340°C (644°F) to about 470°C (878°F), a pressure from about 3.5 MPa (500 psig) to about 30 MPa (4351 psig), suitably 5.5 MPa (800 psig) to about 19.3 MPa (2800 psig), preferably 6.8 MPa (1000 psig) to about 13.8 MPa (2000 psig), or more preferably no more than about 10.3MPa (1500 psig), and a reactor liquid residence time from about 0.1 to about 8 hrs, preferably 2 to about 6 hrs, or 1 to about 5 hrs, or about greater than 3 hrs.

[0047] In another exemplary embodiment of the present disclosure, the LPH reactor 150 may be a continuous stirred tank reactor (CSTR). Operating conditions in the CSTR 150 may be as given above but may preferably include a temperature from about 300°C (572°F) to about 500°C (932°F), a pressure from about 6.8 MPa (1000 psig) to about 13.8 MPa (2000 psig), and a residence time of about 30 mins, to about 8 hours. From the LPH reactor 150, the upgraded biooil stream is taken in line 154.

[0048] In an aspect, the LPH reactor 150 may be selected from a bubble column reactor, a slurry reactor, and an ebullated bed reactor to facilitate contact and mixing of gases with liquid or slurry materials. Other types of reactors may be used to facilitate contact and mixing.

[0049] In another aspect, the LPH reactor 150 may be a once-through reactor for processing the streams to produce the upgraded bio-oil stream.

[0050] Under hydrotreating conditions, the catalyst in the LPH reactor 150 may hydrodeoxygenate the mixed stream in line 142. In an aspect, the catalyst in the LPH reactor 150 may hydrodeoxygenate carbonyl compounds more selectively than other oxygenates such as phenolics and alcohols. The LPH reactor 150 can be run at different severities resulting in different amounts of oxygen in the stabilized product.

[0051] The composition of the material inside the LPH reactor 150 such as the reaction mixture may be characterized by a band area ratio of oxygenates measured by ATR-IR spectroscopy. In an exemplary embodiment, the composition of the reaction mixture inside the reactor 150 should comprise a ratio of oxygenates of one or more of a (C-O) / C ratio from about 0 to about 0.7 or preferably from about 0 to about 0.5, or more preferably from about 0 to about 0.4; a (C=O) / C ratio from about 0 to about 0.5 or preferably from about 0 to about 0.4 or more preferably from about 0 to about 0.3; an OH / C ratio from about 0 to 2.5, or preferably from about 0 to about 1.5, or more preferably from about 0 to about 1; and an O / C ratio from about 0 to 1.7; or preferably from about 0 to about 1 or more preferably from about 0 to about 0.6.

[0052] The upgraded bio-oil stream in line 154 is passed to a hot separator 160. In the hot separator 160, heavy oil is separated from light oil. A hot bottoms stream is taken in line 156 from the bottoms of the hot separator 160. The hot bottoms stream which contains catalyst isseparated and taken in line 156 from the hot separator 160. The hot bottoms stream in line 156 comprises a majority of the catalyst, for example all the catalyst exiting from the reactor 150, may be taken in the hot bottoms stream in line 156. In an aspect, the hot bottoms stream in line 156 may be characterized as a heavy oil stream comprising catalyst. Light oil is taken in a hot overhead stream in line 155 from the hot separator 160. Water is also separated in the hot separator 160 which is taken with the light oil in the hot overhead stream in line 155. The hot separator 160 may be run at a temperature of about 250°C to about 400°C and at a pressure of about the pressure of the reactor 150.

[0053] The hot bottoms stream in line 156 may be passed to a recycle tank 177. A recycle oil stream comprising the catalyst is taken in line 158 from the bottom of the recycle tank 177. A heavy oil stream may be taken from a side of the recycle tank 177. A predominance of the catalyst may be in the recycle oil stream in line 158. The recycle oil stream in line 158 may be recycled to the reactor 150 perhaps through a pump 157.

[0054] The heavy oil stream in line 179 may be taken in such a way to avoid taking the bulk of the catalyst in this stream. In an aspect, the heavy oil stream in line 179 may be separated to remove a heavy oil stream lean of catalyst. Separation may include fdtration, centrifuge, vacuum flashing, or wiped film evaporation to remove catalyst from a marine fuel oil stream lean of catalyst.

[0055] In an embodiment, the heavy oil stream in line 179 may be passed to a catalyst separation vessel 136 for separating catalyst that may be present. In exemplary embodiment, the catalyst separation vessel 136 may be selected from a filtration vessel, a centrifuge, a vacuum distillation column, a wiped film evaporator, or a combination thereof. In the catalyst separation vessel 136, the catalyst is separated to produce a heavy oil product stream which may include the marine fuel oil. The heavy oil product stream is taken in line 137 from the catalyst separation vessel 136. A concentrated catalyst stream comprising catalyst in heavy oil is taken in line 138 from the vessel 136. The recycle oil stream in line 158 may be combined with the concentrated catalyst stream in line 138 to provide a combined recycle oil stream in line 139 which is recycled to the reactor 150. In an exemplary embodiment, the heavy oil product stream in line 137 comprises marine fuel oil.

[0056] A wiped film evaporator (WFE) uses a hinged blade with minimal clearance from the internal surface to agitate the flowing catalyst containing stream to effect separation of catalyst from heavy oil. In the catalyst separation vessel 136 comprising a WFE, the heavy oil stream in line 179 enters tangentially above a heated internal tube and is distributed evenly over an inner circumference of the tube by the rotating blade perhaps at vacuum. Catalyst particles spiral down the wall while bow waves developed by rotor blades generate highly turbulent flow and optimum heat flux. The heavy oil evaporates rapidly and vapors can flow either co-currently or counter-currently against the catalyst particles. In a simple WFE design, heavy oil may be condensed in a condenser located outside but as close to the evaporator as possible.

[0057] Other evaporative techniques may be used to separate the catalyst from the marine fuel oil in the catalyst separation vessel 136.

[0058] The hydrotreating conditions of the LPH reactor 150 for the liquid phase hydrotreating of the bio-oil stream are selectively chosen and the hydrotreating conditions of the LPH reactor 150 can be adjusted to allow for less oxygen conversion along with less hydrogen consumption.

[0059] The hot overhead stream comprising the light oil in line 155 may be cooled and charged to a cold separator 165. In the cold separator 165, gaseous components may be separated from the light oil. The gaseous components are separated and taken in line 164 from the cold separator 165. The cold overhead stream in line 164 may be purified to obtain a hydrogen stream which may be recycled to the reactor 150. A bottoms light oil stream comprising the upgraded bio-oil stream and aqueous components is taken in line 169 from the cold separator 165. The bottoms light oil stream in line 169 comprises water that should be separated from the upgraded bio-oil stream. The cold separator 165 may be operated at a temperature of about 0 to about 75°C and at a pressure of about the pressure of the reactor 150.

[0060] In an embodiment, the bottoms light oil stream in line 169 is passed to an aqueous separator 147 for separating water from the upgraded bio-oil. Water is separated and taken in an aqueous bottoms line 148 from the aqueous separator 147. A light upgraded bio-oil stream is taken in line 159 from the aqueous separator 147 lean in water concentration. The aqueous separator 147 may be operated at a temperature of about 0 to about 75°C and at a pressure of about 0 MPa (gauge) (0 psig) to about 1 Mpa (gauge) (150 psig).

[0061] In accordance with the present disclosure, the light upgraded bio-oil stream in line 159 comprises a sustainable aviation fuel (SAF) precursor. A SAF precursor can be recovered from the light upgraded bio-oil stream in line 159. The SAF precursor comprises one or more oxygenates including the harder-to-convert oxygen in the form of phenolics, which will eventually be treated in a second stage treating unit. In an exemplary embodiment, the second stage treating unit may be a second stage hydrotreating unit. By not needing to fully remove these oxygenates in the first stage upgrading unit, the SAF precursor may provide an advantage to the user to not run the first stage upgrading unit more severely than necessary and not consume additional hydrogen in the LPH reactor 150. It allows the LPH reactor 150 to not to run at a high severity for a full deoxygenation and run at severity which may provide only deoxygenation up to the point of a usable heavy fuel oil or marine fuel oil. A majority of the remaining oxygen may be taken with the SAF precursor. The SAF precursor is an intermediate stream which is highly cyclic comprising naphthenes and aromatics and a high phenolics content. The SAF precursor may be passed to one or both of a fractionation step and a second stage hydrotreating step to remove the oxygen and produce a sustainable aviation fuel as described below in detail.

[0062] In an embodiment, the light upgraded bio-oil stream in line 159 may be fractionated in a fractionation column 170 to separate the light upgraded bio-oil stream into one or more hydrocarbon streams. The fractionation column 170 may be operated at vacuum pressure. In an embodiment, fractionation column 170 may be operated at an overhead pressure of about 34 kPa (gauge) (5 psig) to about 173 kPa (gauge) (25 psig), and a bottoms temperature of about 500°C (932°F) to about 750°C (1382°F) or about 500°C (932°F) to about 600°C (1112°F).

[0063] The light upgraded bio-oil stream in line 159 may be passed to the fractionation column 170 to provide an overhead stream in line 171. The overhead stream in line 171 may be cooled and passed to a receiver 173 to further separate the overhead stream. From the receiver 173, LPG and light gases are separated in an overhead receiver stream in line 172. The liquid stream in line 174 from the receiver 173 is separated into a reflux stream in line 175 and a naphtha stream in line 176. The reflux stream in line 175 is recycled back to the fractionation column 170. A side cut stream may be taken in a side line 181 from a side of the fractionation column 170. From the bottoms of the fractionation column 170, a bottom stream may be taken inline 178. A reboiling stream may be taken from the bottom stream in line 178, heated in the reboiler 183 and a reboiled stream in line 185 may be passed to the fractionation column 170. A diesel product stream may be taken in line 186 from the bottom stream of the fractionation column 170.

[0064] In an embodiment, the side cut stream in the side line 181 comprises the SAF precursor. The side cut stream in the side line 181 may comprise the SAF precursor for recovering the SAF stream. In an aspect, the side cut stream in the side line 181 has a T10 of more than about 110°C, and a final boiling point of no more than about 500°C. The side cut stream in the side line 181 has a T10 of more than about 110°C, preferably a T10 of more than about 150 °C, and more preferably a T10 of no more than about 160°C. The side cut stream in the side line 181 has a flash point of at least about 38°C, preferably a flashpoint of greater than about 40°C. The side cut stream in the side line 181 generally comprises about 5 to about 50 wt% aromatics and preferably comprises no more than about 35 wt% aromatics. The aromatic content of the side cut stream in the side line 181 is a function of the feed to the LPH as well as the catalyst used and the pressure, and temperature of the LPH. The side line 181 generally comprises no more than about 14 wt% hydrogen, preferably no more than 13% hydrogen. The side line 181 generally comprises no more than about 12 wt% oxygen and preferably no more than 9 wt% oxygen.

[0065] In another embodiment, no side-cut stream 181 is taken from the fractionator 170. In such an embodiment, the SAF precursor, perhaps together with heavier diesel product precursors, may be reboiled in the reboiler 183 and a stream comprising the SAF precursor as well as perhaps a diesel product precursor stream may be taken in line 286.

[0066] In another embodiment, no side-cut stream 181 is taken from the fractionator 170. In such an embodiment, the SAF precursor, perhaps together with a lighter naphtha product precursors, may be condensed in the overhead line 171 and a stream comprising a naphtha product precursor and the SAF precursor may be taken in line 276.

[0067] In an exemplary embodiment, a portion or an entirety of the side cut stream in the side line 181 or the overhead stream in line 176 or a bottoms stream in line 186 if no side cut is taken may be hydrotreated in a second stage hydrotreating unit 187 to produce a SAF stream or SAF blending component. In an embodiment, a hydrotreating charge stream in line 182 may betaken from the side cut stream in the side line 18 Ito be hydrotreated in the hydrotreating unit 187. In an aspect, the hydrotreating charge stream in line 182 may comprise a portion or an entirety of the side cut stream in the side line 181.

[0068] In an aspect, a portion of the naphtha stream in line 176, or a portion of the diesel stream in line 186 may be charged to the second stage hydrotreating unit 187 to be hydrotreated with the hydrotreating charge stream in line 182. In an exemplary embodiment, a naphtha charge stream may be taken in line 276 from the naphtha stream in line 176, and a diesel charge stream may be taken in line 286 from the diesel stream in line 186. One or both of the naphtha charge stream in line 276 and the diesel charge stream in line 286 may be charged to the second stage hydrotreating unit 187. A hydrotreating hydrogen stream in line 189 is also passed to the second stage hydrotreating unit 187. In an embodiment, the naphtha charge stream in line 276 and the diesel charge stream in line 286 may be combined with the portion of the side cut stream in the side line 182 to produce a hydrotreating charge stream which is hydrotreated in the second stage hydrotreating unit 187. A valve 21 is provided on the diesel charge stream in line 286, and a valve 41 is provided on the naphtha charge stream in line 276 to regulate their flow into the second stage hydrotreating unit 187. A portion or an entirety of the side cut stream in the side line 181 may be taken in line 182 and charged to the second stage hydrotreating unit 187 by controlling a valve 31 on line 181. Alternatively, a hydrotreating charge stream or streams can be stored in a tank or transported to a hydrotreating reactor in a different location.

[0069] The second stage hydrotreating unit 187 may comprise a second stage hydrotreating reactor, a separation section. The separation section may comprise a hot separator, a cold separator, a stripping column, and a fractionation column. In an exemplary embodiment, the second stage hydrotreating unit 187 may comprise a fixed bed hydrotreating reactor. The hydrotreating charge stream comprising one or more of the side cut stream in the side line 182, the naphtha charge stream in line 276 and the diesel charge stream in line 286 may be hydrotreated in the second stage hydrotreating reactor to produce a hydrotreated effluent stream. One or more of the side cut stream in the side line 182, the naphtha charge stream in line 276 and the diesel charge stream in line 286 may be contacted with a hydrotreating catalyst, in the presence of the hydrotreating hydrogen stream in line 189, and optionally a recycle stream, at thehydrotreating conditions to produce a hydrotreated effluent stream comprising a sustainable aviation fuel stream.

[0070] The second stage hydrotreating in the second stage hydrotreating reactor may saturate the aromatic, olefinic or unsaturated portions of the hydrotreating charge stream. The hydrotreating catalyst also catalyzes hydrodeoxygenation reactions to remove oxygen functional groups from the oxygenated hydrocarbon molecules in the hydrotreating charge stream which are converted to water and carbon oxides. The hydrotreating catalyst also catalyzes hydrodenitrogenation and hydrodesulfization reactions. Essentially, the hydrotreating reaction hydrodeoxygenates and hydrotreates the hydrotreating charge stream

[0071] The hydrotreating catalyst may be provided in one, two or more beds and employ interbed hydrogen quench streams from the hydrogen quench stream. The hydrotreating catalyst may comprise sulfided forms of molybdenum, nickel, nickel / molybdenum, nickel / tungsten or cobalt / molybdenum dispersed on a high surface area support such as alumina or in an unsupported form. Other catalysts include one or more noble metals dispersed on a high surface area support. Non-limiting examples of noble metals include platinum and / or palladium dispersed on an alumina support such as gamma-alumina. Suitable hydrotreating catalysts include BGB-300, or BGB-350, or BDO 200, or BDO 300, or BDO 400, or HYT-6119, or HYT-6219, or HYT-6319, or HYT-4118, or HYT-4119 available from UOP LLC in Des Plaines, Illinois. The hydrotreating reaction temperature may range from between about 271°C (520°F) and about 427°C (800°F) and preferably between about 304°C (580°F) and about 400°C (752°F). Generally, hydrotreating conditions include a pressure of about 700 kPa (100 psig) to about 21 MPa (3000 psig).

[0072] The hydrotreated effluent stream sent to a separation section where liquid / gas separation and oil / water separation occurs. The hydrotreated effluent stream may be separated in the hot separator, the cold separator, or the stripping column and fractionated in the fractionation column to produce sustainable aviation fuel stream. In the separation section, gas, oil, and aqueous streams are separated according to practices widely known in the art. A portion of gas stream may be taken as an off-gas product and a portion of gas stream may be compressed and recycled to the second stage hydrotreating reactor. An aqueous waste stream may be taken separated from the cold separator. The separated effluent stream may be stripped andfractionated to produce a sustainable aviation fuel stream. A naphtha product stream, and a diesel product stream may also be taken from the fractionation column. A recycle stream may also be taken from fractionation section 221 and recycled to second stage hydrotreating reactor. The sustainable aviation fuel stream is discharged in line 188 from the second stage hydrotreating unit 187.

[0073] In an embodiment, the sustainable aviation fuel stream in line 188 comprises a T10 of more than about 110°C, preferably a T10 of more than about 150 °C, and more preferably a T10 of no more than about 160°C, measured for example by ASTM method D2887 simulated distillation GC.

[0074] In an embodiment, the sustainable aviation fuel stream in line 188 comprises a T90 of no more than about 285°C. In an embodiment the sustainable aviation fuel stream in line 188 comprises a T99 of no more than about 295°C. In an embodiment the sustainable aviation fuel stream in line 188 comprises a final boiling point of no more than about 300°C, measured for example by ASTM method D2887 simulated distillation GC.

[0075] In another embodiment, the sustainable aviation fuel stream in line 188 has a flash point of at least about 38°C, preferably a flashpoint of greater than about 40°C.

[0076] In an aspect, the sustainable aviation fuel stream in line 188 comprises about 2 to about 30 wt% aromatics, preferably about 2 to about 25 wt% aromatics. In an aspect, the sustainable aviation fuel stream in line 188 comprises no more than about 15 wt% hydrogen, and suitably no more than about 14 wt% hydrogen and preferably no more than about 13.7% hydrogen. In an aspect, the sustainable aviation fuel stream in line 188 comprises no more than about 1 wt% oxygen and preferably comprises no more than about 0.2% oxygen. Most preferably the sustainable aviation fuel stream in line 188 comprises no more than about 0.1% oxygen (the detection limit for oxygen by combustion method U649)..

[0077] In an aspect, the sustainable aviation fuel stream in line 188 may be a sustainable aviation fuel blend stock for blending with a fuel stream. The sustainable aviation fuel blend stock may be blended with a renewable fuel stream for example sustainable paraffinic kerosene stream to produce a blended sustainable aviation fuel stream. Alternatively, the sustainable aviation fuel blend stock may be blended with a petroleum stream to produce a blended sustainable aviation fuel stream. Properties and composition of the sustainable aviation fuelcomposition of the present disclosure may refer to the composition of the sustainable aviation fuel blend stock.

[0078] The sustainable aviation fuel stream in line 188 may be analyzed to measure physical properties such as viscosity, density, freeze point, pour point, smoke point, and flash point. Distillation properties and compositional properties such as concentration of elemental carbon, hydrogen, oxygen, and nitrogen may be measured as well. Physical, distillation and composition properties may be measured for instance using appropriate methods known in the art, for instance those specified in ASTM D7566 “Standard Specification for Aviation Turbine Fuel Containing Synthesized Hydrocarbons”. The sustainable aviation fuel stream in line 188 may be further characterized by other methods known in the art such as phenolic acid number titration and two-dimensional gas chromatography (GCxGC).

[0079] In an aspect, the sustainable aviation fuel stream in line 188 comprises a density of between about 0.80 and about 0.85 g / cm3measured at 15°C, for instance by ASTM method D4892. Preferably the sustainable aviation fuel stream in line 188 comprises a density of less than about 0.84 g / cm3measured at 15°C.

[0080] The level of oxygen that may remain present in the aviation fuel stream in line 188 is vanishingly small, typically less than the detection limit of 0.1 wt% measured by oxygen in organics by combustion method U649. The oxygenates that may remain present in the sustainable aviation fuel stream in line 223 may include one or more of phenols, aldehydes, esters, carboxylic acids, ketones, hydroxyls, ethers, sugars, and alcohol groups.

[0081] Further, the trace oxygenates remaining in the sustainable aviation fuel stream in line 188 may comprise primarily phenolic compounds. The concentration of phenols in the sustainable aviation fuel stream in line 188 may be measured by phenolic acid titration. In an exemplary embodiment, the phenolic compounds may include cresol and n-propyl phenol. In an exemplary embodiment, the sustainable aviation fuel stream in line 188 may comprise from about 0.02 millimoles to about 0.10 millimoles of phenolic compounds per gram. The concentration of phenolic compounds may be measured by the method of C. Dence, Determination of Carboxyl Groups, S. Lin Methods in Lignin Chemistry, Springer Series in Wood Science. Springer, Berlin, Heidelberg 458-464. https: / / doi.org / lC'.1007 / 978-3-642-74065- 7. The details of the acid number test are as below:

[0082] 0.05N tetra-n-butylammonium hydroxide solution (TnBAH): Prepared by diluting 50.0 mL of LON TnBAH (Aldrich, SAP# 1014519, 100 mL) solution to 1.00 L in isopropanol. Components were mixed thoroughly before transferring the solution to a Dosimat bottle. The LON TnBAH solution was blanketed with nitrogen and stored in the refrigerator.

[0083] Benzoic Acid: p-Hydroxybenzoic Acid, was stored in a dessicator when not in use.

[0084] Hydrochloric Acid additive solution: 2 mL of concentrated HC1 was added to 100 mL of deionized water and mixed thoroughly. 4 mL of this solution was added to -140 mL of dimethylformamide (DMF) for titration of samples.Standardization of the Titrant:

[0085] 0.15-0.20 g of dried benzoic acid was added into a titration beaker and the weight was recorded to the nearest 0.1 mg. 120 mb of DMF was added and titrate with the TnBAH solution. The standardization was done in duplicate. Normality was calculated to 3 significant figures as per the below formula:g Benzoic acidN = - - - (mL titrant)(0.12212)

[0086] Standardization was repeated every 3 hours when using this procedure.Titration of Samples:

[0087] Prior to the first sample analysis, 0.05-0.08 g of p-hydroxybenzoic acid was weighed into a titration beaker. 140 mL of DMF and 4 mL of the HC1 additive solution was added. The resultant solution was titrated through the 3rdinflection. This was the blank used to calculate the HC1 correction and can be used as a QC for the Phenolic Hydroxyl titrations.

[0088] 0.3-0.4 g of lignin and 0.05-0.08 g of p-hydroxybenzoic acid were weighed into a titration beaker. 140 mL of DMF and 4 mL of the HC1 additive solution were added. Beaker was blanketed with nitrogen and stirred for 5 minutes before titration. Titration was performed with 0.05N TnBAH to the 3rdinflection.Calculations:

[0089] The theoretical titer of the internal standard used was calculated in the blank or sample titration:gpHBAa (mL) =0.13812 (N)and HC1 interference was calculated from the blankc (mL) = [(measured volume to reach 2nd inflection of blank) - (measured 1st inflection)] - (a (mL, calculated above)),then,[(y) - (x) - (c) - (a)]NmEq carboxyl / g sample = - — - [(z) - (y) - (a)]NmEq phenolic hydroxyls / g sample = - wwhere,x = mL at first inflection point;y = mL at second inflection point;z = mL at third inflection point.

[0090] The foregoing method was used to measure acid number typically without use of the p-hydroxybenzoic acid internal standard for expedience. However, use of the internal standard is typically recommended. For acid number, carboxyl acid number and phenolic acid number values were measured using the aforesaid procedure for both the heavy oil product stream and the light oil product stream.

[0091] From the phenolic acid number, which is reported as mgKOH / g, a molar concentration of phenolics is calculated by dividing by 1000 times the molar mass of KOH.

[0092] The sustainable aviation fuel stream in line 223 comprises no detectable oxygen which may be less than 0.1 wt% by combustion analysis by ASTM-U649. The sustainable aviation fuel stream in line 188 has several particular advantages or complimentary characteristics compared to other sustainable jet fuels or blend stocks. In an aspect, the sustainable aviation fuel stream in line 188 comprises about 5 to about 30 wt% aromatics, no more than about 15 wt% hydrogen, and no more than about 1 wt% oxygen. In some exemplary embodiments, the sustainable aviation fuel stream in line 188 may comprise no more than about 14 wt% hydrogen. In particular embodiments the sustainable aviation fuel stream in line 188 may comprise no more than about 13.7 wt% hydrogen. In some exemplary embodiments, the sustainable aviation fuel stream in line 188 may comprise no more than about 0.2 wt% oxygen. In particularly exemplary embodiments, the sustainable aviation fuel stream in line 188 maycomprise no more than about 0.1 wt% oxygen. In an aspect, the sustainable aviation fuel stream in line 188 may comprise a Bromine index (mgBn / IOOg) of less than about 800, measured for example by UOP method U304. In exemplary embodiments bromine index is less than about 300. Bromine index is equivalent to 1000 times the bromine number.

[0093] The sustainable aviation fuel stream in line 188 has about 2 to about 30 wt% aromatics. In exemplary embodiments the sustainable aviation fuel stream in line 188 has about 5 to about 25 wt% aromatics The sustainable aviation fuel stream in line 188 may comprise some polyaromatics such as diaromatics. In an exemplary embodiment, the sustainable aviation fuel stream in line 188 may comprise no more than about 3 wt% diaromatics, suitably no more than 2 wt % diaromatics and preferably no more than 1 wt % diaromatics as measured by comprehensive two-dimensional gas chromatography (GCXGC). In another exemplary embodiment, the sustainable aviation fuel stream in line 188 may comprise no more than about 2 wt % diaromatics. In a preferred embodiment, the sustainable aviation fuel stream in line 188 may comprise no more than about 3 wt % diaromatics, suitably no more than 2 wt % diaromatics and preferably no more than 1 wt % diaromatics. Aromatics content may also be measured by other GC based methods such as ASTM D8267 or D8368. The sustainable aviation fuel stream in line 188 comprises a majority of cyclic hydrocarbons, predominantly naphthenes and polynaphthenes (multi-ring cycloparaffms such as decalin) which is also indicated by a lower hydrogen content than typical paraffinic blend stocks. In an exemplary embodiment, the sustainable aviation fuel stream in line 188 comprises at least 50 wt% naphthenes as measured by comprehensive two-dimensional gas chromatography (GCXGC). In this method polynaphthenes are distinguished from aromatics by utilizing a polar solid phase extraction of aromatics and analyzing the sample both before and after solid phase extraction. In another exemplary embodiment, the sustainable aviation fuel stream in line 188 has a smoke point of at least about 18 mm when analyzed by a smoke point method such as ASTM DI 322, IP 598 or ASTM U1000. In a preferred embodiment the sustainable aviation fuel stream in line 188 has a smoke point of at least about 25 mm. The high smoke point is particularly advantageous for a jet fuel or jet fuel blend stock. Cyclic components like naphthenes and aromatics are known to decrease smoke point and cause soot in exhaust. This jet fuel composition has high levels ofcyclic components, but the types or amounts of cyclic components are not sufficient to reduce smoke point to undesirable levels.

[0094] The sustainable aviation fuel stream in line 188 comprises about 2 to about 30 wt% aromatics including highly saturated naphthenes as measured by comprehensive two-dimensional gas chromatography (GOGC). The sustainable aviation fuel stream in line 188 has a low kinematic viscosity which may be lower than the ASTM D7566 Table 1 specification for jet fuel. Kinematic viscosity may be measured by ASTM methods D445, D7042, D7945 or other kinematic viscosity methods known in the art. In an exemplary embodiment, the sustainable aviation fuel stream in line 188 comprises a kinematic viscosity at-40°C of no more than about 7 mm2 / s and no more than about 12 mm2 / s at 20°C. In exemplary embodiments the sustainable aviation fuel stream in line 188 comprises a kinematic viscosity at -40°C of no more than about 5.5 mm2 / s and no more than about 11.1 mm2 / s at 20°C. The low viscosity of this aviation fuel is particularly advantageous as a blend stock since other sustainable aviation fuel blend stocks tend to have higher viscosity and require blending with low viscosity blend stocks or a limit on their blending to still meet viscosity specifications. In another exemplary embodiment, the sustainable aviation fuel stream in line 188 comprises a cloud point of less than about -40°C and a pour point of less than about -57°C and a freeze point of less than about -60°C The low freeze point of this aviation fuel is particularly advantageous as a blend stock, since other sustainable aviation fuel blend stocks tend to have high freezing points at or around the specification limit.

[0095] The sustainable aviation fuel stream in line 188 may have a high density values due to the high presence of cyclic hydrocarbons. In some embodiments the density of the sustainable aviation fuel is higher than the A-l jet fuel specification, and in these scenarios blending the sustainable aviation fuel blend-stock with other jet fuel blend stocks may be required. In an exemplary embodiment, density of the sustainable aviation fuel stream in line 188 may be about 0.81 to about 0.85 grams per cubic centimeter measured at 15°C.

[0096] The sustainable aviation fuel stream in line 188 generally has a flashpoint that is at or above the A-l specification for jet fuel in ASTM D7566 of 38 °C. In fact, the flashpoint of the sustainable aviation fuel stream in line 188 has a high flash point even if it is fractionated with low initial boiling or T10 boiling point. Thus, this stream may be envisaged as a blend stock witha T10 lower than the ASTM D7566 A-l jet fuel specification (204 °C) while also having a flash point of more than 38°C. In an exemplary embodiment, the sustainable aviation fuel stream in line 188 has a flash point of no less than about 38°C, preferably no less than about 40°C, more preferably has a flash point of no less than about 45°C. The sustainable aviation fuel stream in line 188 has a freeze point that is measured by ASTM D7153, D7154, D2386 or other freeze point methods known in the art. The sustainable aviation fuel stream in line 188 may have a freeze point of no more than about -40°C, suitably nor more than about -60°C, or preferably no more than about -65°C.

[0097] In an aspect, the sustainable aviation fuel stream in line 188 may be used as a blend stock for blending with one or both of a bio-derived fuel stream and a petroleum-derived fuel stream. The sustainable aviation fuel stream in line 188 may be blended with a highly paraffinic jet fuel produced from triglyceride feedstocks such as fats, oils and greases or one produced from methanol, ethanol or Fischer-Tropsch liquids. These other sources of renewable jet fuel blends often have viscosities that have high freeze points, and low densities, and require blending with low viscosity fossil kerosene which are not consistently available in the refinery market. Thus, the sustainable aviation fuel stream in line 188 can be a superior blend stock over the typical paraffinic jet fuel blend stock.

[0098] Another exemplary embodiment of the process of producing a sustainable aviation fuel 101 is shown in FIG. 2. Elements in FIG. 2 with the same configuration as in FIG. 1 will have the same reference numeral as in FIG. 1. Elements in FIG. 2 which have a different configuration as the corresponding element in FIG. 1 will have the same reference numeral but designated with a prime symbol (‘). ‘The configuration and operation of the embodiment of FIG.2 is essentially the same as in FIG. 1 with the following exceptions.

[0099] In the embodiment shown in FIG. 2, the light upgraded bio-oil stream in line 159 is hydrotreated in the second stage hydrotreating unit 187 to produce a SAF stream. The process 101 may comprise the fractionation column 170 to fractionate a hydrotreated stream from the second stage hydrotreating unit 187.[000100] As shown in FIG. 2, the light upgraded bio-oil stream in line 159 may be hydrotreated in the second stage hydrotreating unit 187. The second stage hydrotreating unit 187 may comprise a second stage hydrotreating reactor, a separation section. The separation section maycomprise a hot separator, a cold separator, a stripping column, and a fractionation column. The light upgraded bio-oil stream in line 159 may be passed to the hydrotreating reactor comprising the hydrotreating catalyst in the hydrotreating unit 187. In the hydrotreating reactor, the light upgraded bio-oil stream in line 159 is contacted with a hydrotreating catalyst in a hydrotreating catalyst bed in the presence of the hydrotreating hydrogen at hydrotreating conditions to saturate the olefinic or unsaturated portions of the light upgraded bio-oil stream. The hydrotreating catalyst also catalyzes hydrodeoxygenation reactions to remove oxygenate functional groups from the hydrocarbon molecules in the light upgraded bio-oil stream which are converted to water and carbon oxides. Essentially, the hydrotreating reaction hydrodeoxygenates the light upgraded bio-oil stream, as well as saturating aromatics. The hydrotreating catalyst and the hydrotreating conditions may be the same as described earlier for FIG. 1.[000101] A hydrotreated stream comprising the sustainable aviation fuel stream is discharged from the hydrotreating unit 187 in line 188’. In an aspect, the hydrotreated stream in line 188’ is a SAF precursor stream from which sustainable aviation fuel can be recovered.[000102] In an embodiment, the hydrotreated stream in line 188’ may be fractionated in the fractionation column 170 to produce a sustainable aviation fuel stream or a blend stock.Operating conditions of the fractionation column 170 may be the same as described earlier for FIG. 1. The overhead stream in line 171’ may be passed to a receiver 173 to further separate the overhead stream. From the receiver 173, LPG and light gases are separated in an overhead stream in line 172’. The liquid stream in line 174’ from the receiver 173 is separated into a reflux stream in line 175’ and a naphtha stream in line 176’. The reflux stream in line 175’ is recycled back to the fractionation column 170. A sustainable aviation fuel stream may be taken in a side line 181’ from a side of the fractionation column 170. From the bottoms of the fractionation column 170, a bottom stream may be taken in line 178’. A reboiling stream may be taken from the bottom stream in line 178’, heated in the reboiler 183 and a reboiled stream in line 185’ may be returned to the fractionation column 170. A diesel product stream may be taken in line 186’ from the bottom of the fractionation column 170. In an embodiment, the hydrotreated stream in line 181’ may be a SAF blend stock stream for blending with other fuels including renewable and fossil-based fuel streams. In an exemplary embodiment, the hydrotreated stream in line 181’ may be taken as a SAF blend stock stream for blending with a renewable jet fuel stream.[000103] In an aspect, the sustainable aviation fuel stream in the side line 181’ has a T10 of more than about 110°C and a final boiling point of no more than about 300°C.[000104] In an embodiment, the sustainable aviation fuel stream in line 181’ comprises a T10 of more than about 110°C, preferably a T 10 of more than about 150 °C, and more preferably a T10 of no more than about 160°C.[000105] In another embodiment, the sustainable aviation fuel stream in line 181’ has a flash point of at least about 38°C, preferably a flashpoint of greater than about 40°C.[000106] In an aspect, the sustainable aviation fuel stream in line 181’ comprises about 5 to about 25 wt% aromatics, no more than about 15 wt% hydrogen, no more than about 1 wt% oxygen and a final boiling point of no more than about 300°C.[000107] The sustainable aviation fuel stream in line 181’ may be used as a sustainable aviation fuel blend stock for blending with an aviation fuel stream. The sustainable aviation fuel blend stock may be blended with a renewable fuel stream for example a jet fuel stream. Alternatively, the sustainable aviation fuel blend stock may be blended with a fossil aviation fuel stream. The sustainable aviation fuel stream in the side line 181’ may have a similar composition and properties as described earlier for FIG. 1.EXAMPLES[000108] Kerosene or sustainable aviation fuel blending component was produced from bio-oil in two reaction steps. First, bio-oil from thermal pyrolysis of softwood or hardwood was partially deoxygenated and stabilized in a 2-liter continuous stirred tank reactor, serving as the liquid phase hydrotreating (LPH) step. Of the product produced from the stirred tank reactor, a light stabilized oil and a heavy stabilized oil was collected. Three different light oils were produced in these examples. The light stabilized oils were then hydrotreated in a fixed bed reactor to produce a liquid product comprising a kerosene fraction. In some cases, the liquid product was further fractionated to isolate a blending component for sustainable aviation fuel.[000109] Bio-oil was stored in a storage tank. The bio-oil stream was pumped and kept well mixed in the mixer. A molybdenum- containing catalyst and a soluble sulfur compound were also blended into the stream. The blended feed was pumped at a specified flow rate as per the reactor residence time for the liquid phase hydrotreating (LPH). A hydrogen gas stream wasadded into the bio-oil feed stream upstream of the reactor. After reaction, the product stream went through hot separators, cold separators, and an oil-water separator to finally provide a light oil product stream, a heavy oil product stream, and an aqueous stream. In all runs, the heavy oil product stream was recycled back into the reactor to provide a source of recycled, activated catalyst and deoxygenated oil. An upgraded light stabilized bio-oil stream was discharged from the LPH reactor, corresponding to stream 159. The light stabilized bio-oil stream had relative density of 0.88 g / cm3, an oxygen content of 8.56% by ASTM-U649), a nitrogen content of 2643 wppm by ASTM-D4629, a total carboxylic acid number 82.6 mg KOH / g, phenolic acid number of 92.7 mg KOH / g and simulated distillation ASTM D2887. Conditions for generation of the upgraded light stabilized bio-oil are shown in Table 1.[000110] The light stabilized bio-oil stream was hydrotreated by contacting with nickelmolybdenum based hydrodeoxygenation / hydrotreating catalysts BGB-350 and BDO-400, available from Honeywell UOP in Rosemont, IL. The second stage hydrotreating was done in a fixed bed hydrotreating reactor in the presence of hydrogen for >500 hours. Conditions for hydrotreating were 1800 psig outlet pressure, 1.0 hr'1liquid hour space velocity, 10,000 standard cubic feet of hydrogen flow per barrel of feed and 690-700F operating temperature. Conditions for generation of the hydrotreated liquid product containing the kerosene blending component are shown in Table 1.Table 1[000111] The hydrotreated product produced in Example 1 was fractionated into several fractions. Two of the fractions correspond to the boiling range of sustainable aviation fuel. The properties of the fractions collected between 149-204°C (300-400°F) and 204-288°C (400-550°F) were considered the exemplary sustainable jet fuel blend stocks. The 149-204°C product comprised 20.8% of the total liquid product and the 204-288°C product comprised 19.2% of the total liquid product. These two product cuts were analyzed for density, nitrogen, simulated distillation, flashpoint, smoke point, cloud point, pour point, kinematic viscosity, freeze point, H by NaMR, organic oxygen concentration, acid number, and phenolic acid number. In addition, the products were also analyzed by GCxGC to determine the content of mono- and poly- cyclic naphthenes as well as aromatics. Compositional properties of the overall 149-288°C material were calculated and some physical properties such as viscosity, smoke point, cloud point, pour point and freeze point were measured on the physically composited sample. The results of the individual fractions and the composited fraction are as below in the Table 2:Table 2< < < < < << < << < <The results of the analysis of the two product cuts as per simulated distillation are shown below in Table 3.Table 3[000112] The hydrotreated product produced in Example 2 was fractionated into several fractions. Two of the fractions correspond to the boiling range of sustainable aviation fuel. The properties of the fractions collected between 149-205°C (300-401°F) and 205-270°C (401-518°F) were considered the exemplary sustainable jet fuel blend stocks. The 149-204°C product comprised 22.9% of the total liquid product and the 204-288°C product comprised 22.4% of the total liquid product. These two product cuts were analyzed for density, nitrogen, simulated distillation, flashpoint, smoke point, cloud point, pour point, kinematic viscosity, freeze point, Hby NMR, organic oxygen concentration, acid number, and phenolic acid number. In addition, the products were also analyzed by GCxGC to determine the content of mono- and poly-cyclic naphthenes as well as aromatics. Compositional properties of the overall 149-270°C material were calculated and some physical properties such as viscosity, smoke point, cloud point, pour point and freeze point were measured on the physically composited sample. The results of the individual fractions and the composited fraction are as below in Table 4.Table 4< < < < < << < <<^measured on physically combined sample^Calculated from two fractionated cuts“After CdC12 and Hg washes to remove dissolved H2SThe results of the analysis of the two product cuts as per simulated distillation are as below in Table 5 below.Table 5[000113] The hydrotreated product produced in Example 3 was fractionated into three fractions. The middle fraction corresponds to the boiling range of sustainable aviation fuel. The fraction collected between 142°C-277°C was considered the exemplary sustainable jet fuel blend stock. The 142°C-277°C product comprised 47.0% of the total liquid product. This product was analyzed for density, simulated distillation, flashpoint, smoke point, kinematic viscosity, freeze point, H by NMR, organic oxygen concentration, acid number, and phenolic acid number. In addition, the products were also analyzed for aromatics content by ASTM method D8269. The results are shown in Table 6. The density and aromatics content of the fractionated product inthis example are slightly above the limits set for jet fuel A by ASTM D1655-24. If utilized as-is the composition in this example would serve as a blending component and would be blended with another aviation fuel blending component (conventional or synthetic) in order to reduce the density and aromatic content. Alternatively, it is envisioned based on the density and aromatic content of the full range liquid product and the products from other examples, that utilizing a lower endpoint or a lower initial boiling point in fractionating this product would produce a composition with density less than 0.84 g / cm3 and aromatic content less than 25wt%.Table 6<<<<<<aFull range liquid product aromatics was analyzed by D8368[000114] Table 7 shows simulated distillation D2887 for the feed to the hydrotreating reactor used for Example 3, along with the full range liquid product and 142-277 °C fractionated jet fuel blending component.Table 7<>SPECIFIC EMBODIMENTS[000115] While the following is described in conjunction with specific embodiments, it will be understood that this description is intended to illustrate and not limit the scope of the preceding description and the appended claims.[000116] A first embodiment of the present disclosure is a sustainable aviation fuel composition, the sustainable aviation fuel composition comprising a T10 of more than about 110°C and a final boiling point of no more than about 300°C, about 5 to about 25 wt% aromatics, no more than about 15 wt% hydrogen, no more than about 1 wt% oxygen, and has a flash point of at least about 38°C. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the sustainable aviation fuel composition comprises a T10 of no more than 160 °C. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the sustainable aviation fuel composition comprises a T10 of at least about 150 °C. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the sustainable aviation fuel composition comprises a flashpoint of at least 40 °C. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the sustainable aviation fuel composition comprises at least 50 wt% naphthenes. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the sustainable aviation fuel composition has a flash point of at least about 38°C. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the sustainable aviation fuel composition has a boiling point of about 300°F to about 550°F. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the sustainable aviation fuel composition comprises a smoke point of at least about 20 mm. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the sustainable aviation fuel composition comprises a cloud point of less than about -40°C. An embodiment of the present disclosure is one, any or allof prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the sustainable aviation fuel composition comprises a pour point of less than about -57°C. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the freeze point is no more than about -60°C. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the sustainable aviation fuel composition comprises a kinematic viscosity at -20°C of no more than about 7 mm2 / s. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the sustainable aviation fuel composition comprises no more than about 2 wt% diaromatics. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the sustainable aviation fuel composition is a blend stock for blending with one or both of a bio-derived fuel stream and a petroleum-derived fuel stream.[000117] A second embodiment of the present disclosure is a sustainable aviation fuel composition, the sustainable aviation fuel composition comprising a kinematic viscosity at -20°C of no more than about 7 mm2 / s and a freeze point of less than about -60°C, about 5 to about 25 wt% aromatics, no more than about 15 wt% hydrogen, and no more than about 1 wt% oxygen. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the sustainable aviation fuel composition comprises a T10 of more than 110°C and a final boiling point of no more than 300°C. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the sustainable aviation fuel composition comprises no more than about 3 wt% diaromatics. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the sustainable aviation fuel composition has a freeze point of less than about -65°C. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the sustainable aviation fuel composition comprises at least 50 wt% naphthenes.[000118] A third embodiment of the present disclosure is a process of producing sustainable aviation fuel, comprising reacting a bio-oil stream with hydrogen in the presence of a catalyst in a liquid phase reactor to produce an upgraded bio-oil stream; and hydrotreating the upgraded biooil stream to produce a sustainable aviation fuel stream, the sustainable aviation fuel stream comprising no more than about 25 wt% aromatics, no more than about 15 wt% hydrogen, and no more than about 1 wt% oxygen. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph wherein the reacting a bio-oil stream with hydrogen in the presence of a catalyst in a liquid phase reactor to produce an upgraded bio-oil stream is conducted at a temperature of no more than about 410°C and a pressure of more than about 8 MPa(g). An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph further comprising separating the upgraded bio-oil stream to provide a light oil stream and a heavy oil stream; and hydrotreating the light oil stream to produce the sustainable aviation fuel stream,. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph further comprising fractionating the light oil stream to produce a side cut stream or an overhead stream; and hydrotreating the side cut or overhead stream to produce the sustainable aviation fuel stream. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph further comprising hydrotreating the light oil stream to produce a hydrotreated stream; and fractionating the hydrotreated stream to produce the sustainable aviation fuel stream. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph wherein the side cut stream or overhead stream comprises from about 0.02 millimoles to about 0.10 millimoles of phenolic compounds per gram. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the side cut stream or overhead stream has a cut point of about 148°C to about 290°C.[000119] Without further elaboration, it is believed that using the preceding description that one skilled in the art can utilize the present disclosure to its fullest extent and easily ascertain the essential characteristics of this disclosure, without departing from the spirit and scope thereof, tomake various changes and modifications of the disclosure and to adapt it to various usages and conditions. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limiting the remainder of the disclosure in any way whatsoever, and that it is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.[000120] In the foregoing, all temperatures are set forth in degrees Celsius unless otherwise indicated, and all parts and percentages are by weight, unless otherwise indicated.

Claims

CLAIMS1. A sustainable aviation fuel composition, the sustainable aviation fuel composition comprising a T10 of at least about 110°C and a final boiling point of no more than about 300°C, about 5 to about 25 wt% aromatics, no more than about 15 wt% hydrogen, no more than about 1 wt% oxygen, and has a flash point of at least about 38°C.

2. The sustainable aviation fuel composition of claim 1 comprising a T10 of no more than 160 °C.

3. The sustainable aviation fuel composition of claim 2 comprising a flashpoint of at least 40 °C.

4. The sustainable aviation fuel composition of claim 1 comprising a T10 of at least about 150 °C.

5. The sustainable aviation fuel composition of claim 1, wherein the sustainable aviation fuel composition comprises at least 50 wt% naphthenes.

6. The sustainable aviation fuel composition of claim 1, wherein the sustainable aviation fuel composition comprises a smoke point of at least about 20 mm.

7. The sustainable aviation fuel composition of claim 1, wherein the sustainable aviation fuel composition comprises a cloud point of less than about -40°C.

8. The sustainable aviation fuel composition of claim 1, wherein the sustainable aviation fuel composition comprises a pour point of no more than about -57°C.

9. The sustainable aviation fuel composition of claim 1, wherein the sustainable aviation fuel composition comprises a kinematic viscosity at -20°C of no more than about 7 mm2 / s.

10. The sustainable aviation fuel composition of claim 1, wherein the sustainable aviation fuel composition comprises no more than about 3 wt% diaromatics.

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