WO2025072600A1 - Catalytic decarboxylation/decarbonylation of oleaginous feeds including rosin acids to sustainable aviation fuel blendstock - Google Patents

Abstract

The present disclosure concerns systems and methods for the upgrade of distilled tall oil (DTO) to synthetic aromatic kerosene (SAK) for use as Sustainable Aviation Fuel (SAF) blendstock via decarboxylation/ decarbonylation. By introducing a metal-scaffold catalyst, a DTO feedstock with rosin acids can undergo decarboxylation and/or decarbonylation throughout the steps as described herein. The catalysts maintain deoxygenation activity while avoiding excessive cracking. The system and methods further provide a blendstock that swells seals in aircraft systems.

Description

129529-134 1 CATALYTIC DECARBOXYLATION/DECARBONYLATION OF OLEAGINOUS FEEDS INCLUDING ROSIN ACIDS TO SUSTAINABLE AVIATION FUEL BLENDSTOCK CROSS-REFERENCE TO RELATED APPLICATIONS [0001] The present application claims priority to U.S. Provisional Patent Application 63/586,170, filed September 28, 2023, the content of which is hereby incorporated by reference in its entirety. FIELD [0002] The present disclosure concerns systems and methods to upgrade oleaginous materials such as fats, oils, and greases (FOG) as well as rosin acids into sustainable aviation fuel. BACKGROUND [0003] The reduction of greenhouse gas emissions and the diversion of low-quality waste oils away from sewer systems and landfills represent two goals that can be accomplished through novel technology to produce Sustainable Aviation Fuel (SAF). Indeed, the oil fraction of a) algae cultivated using greenhouse gases produced from the combustion of fossil fuels; and/or of b) the millions of tons of brown grease currently landfilled – to name only two sources of FOG – can be upgraded to SAF along with other feedstock (e.g., rosin) by catalysts capable of deoxygenating these feeds via decarbonylation/decarboxylation (deCOx). SUMMARY [0004] A 1^st aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns a system for producing one or more hydrocarbons for sustainable aviation fuel (SAF) comprising a catalyst composition comprised of 2 to 20 wt.% of a metal on a support; heat energy at a temperature of from about 250 °C to about 500 °C; pressure ranging from 1 to about 40 bar; and a feedstock of one or more fats, oils, and greases (FOGs) comprising mono-, bi- , or tri-glycerides, fatty acids, fatty acid esters, and/or rosin acids, such as yellow grease, brown grease, tall oil, algae oil, rosin, isomerized fatty acids, or any combination thereof. [0005] A 2^nd aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the system of the 1^st aspect, wherein the metal is selected from iron, nickel, copper, or a combination thereof. 129529-134 2 [0006] A 3^rd aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the system of the 1^st or 2^nd aspect, wherein the metal is nickel, copper, or a combination of nickel and copper. [0007] A 4^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the system of the 3^rd aspect, wherein the metal is a combination of nickel and copper. [0008] A 5^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the system of the 4^th aspect, wherein the metal is of a ratio of nickel to copper of about 4:1. [0009] A 6^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the system of the 1^st aspect, wherein the support is comprised of an alumina, another oxide, and/or a zeolite or zeotype material. [0010] A 7^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the system of the 1^st or 6^th aspect, wherein the support comprises SAPO- 11. [0011] An 8^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the system of the 1^st aspect, wherein the feedstock comprises rosin at an amount of about 20-50 percent of the content of the feedstock. [0012] A 9^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the system of the 1^st aspect, further comprising a steam reforming zone. [0013] A 10^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns a method for producing one or more hydrocarbons for sustainable aviation fuel (SAF) comprising preparing a feedstock of one or more FOGs with one or more rosin acids added therein and providing heat and a catalyst composition, wherein the catalyst composition comprises a metal and a support. [0014] An 11^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 10^th aspect, wherein the metal is selected from iron, nickel, copper, or a combination thereof. [0015] A 12^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 10^th or 11^th aspect, wherein the metal is nickel, copper, or a combination of nickel and copper. 129529-134 3 [0016] A 13^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 12^th aspect, wherein the metal is a combination of nickel and copper. [0017] A 14^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 13^th aspect, wherein the metal is of a ratio of nickel to copper of about 4:1. [0018] A 15^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 10^th aspect, wherein the support is an alumina, another oxide, and/or a zeolite or zeotype material. [0019] A 16^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 10^th or 15^th aspect, wherein the support comprises SAPO-11. [0020] A 17^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 10^th aspect, wherein the feedstock comprises rosin at an amount of about 20-50 percent of the content of the feedstock. [0021] An 18^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 10^th aspect, wherein the heat is provided at a temperature of about 250 to 500 °C. [0022] A 19^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 10^th aspect, wherein the produced hydrocarbons include one or more of an alkane, an iso-alkane, a cyclo-alkane, and an aromatic. [0023] A 20^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 10^th aspect, further comprising a hydrogenation step of the feedstock with a platinum group metal. [0024] A 21^st aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 20^th aspect, wherein the platinum metal is selected from ruthenium, platinum, rhodium, palladium, or a combination thereof. [0025] A 22^nd aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 20^th or 21^st aspect, wherein the hydrogenation step is performed with a sulfided catalyst. 129529-134 4 [0026] A 23^rd aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 22^nd aspect, wherein the sulfided catalyst is sulfided NiMo and/or sulfided NiW. [0027] A 24^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 20^th, 21^st, 22^nd, or 23^rd aspect, wherein the hydrogenation step is performed in the presence of a base metal. [0028] A 25^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 24^th aspect, wherein the base metal is selected from nickel, molybdenum, tungsten, iron, lead, zinc, copper, tin, germanium, titanium, cobalt, rhenium, chromium, uranium, indium, gallium, thallium, dysprosium, or a combination thereof. [0029] A 26^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 10^th or 20^th aspect, wherein preparing the feedstock comprises removing contaminants from the feedstock. [0030] A 27^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 26^th aspect, wherein contaminants are removed by providing the feedstock over a guard bed. [0031] A 28^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 26^th aspect, wherein removing the contaminant includes filtration of the feedstock and/or solvent extraction of the feedstock. [0032] A 29^th aspect of the present disclosure, either alone or in combination with any other aspect herein, concerns the method of the 10^th or 20^th aspect, further comprising processing obtained products through isomerization and/or cyclization. BRIEF DESCRIPTION OF THE DRAWINGS [0033] FIG. 1A shows temperature-programmed reduction for NCSAPO. [0034] FIG. 1B shows t temperature-programmed desorption for NCSAPO. [0035] FIG. 1C shows Ni 2p XPS for fresh NCSAPO. [0036] FIG. 2A shows composition of DTO (t=0) and of the product mixtures of DTO upgrading at 480 C over NCSAPO at a WHSV of 1 h^-1 _. This experiment was performed in duplicate, resulting in an average yield of aromatics of ~86% with standard deviation of ±4.98. [0037] FIG. 2B shows composition of the gas exhaust. This experiment was performed in duplicate, resulting in an average yield of aromatics of ~86% with standard deviation of ±4.98. 129529-134 5 [0038] FIG.3A shows carbon number of the liquid products of DTO upgrading at 480 °C over NCSAPO at a WHSV of 1 h^-1 as a function of TOS. [0039] FIG. 3B shows jet fuel boiling point (JFBP) range classification of liquid products. [0040] FIG. 4A shows composition of DTO (t=0) and of the product mixtures of DTO upgrading at 480 °C over NCSAPO at a WHSV of 8 h^-1. This experiment was performed in duplicate, resulting in an average selectivity to aromatics of ~86% with standard deviation of ±6.5. [0041] FIG. 4B shows composition of the gas exhaust. This experiment was performed in duplicate, resulting in an average selectivity to aromatics of ~86% with standard deviation of ±6.5. [0042] FIG.5A shows carbon number of the liquid products of DTO upgrading at 480 °C over NCSAPO at a WHSV of 8 h^-1 as a function of TOS. [0043] FIG. 5B shows jet fuel boiling point (JFBP) range classification of liquid products. [0044] FIG.6A shows composition and class of aromatics present in DTO upgrading products WHSV – 1 h^-1 _. [0045] FIG.6B shows composition and class of aromatics present in DTO upgrading products WHSV – 8 h^-1. [0046] FIG. 7A shows Ni 2p photoelectron spectrum (of NCSAPO. [0047] FIG. 7B shows Cu 2p photoelectron spectrum of NCSAPO. [0048] FIG. 8A shows TEM micrograph for spent NCSAPO before regeneration. [0049] FIG. 8B shows elemental mappings of composite elements. [0050] FIG. 8C shows elemental mappings of Ni. [0051] FIG. 8D shows elemental mappings of Cu. [0052] FIG. 8E shows elemental mappings of Al. [0053] FIG. 8F shows elemental mappings of Si. [0054] FIG. 8G shows particle size distribution (8F) metallic composition [WHSV – 1h^-1]. [0055] FIG. 9A shows TEM micrograph for spent NCSAPO after regeneration. [0056] FIG. 9B shows elemental mappings of composite elements. [0057] FIG. 9C shows elemental mappings of Ni. [0058] FIG. 9D shows elemental mappings of Cu. [0059] FIG. 9E shows elemental mappings of Al. [0060] FIG. 9F shows elemental mappings of Si. [0061] FIG. 9G shows particle size distribution (8F) metallic composition [WHSV – 1h^-1]. 129529-134 6 [0062] FIG. 10A shows thermogravimetric analysis of spent catalysts before and after regeneration at WHSV = 1 h^-1. [0063] FIG. 10B shows thermogravimetric analysis of spent catalysts before and after regeneration at WHSV = 8 h^-1 [0064] FIG. 11 shows a scheme for the proposed reaction pathway of DTO to SAK over NCSAPO catalyst. [0065] FIG. 12 shows the reaction scheme demonstrating deCO_x/isomerization/cyclization to yield SAF. DETAILED DESCRIPTION [0066] The present disclosure concerns systems and methods for upgrading oleaginous materials, including fats, oils, and greases (FOG) to hydrocarbons for use as a fuel, such as sustainable aviation fuel (SAF). These materials represent an attractive portfolio of feedstocks for sustainable fuel production since many waste FOG – including tall oil and brown grease (BG) – cannot be readily converted to biodiesel due to their high free-fatty acid concentrations. In some aspects, the FOG feedstocks of the present disclosure may include mono-, di-, and tri-glycerides, free fatty acids (FFAs), and fatty acid alkyl esters (FAAEs) such as fatty acid methyl esters (FAMEs) or fatty acid ethyl esters (FAEEs). The aliphatic carbon chains in the glycerides, FFAs, or FAAEs can be saturated or mono-, di-, or poly-unsaturated. Notably, millions of tons of these waste materials are landfilled each year. Additionally, the upgrading of biologically-derived oils – such as those contained in the algae oil (AO) from carbon capture and utilization systems leveraging the photosynthetic activity of microalgae – to hydrocarbons offers a way to recycle the carbon captured from the combustion of fossil fuels. [0067] In some aspects, the system and methods of the present description concern introducing an oleaginous material feedstock containing one or more rosin acids into a reaction chamber and contacting the feed with a catalyst. The oleaginous material or feedstock may include fats, oils, and/or greases. In some aspects, the oleaginous material or feedstock may include brown grease (BG) and/or yellow grease (YG) and/or tall oil fatty acids and/or algae oil and/or isomerized fatty acids. Such may include a collection of combined fats, oils, and/or greases of varying viscosities. In some aspects, the oils and/or fats and/or greases may be of animal and/or plant origin. In some aspects, the oleaginous material may include waste materials, such as from food preparations, butchering, grease traps, cooking, and the like where oleaginous waste may be expected to occur. It will be understood that oleaginous material need not be constituted by any particular amount of hydrocarbon, lipid, carbohydrate, protein, sterol, triglyceride, fatty acid, alkane, alkene, cyclic 129529-134 7 hydrocarbon, phenol, or similar components, but instead can be provided as a non-descript oleaginous mass or collection of fats, oils, and greases (FOGs). In some aspects, the FOG feedstocks of the present disclosure may include mono-, di-, and tri-glycerides, free fatty acids (FFAs), and/or fatty acid alkyl esters (FAAEs), such as fatty acid methyl esters (FAMEs) or fatty acid ethyl esters (FAEEs). [0068] In some aspects, the system and methods of the present description concern contacting the oleaginous material with a catalyst composition to produce hydrocarbons, such as paraffinic hydrocarbons, isomerized hydrocarbons, cyclic hydrocarbons and/or aromatic hydrocarbons. In some aspects, the catalyst composition includes a catalyst that may include one or more metals supported, retained, linked, or bound to a carrier, support, or scaffold material. In some aspects, the metal is nickel, palladium, platinum, iron, ruthenium, cobalt, rhodium, or copper. In some aspects, the metal is a combination of these metals, such as nickel promoted with copper and/or iron. In some aspects, the metal is two or more metals in combination and at a ratio to each other, such as metal1 and metal2 , wherein the ratio is of about 10:1 to about 1:10, including about 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, and 1:9. In some aspects, metal₁ is nickel and metal2 is copper and/or iron. [0069] In some aspects, the carrier is a metallic oxide such as alumina, zirconia, ceria, titania, silica, a combination thereof, or a mixed metal oxide. In some aspects, the carrier is a combination of metallic oxides, such as silica and aluminina. In some aspects, the carrier may include a phosphorous or a phosphorous oxide, such as PO₄ or P₂O₅. In some aspects, the carrier is a zeotype or zeolite such as SAPO-11, SAPO-31, SAPO-34, SAPO-41, ZSM-5, ZSM-11, ZSM-22, or ZSM- 23. In some aspects, the system and the method include contacting oleaginous material with a catalyst composition that further provides the presence of a rosin. In some aspects, the catalyst is a non-sulfided catalyst. In some aspects, the catalyst is a nitrated metal catalyst. In some aspects, the catalyst is nickel nitrate or a copper nitrate. In some aspects, the catalyst is of a nitrated metal precursor. [0070] In some aspects, the present disclosure concerns the upgrade of distilled tall oil (DTO) to synthetic aromatic kerosene (SAK). As set forth in the Examples herein, Sustainable Aviation Fuel (SAF) blendstock was achieved via decarboxylation/ decarbonylation, a process that offers an attractive alternative to hydrodeoxygenation that allows the use of lower amounts and pressures of hydrogen, feedstocks of low purity and cost, and simple supported metal catalysts. As set forth in the examples, a mixture of the catalyst and SiC used as diluent (0.5 g of each, particle size 150– 300 μm) was used to establish a catalyst bed held in place using a stainless-steel frit. The catalyst 129529-134 8 was then reduced under flowing H₂ at 400 °C for 3 h before adjusting the temperature to 480 °C and pressurizing the reactor with H2 to 580 psi. A liquid solution of the feed in dodecane (50 wt. % DTO and 50 wt. % dodecane) was introduced to the system at a rate of 0.02 mL/min – which corresponds to a weight hour space velocity (WHSV) of 1 h^-1 (calculated ignoring the SiC diluent and the dodecane solvent) – along with a flow of H₂ (60 sccm). A liquid gas separator (kept at 0 °C) placed downstream from the catalyst bed was used to collect liquid samples, incondensable gases being collected for GC analysis. Quantitative conversion of DTO was obtained over Ni- Cu/SAPO-11 operated in a continuous mode for 144 h with a regeneration step after 72 h time- on-stream. Reaction products included all component types present in commercial jet fuel, namely, n-alkanes, iso-alkanes, cycloalkanes, and aromatics, with high selectivity (>80%) to aromatics within the jet fuel boiling point range. [0071] In some aspects, the catalyst includes a metal and a support. In some aspects, the metal may be nickel, iron, copper, or combinations thereof such as nickel-copper, nickel-iron, and nickel-iron-copper compounds. In some aspects, the metal may be of about 0.5 to about 50 % by weight of the catalyst, including about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, and 45 %. In some aspects, the support may include an alumina, zirconia, titania, ceria, silica, a combination thereof, or a mixed metal oxide, and/or a zeolite or zeotype material. In some aspects, the zeolite or zeotype may include BEA, MOR, MFI, FAU, zeolite Y, ZSM, SAPO, SM3 or combinations thereof. [0072] In some aspects, the system and methods of the present disclosure concern application of rosin as part of the feedstock for deCOx of the oleaginous material or FOGs. In some aspects, the rosin may include one or more rosin acids, including abietic acid, neoabietic acid, palustric acid, levopimaric acid, dehydroabietic acid, pimaric acid, sandaracopimaric acid, isopimaric acid, or combinations thereof. In some aspects, the rosin may include two or more rosin acids. In some aspects, the rosin is of about 1 to about 90 % by weight of the feed, including about 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, and 85 %. [0073] In some aspects, the systems and the methods of the present disclosure require heat or other form of energy to assist in the deCOx reactions set forth herein to assist in the production of paraffinic hydrocarbons, isomerized hydrocarbons, cyclic hydrocarbons and/or aromatic hydrocarbons. In some aspects, the system and the methods set forth herein require that heat be applied at temperatures of about 250 °C to about 500 °C, including about 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, and 490 °C. 129529-134 9 [0074] In some aspects, the systems and methods of the present disclosure require supply of hydrogen gas or H₂ and pressures from 1 to 40 bar, including about 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, and 35 bar. [0075] In some aspects, the system and methods of the present description provide for the production of paraffinic hydrocarbons, isomerized hydrocarbons, cyclic hydrocarbons and/or aromatic hydrocarbons through the conversion of oleaginous material. In some aspects, the catalyst promotes decarboxylation and/or decarbonylation of the oleaginous materials including rosin. For example, a fatty acid can undergo decarboxylation and/or decarbonylation (both collectively referred to as deCO_x) in the presence of the catalyst to form carbon dioxide and a linear alkane or carbon monoxide and a linear alkene. Under hydrodeoxygenation (HDO), with the addition of three hydrogen gas molecules, only water and a linear alkane result. The reactions of decarboxylation and/or decarbonylation can utilize non-sulfided catalysts with lower pressures of H₂, whereas hydrodeoxygenation utilizes sulfide catalysts with high pressures of H₂. An overview of the different reactions is set forth in equation I:

[0076] Table 1 below sets forth as comparison between HDO and deCO_x reactions. Table 1. How proposed technology will overcome key challenges of HEFA technology

129529-134 10

[0077] Among the advantages summarized in Table 1, the ability of deCOx to upgrade inedible, waste, and algal bioresources – whose sustainable potential exceeds 0.8 billion tons from tall oil fatty acids and rosin alone – is of particular note. Indeed, while blends of conventional jet fuel and ≤50% AJF from HEFA are already approved, a variety of biomass or waste resources can ^be upgraded via deCO_x to obtain bio-derived jet fuel blends showing optimal composition, properties, cost, and emissions. For instance, the deCOx of ester or fatty acid feeds and rosin can respectively afford n-alkanes and cyclo-alkanes, the former contributing high specific energy and the latter satisfying seal swelling requirements in drop-in AJF free of aromatics. Complimentarily, deCO_x coupled with isomerization and cyclization can afford a drop-in AJF with improved cold- flow and seal swelling properties in a single step. [0078] In some aspects, the systems and methods of the present disclosure allow for the production of cyclic hydrocarbons through the contact between the oleaginous materials including rosin and the catalysts described herein. In some aspects, rosin is added to the feedstock. For example, the presence of one or more rosin acids provide additional compounds for the deCO_x reactions provided in the system and methods. For example, abietic acid can undergo deCOx reactions to produce norabietane, 18-norabieta-8,11,13-triene, and norabieta-4,8,11,13-tetraene. [0079] In some aspects, following deCOx, the products may be further processed through steps such as isomerization and/or cyclization to provide for iso-alkanes and/or cycloalkanes. [0080] In some aspects, the system and the methods of the present disclosure include options to remove contaminants from the feedstock. Such may include alkali metals such as sodium and potassium that may be present from the source materials used to generate the oleaginous material. Such may also include water. Such may also include detergents or surfactants. In such aspects, an optional first step is to remove contaminants prior to contact with the catalysts compositions as described herein. In certain aspects, providing the feedstock to a guard bed, such as an alumina guard bed with optional demetallation catalysts. In some aspects, such steps may include filtration 129529-134 11 and/or solvent extraction. In some aspects, the oleaginous material or feedstock may be hydroprocessed prior to contact with the catalyst compositions as described herein. [0081] In some aspects, the oleaginous material or feedstock may additional undergo a hydrogenation step with a platinum group metal, such as ruthenium, platinum, rhodium, palladium, or combinations thereof. Such may occur prior to or post contact with the catalyst compositions described herein. In some aspects, hydrogenation may be with a sulfide catalyst, such as sulfided NiMo and/or sulfides NiW. In some aspects the hydrogenation may be with a base metal such as nickel, molybdenum, tungsten, iron, lead, zinc, copper, tin, germanium, titanium, cobalt, rhenium, chromium, uranium, indium, gallium, thallium, dysprosium, or combinations thereof. [0082] In some aspects, the system and the methods of the present disclosure may optionally include a steam reforming zone to provide hydrogen to any other zone set forth herein, such as a deCO_x zone, as well as a hydrogenation zone, an isomerization zone, or a hydrocracking zone. [0083] In some aspects, the catalysts and catalyst compositions of the present disclosure may be recycled and/or regenerated to allow for their re-application to the systems and/or methods of the present disclosure. [0084] The Examples presented herein demonstrate the catalytic conversion of distilled tall oil (DTO) to SAF blendstock via deCOx. The feed was upgraded over a bimetallic Ni-Cu catalyst with SAPO-11 as support. A continuous experiment was conducted in a fixed-bed reactor at a WHSV of h^-1, comprising two 72-hour cycles with an intermediate catalyst regeneration step. The results revealed that DTO conversion remained quantitative throughout the run, and the yield of aromatics was ≥80% regardless of TOS. In addition, 67% of the liquid products fell within the jet fuel range (CN and BP) at all reaction times sampled. This indicates that the NCSAPO catalyst maintained its deoxygenation activity while avoiding excessive cracking.Further, the synthetic aromatic kerosene blendstock produced showed remarkable potential for swelling the seals used in aircraft fuel systems. EXAMPLES [0085] The primary goal of this technology is to deoxygenate oleaginous feedstocks including rosin to produce SAF, special preference being given to reaction products that display adequate boiling point, cold-flow, and seal-swelling properties for aviation applications. Given that excellent results on the conversion of BG, YG and AO to fuel-like hydrocarbons via deCO_x have been obtained using industrially-relevant conditions, initial experiments have focused on the upgrading of rosin-containing mixtures using similar conditions. As a starting point, distilled tall 129529-134 12 oil (DTO) – an inexpensive biomaterial stemming from the pulping process comprising ca. 50% fatty acids, 30% rosin acids and 20% neutral polycyclic oxygenated species such as sterols – has been upgraded. The gaseous and liquid products of reactions have been monitored as a function of time on stream by residual gas analysis (RGA) and simulated distillation gas chromatography- mass spectrometry. This has provided information regarding the boiling point distribution of the product mixture, but also its chemical composition, as a function of reaction time. Based on the results of initial experiments, the constituents of AO, BG, and YG have been included in co- processing experiments where the feedstock has been combined with CTO and/or rosin at various ratios to identify the feedstock composition leading to the liquid products most suitable for use as a drop-in SAF. Some of these experiments have revealed the need for additional isomerization, which has been achieved using zeolitic supports (such as SAPO-11) instead of alumina. The experiment affording the best results has been extended into a 72-hour run followed by on-line regeneration and another 72-hour cycle to assess the impact of both feedstock and time on stream on catalyst activity, selectivity, stability, and recyclability. The higher volume of SAF resulting from this experiment allows for a more thorough evaluation to be performed using ASTM methods with which the applicants are familiar. [0086] Catalyst preparation and characterization [0087] Catalysts were prepared via incipient wetness impregnation – using Ni(NO3)2 • 6H2O (Alfa Aesar) and Cu(NO₃)₂ • 3H₂O (Sigma Aldrich) as metal precursors and SAPO-11 (ACS MATERIAL) as the support – targeting a Ni loading of 10 wt. % and Cu loading of 2.5 wt. %. After drying under vacuum overnight at 60 °C, the catalysts were calcined at 500 °C for 3 h in static air. [0088] The elemental composition of the different catalysts synthesized was confirmed via inductively coupled plasma optical emission spectroscopy (ICP OES) on a Varian 720-ES analyzer enhanced with an autosampler. About 0.1g of the catalyst sample was weighed and dissolved in 10 mL of hydrochloric and nitric acids. This solution was heated at 90°C for at least 30 minutes until its volume was reduced to 5 mL. Afterwards, the samples were cooled to ambient temperature and diluted to a total volume of 25 mL. Osmium was employed as an internal standard. [0089] The textural properties (surface area, average pore radius, and pore volume) of the catalysts were determined via N₂ physisorption using previously described instrumentation and methods. X-ray diffraction (XRD) measurements were conducted on a Phillips X'Pert diffractometer using Cu Kα radiation. The X-ray diffractograms were recorded in the range of 10- 129529-134 13 90° with a step size of 0.02°. The Scherrer equation was applied to the (111) facet of NiO peak to calculate the average NiO particle size. The thermogravimetric analysis (TGA) of spent catalysts was carried out using a Discovery Q500 thermogravimetric analyzer (TA Instrument, USA). Prior to TGA, the catalysts were dried overnight in a vacuum oven at 60 °C. The samples were heated in air flow (50 mL/min) from ambient temperature to 800 °C at a rate of 10 °C/min. [0090] Temperature programmed-reduction (TPR) and ammonia temperature-programmed desorption (NH3-TPD) measurements were performed to respectively study catalyst reducibility and acidity using a Micromeritics AutoChem II chemisorption analyzer equipped with a thermal conductivity detector (TCD) and a Pfeiffer Thermostar Mass Spectrometer (MS) detector. For TPR, 250 mg of catalyst were pulverized to a size <150 µm before placing the resulting powder in a quartz U-tube reactor and connecting the latter to the instrument. The system was purged with Ar for 5 min prior to switching the gas flow to 100 sccm of 10% H₂/Ar and waiting until the TCD signal stabilized. The reactor was then heated from room temperature to 900 °C at a rate of 10 °C/min, the sample temperature being monitored using a thermocouple placed inside the catalyst bed. Detailed procedures about the NH₃-TPD measurements are available in a previous report. Briefly, the prepared catalysts were reduced under 60 sccm of 10% H2/Ar at 350 °C for 3 h. Afterwards, the system was flushed with Ar at 400 °C and the same gas was used to cool down the catalyst bed to 30 °C. NH₃ was adsorbed at this temperature by flowing 100 sccm of 1% NH₃/N₂ for 1 h, after which physisorbed NH₃ was purged with Ar. Finally, the temperature of the system was ramped from 30 °C to 500 °C at a rate of 10 °C/min. [0091] The surface concentration (in at. %) of the elements comprising the catalyst and the oxidation state of the metals at the catalyst surface were determined via X-ray photoelectron spectrometry (XPS) using previously described equipment and methods. Briefly, XPS analyses were performed using a PHI 5000 Versaprobe apparatus using a monochromatic Al Kα1 X-Ray source that is enhanced with energy of 1486.6 eV, accelerating voltage of 15 kV, power of 50 W, and spot size diameter of 200 µm. Fresh and spent catalyst samples were reduced under a flow of H2 at 350 °C for 3 h before XPS analysis. XPS spectra were processed using the CasaXPS software package. [0092] Transmission electron microscopy (TEM) measurements were performed using a Thermo Scientific Talos F200X analytical electron microscope enhanced with a SuperX system that is made up of 4 windowless silicon drift detectors (SDD) as reported in previous works. Briefly, ~0.1 mg of each catalyst was sonicated in water for about 20 minutes, after which a drop of the suspension was carefully placed on top of a 400-mesh lacey carbon Au grid and 129529-134 14 subsequently allowed to dry in air. The catalyst-loaded grids were then introduced into the analytical electron microscope (which was operated at 200 keV) for imaging and elemental mapping. [0093] Catalyst testing [0094] Distilled tall oil (DTO) was upgraded in a fixed-bed stainless steel tubular reactor (1/2 in o.d.) equipped with an HPLC pump. A mixture of the catalyst and SiC used as diluent (0.5 g of each, particle size 150–300 μm) was used to establish a catalyst bed held in place using a stainless- steel frit. The catalyst was then reduced under flowing H2 at 400 °C for 3 h before adjusting the temperature to 480 °C and pressurizing the reactor with H₂ to 580 psi. A liquid solution of the feed in dodecane (50 wt. % DTO and 50 wt. % dodecane) was introduced to the system at a rate of 0.02 mL/min – which corresponds to a weight hour space velocity (WHSV) of 1 h^-1 (calculated ignoring the SiC diluent and the dodecane solvent) – along with a flow of H₂ (60 sccm). A liquid gas separator (kept at 0 °C) placed downstream from the catalyst bed was used to collect liquid samples, incondensable gases being collected using Tedlar^® bags for GC analysis. Additional details regarding the equipment and methods employed can be found in previous contributions. [0095] Product analysis [0096] The identity and quantity of all compounds in the feed employed and the liquid products collected were determined via dual detection GC using instrumentation and methods described in previous contributions. Briefly, analyses were performed using an Agilent 7890A GC equipped with an Agilent 5977A extractor MS detector and flame ionization detector (FID). The inlet was operated in split mode (split ratio 25:1; split flow 50 mL/min) using an initial temperature of 100 °C. Inlet temperature was increased immediately upon injection (at a rate of 8 °C/min) to a final temperature of 320 °C, which was maintained for the duration of the analysis. The initial oven temperature of 45 °C was increased upon injection first to 325 °C (at a rate of 4 °C/min) and then to 400 °C (at a rate of 10 ◦C/min). This temperature was then maintained for 12.5 minutes, making the total run time 90 minutes. An Agilent J&W DB-5HT column (30 m × 250um × 0.1um) rated to 450 °C was employed along with a constant He flow of 2 mL/min. Quantification was performed using cyclohexanone as internal standard. Agilent Chemstation and Separation Systems Inc. SimDis Expert 9 software were used to perform chromatographic programming and to process the chromatographic data acquired. Solvents (i.e., chloroform and dodecane) were quenched and subtracted prior to data processing. The incondensable gaseous samples collected were analyzed using an Agilent 3000 Micro-GC (Santa Clara, CA, USA) enhanced with 5 Å molecular sieve, alumina, PoraPLOT U, OV-01 columns, and a thermal conductivity detector 129529-134 15 (TCD). The GC calibration was performed for all light gaseous hydrocarbons C1–C6 alkanes and alkenes, as well as CO and CO2. [0097] Seal swelling studies [0098] To evaluate the seal swelling capacity of the aromatic-rich product mixture obtained from DTO upgrading, dodecane was added to obtain a sample containing 20% vol. of aromatics, which is a typical aromatic content in conventional Jet A-1 fuel. Dodecane was chosen not only because it is the same solvent used in upgrading experiments, but also because this compound has negligible seal swelling properties. 214 Buna-nitrile O-rings (durometer 70A, black) with a nominal inside diameter of 0.98 inches were purchased from Mr. O-Ring sealing company and used as received. Seal swelling studies were performed following the method described in ASTM D471 in order to ascertain the physical properties (such as hardness, tensile strength, and elongation) before and after immersion along with the change in volume of the rubber. Additionally, the tensile properties – tensile strength and ultimate elongation – and type M hardness were determined for the O-rings following the methods described in ASTM D2240 and ASTM D1414 and using an Instron 4465 CRE apparatus equipped with 0.25” diameter spools (Smithers). The O-ring fluid immersion and aging lasted for 3 days, with the temperature of the laboratory being kept constant at 23 °C. [0099] Results and Discussion [00100] Fresh catalysts characterization [00101] The textural properties (surface area, pore volume, and pore diameter) of the 10% Ni- 2.5% Cu/SAPO-11 (NCSAPO) catalyst and of the bare support (as determined by N₂ physisorption) are included in Table 2. The bare SAPO-11 support displays a higher surface area than NCSAPO, which agrees with previous reports on Ni-Cu promoted on SAPO-11 catalysts. The deposition of Ni and Cu on SAPO-11 led to some degree of pore filling by metal nanoparticles and the associated decrease in the surface area of the support. Notably, the deposition of Ni and Cu on SAPO-11 also led to a significant increase in the average pore diameter, which suggests that the aforementioned pore filling mainly impacted the micropores of the support. Similar results have been reported by other researchers, who observed that the deposition of Ni or Ni and Fe on SAPO-11 by incipient wetness impregnation led to an increase in average pore size. Table 2. Textural properties of SAPO-11 and of the fresh NCSAPO catalyst used in this study. 129529-134 16 Avg. Metal BET Pore Avg. pore H₂ NiO specific Acidity Catalyst surface volume diameter Uptake 2 ³ particle SA (µmol/g) area (m /g) (cm /g) (nm) (cm³/g) size (nm) (m²/g) SAPO-11 158.8 0.059 2.1 - - - 456* NCSAPO 43.2 0.067 5.8 15.4 0.005 1.83 66.1 [00102] The diffraction peaks at 9.6 , 16.1 21.2 , and 23.3 can all be attributed to the carrier, while the peaks at 37.3 , 43.3 , and 62.9 respectively represent the (111), (200), and (220) planes of NiO. The absence of CuO peaks can be explained by the relatively low Cu loading (2.5%) and/or to CuO being well dispersed on the SAPO-11 support. This is consistent with the TEM-EDS micrographs (vide infra), which show that although copper exists in close association with Ni, the weight percent of Cu in the metallic phase is relatively lower than Ni. The Scherrer equation was applied to the diffraction peak at 43.3 to determine the average NiO particle size, which was determined to be 15.4 nm (Table 2). H2-pulse chemisorption, which was performed after the reduction of the calcined catalysts to ascertain the number of surface-active metal sites, afforded a hydrogen uptake of 0.005 cm³/g and a metal-specific surface area of 1.83 m²/g (see Table 1). In general, large NiO particles (15.4 nm) lead to relatively lower Ni surface area for NCSAPO when also considering metal loading and/or dispersion. This leads to an overall decrease in the ratio of surface-active metal sites to total Ni loading, which suggests increased Ni loading will not lead to an improvement in performance. This effect has been confirmed by a report performed by Lyu et al. (2019) on a Ni/SAPO-11 catalyst where higher NiO concentration led to NiO particle aggregation, hence lowering the number of surface nickel atoms after catalyst reduction. [00103] The H₂-TPR of calcined NCSAPO was performed to study the reducibility of the supported metals (see Fig.1A). While the distinct shoulder with a maximum at 190 ºC is indicative of the reduction of unalloyed copper oxide particles, the main peak with a maximum at 300 ºC corresponds to the reduction of a mixed metal oxide containing both Ni and Cu to a Ni-Cu alloy. This reduction event takes place at a lower temperature than the 350–650 C reported by other authors for similar Ni-Cu/SAPO-11 catalysts, which can be explained by the smaller metal particle size reported in those contributions (9.1–10.7 nm) leading to stronger metal support interactions 129529-134 17 that hamper metal reduction. The sharp peak with a maximum of around 885 C may be attributed to the reduction of nickel aluminate spinel, whose existence on the SAPO-11 support framework and high temperature reduction has been reported by other authors. [00104] The NH3-TPD of reduced NCSAPO was performed to study the acidity of the catalyst used in this work and resulted in the desorption profile shown in Fig. 1B. The fact that most NH₃ is desorbed below 250 C suggests that most acid sites are weak in strength, while the minority of the NH3 desorbed above 250 °C is indicative of sites of moderate acidity. Saliently, the absence of peaks above 350 C shows an absence of strong acid sites, which suggests that any strongly acidic sites on SAPO-11 are blocked when the metals are loaded on the support. Tellingly, the total acidity for NCSAPO was estimated to be 66.1 µmol/g (see Table 2), which is lower than that reported for the bare SAPO-11 support (456 µmol/g) and monometallic Ni/SAPO-11(398 µmol/g). It has been reported that the low acidity of Ni-Cu/SAPO-11 relative to the bare support and monometallic Ni/SAPO-11 may arise from the coverage of SAPO-11 acid sites by metal particles, thereby enhancing the isomerization reaction. [00105] Fig. 1C shows the Ni 2p x-ray photoelectron spectra of the fresh NCSAPO catalysts, which matches the XPS spectra of Ni/SAPO-11 catalysts reported by other authors. The deconvolution of the Ni 2p peak shows contributions corresponding to metallic nickel, nickel oxide, and a nickel satellite peak. Signals at 854.25 eV and 855.62 eV correspond to metallic Ni and NiO, respectively, these binding energies being similar to those reported for other Ni-Cu formulations. Previous work on bimetallic Ni-Cu catalysts has shown that Cu promotion increases the metallic nickel (Ni⁰) surface concentration through the alloying of Ni and Cu, which leads to a close interaction between the metals that greatly facilitates the reduction of NiO to Ni⁰. The quantification of surface Ni present in different oxidation states revealed that 10.15 at% of surface Ni is present in the metallic state even prior to reduction. [00106] Continuous deoxygenation of DTO [00107] DTO was upgraded in a continuous fixed-bed reactor over NCSAPO at 480 C, 580 psi of flowing H₂ (60 sccm), and a WHSV of 1 h^-1 using the equipment and procedures described in section 2.2. This experiment consisted of two 72-hour cycles, between which the catalyst was kept in the reactor as it was washed with hot dodecane, dried, and calcined in flowing hot air, before being re-reduced to study the effect of a typical regeneration treatment on catalyst performance. The results from the analysis of the liquid and gaseous products are shown in Fig. 2A and 2B, respectively. 129529-134 18 [00108] DTO conversion was quantitative during both cycles irrespective of time on stream, which evinces the remarkable activity and stability of the catalyst. The GC-MS analysis of the liquid product mixtures revealed that aromatics comprised >80% of the reaction products irrespective of time on stream (TOS), with the remainder of the liquid products being a mixture of n-alkanes, iso-alkanes, and cycloalkanes. Among the aromatic products detected, the alkyl substituents of polycyclic aromatic hydrocarbons (PAH) – naphthalene, anthracene, and phenanthrene – were found to be particularly prevalent. This is unsurprising given the structure of resin acids, all of which contain three fused six-carbon rings. To further confirm that most of the heavier polycyclic aromatics were generated from the resin acids, TOFA, the component present in DTO was further upgraded for up to 24 hours in a fixed bed reactor at similar operating conditions of 480 °C and a WHSV of 1hr^-1. In this experiment, the product distribution appears to differ completely from the DTO runs performed previously. At 1 h TOS, the aromatics were mainly composed of monoaromatics and substituted monoaromatics, and no trace of heavy aromatics was observed. However, as the reaction progresses to 24h TOS, the selectivity to aromatics approached ~62% with no trace of fused heavier aromatics. These results confirm that the presence of heavier tricyclic aromatics such as phenanthrenes and anthracenes may be obtained from the direct deoxygenation of abietic and dehydroabietic acids, and not the secondary aromatization from monoaromatics formed. These results are in overall agreement with those of Anthonykutty and co-workers in the deoxygenation of DTO over a NiMo catalyst at the same WHSV (1 h^-1). They observed conversions ≥98% to be accompanied by an increased selectivity to aromatics. Although these authors also observed that conversion increased with temperature from 375 to 400 °C, further temperature increases beyond 400 °C led to a drop in conversion over the NiMo catalyst. In contrast, for the NCSAPO catalyst in this study, conversion remained quantitative up to 480 °C. [00109] The incondensable gas products observed, and their variance as a function of TOS, also provide valuable insights. Sown in Fig.2(b) light C1–C3 hydrocarbons (i.e., methane, ethane, and propane) and CO2 comprised the gaseous products detected. While methane is produced through the methanation of COx and/or from the cracking of alkyl chains via the removal of terminal methyl groups, ethane and propane are generated through the internal cracking of alkyl chains. As shown in Fig. 2B, the amount of CO₂ initially detected is negligible but slightly increases and plateaus with TOS. This is consistent with previous studies in which CO2 was determined to adsorb and accumulate as carbonate species on the catalyst surface, which needs to become saturated before CO₂ is observed in the gaseous products. During the first 72 h cycle the 129529-134 19 concentration of C1–C3 hydrocarbons in the gaseous products increases slightly before stabilizing. In contrast, during the second 72 h cycle following catalyst regeneration, the concentration of these gaseous products starts at a lower level but rises progressively with TOS. Hence, while the quantitative conversion of DTO suggests that the overall deoxygenation activity remains constant throughout the experiment, cracking activity changes from one cycle to the next and/or as a function of TOS. Longer experiments might reach the constant levels of cracking observed by others during the continuous conversion of a fatty acid-based feed, albeit that work falls outside the current scope. [00110] The carbon number (CN) of the liquid products generated as a function of TOS is depicted in Fig. 3A. Notably, while CN ranged from C7 to C18, most liquid products fell within the jet fuel CN range (C8–C16). As shown in Fig. 3B, when the liquid products were classified based on their boiling point (BP), 67% of the liquid products were determined to fall within the BP range of Jet A (145–300 °C). [00111] The results above show that DTO can be upgraded at 480 °C over NCSAPO at a WHSV of 1 h^-1 with quantitative DTO conversion for 144 h irrespective of TOS both before and after a typical catalyst regeneration treatment, producing all types of hydrocarbons comprising SAF with an increased selectivity to aromatics (>80%). However, the catalyst displayed negligible deactivation under the aforementioned reaction conditions in the time period investigated. Therefore, the experiment was repeated using a WHSV of 8 h^-1 to study the effects of catalyst deactivation. As expected, due to the much lower residence time of DTO in the catalyst bed, conversion was considerably lower than the quantitative conversion attained at lower space velocity and was observed to decrease with TOS during the first 72 h (see Fig. 4A). A similar effect of space velocity on conversion was reported by Anthonykutty et al., who observed higher conversion of fatty and resin acids over NiMo catalyst at lower space velocity (WHSV = 1 h^-1) and lower conversion at higher space velocities (WHSV = 2 and 3 h^-1). Indeed, when Anthonykutty and co-workers hydrotreated DTO at lower temperatures (325 and 350 C) and higher WHSV (2 and 3 h^-1), in addition to high yields of polycyclic aromatic hydrocarbons, these authors observed n-octadecane and n-heptadecane as the major paraffinic products, along with lower yields of cracking products. The latter is problematic, since n-octadecane and n-heptadecane fall outside the carbon number range of jet fuel (C₈-C₁₆). [00112] The conversion of the TOFA component in DTO was much higher than that of the rosin component, which suggests that the latter is more recalcitrant. This fact and the high selectivity to aromatics observed irrespective of TOS indicates the conversion of TOFA to aromatics. For 129529-134 20 instance, in a study where a feed mainly composed of free fatty acids was upgraded over Zn/zeolite Y, both conversion and aromatic yield initially increased to reach ~73% at 8 h on stream before conversion declined to 31% at 20 h on stream, which the authors attributed to the formation of heavier aromatics resulting in coke-induced deactivation. Results generated from the TGA of the spent catalysts at higher space velocity, which led to the formation of heavy aromatics, suggests that the increased deactivation of the catalysts was due to coking (vide infra). In short, both PAH formation and the resulting deactivation are reduced at lower space velocities. However, for a WHSV of 8 h^-1, a greater yield of heavier aromatics is observed, with a significant decrease in mono- and di-substituted benzenes and naphthalene, which is in total contrast to the observations from WHSV of 1h^-1. Similar activity is observed in the 2^nd 72h (after regeneration), which shows that amidst catalyst regeneration, the yield and selectivity to aromatics are both maintained favoring the yield of heavier compounds – phenanthrenes and anthracenes. [00113] The results reveal that for a WHSV of 8 h^-1, there is an increase in light alkanes concentrations in the gas phase relative to WHSV of 1 h^-1. Additionally, the result also showed that the concentration of substituted benzenes (or monoaromatics) decreased at a WHSV of 8 h^-1 (as seen in FIG.6). These observations can be attributed to the cracking of monoaromatics to light hydrocarbons, resulting in an increased proportion of PAHs in the products and overall decrease in the yield of liquid products. The continuous cracking of (alkyl-) monoaromatics resulted in the formation of light (gaseous) alkanes/alkenes - methane, ethane, and propane, consistent with the observations in Fig.4B. In a similar study, an optimum monoaromatic yield (~32%) was observed at WHSV of 75 h^-1 and 550 °C. However, the yield (and conversion) decreased at an increased WHSV of 80 h^-1, attributed to the cracking of light cycle oil and monoaromatics hydrocarbons, leading to the formation of coke. [00114] The gaseous products of the experiment performed at a WHSV of 8 h^-1 (see Fig. 4B), show distinct differences to the corresponding results obtained at a WHSV of 1 h^-1 (Fig.2B). First, the concentration of incondensable gases in the exhaust is considerably higher, i.e., around 16- 21% instead of <4%. In addition, the concentration of all gases is relatively constant, only decreasing slightly with TOS. These results are also indicative of the different deoxygenation and cracking activities of the catalyst, deoxygenation activity being reduced considerably while cracking activity remained consistent. Additionally, these activity trends are likely not the result of coke-induced deactivation since they can be observed from the onset of the reaction. Finally, the fact that methane and ethane are present in higher amounts than propane suggests that heavier alkanes are cracked to lighter hydrocarbons, which is in line with previous reports. This, coupled 129529-134 21 with the presence of carbon dioxide, suggests that these gases are produced through chain shortening which occurs through the scission of terminal carbons rather than through the hydrogenation of COx. Also observed is the decrease in C1-C3 as the reaction progresses with a concurrent increase in hydrogen concentration. This behavior could be attributed to the competitive adsorption of feed molecules and hydrogen, leading to the irreversible poisoning of the sites responsible for methanation and cracking and thus leading to the evolution of unreactive hydrogen or high hydrogen coverage. [00115] The liquid products recovered from the experiment performed at a WHSV of 8 h^-1 shows significant differences relative to those stemming from the experiment performed at a WHSV of 1 h^-1 in terms of both their CN and their BP (see Fig. 5A and Fig. 5B. Indeed, higher space velocity favored the formation of heavier products (such as C18 hydrocarbons) with a BP above that of Jet A, which comprised the majority (54%) of the liquid products stemming from the experiment performed at WHSV of 8 h^-1 as shown in Fig. 5B. [00116] Typically, the cracking of the alkyl chains of fatty acid and/or long-chain hydrocarbons mainly occurs at higher temperatures and longer residence times to generate fatty acids and n- alkanes with shorter alkyl chains. However, several authors have investigated the DTO deoxygenation reaction scheme, which is dependent on temperature in different reactor systems since DTO deoxygenation itself is favored as temperature increases. It is reported that at low temperatures around 260 °C, most of the material recovered comprises unconverted fatty acids (e.g., oleic and linoleic acids) and resin acids (e.g., abietic and pimaric acids). However, as the temperature increases (350°C and above), the fatty acids are completely deoxygenated to C18 and C17 hydrocarbons. [00117] The effect of temperature was evaluated in the fixed bed reactor using DTO as a feed over NCSAPO with a lower operating temperature of 380 °C and a WHSV of 1 h^-1. A similar result to those from the initial operating temperature (480 °C) was observed with a 100% conversion and product selectivity following the trend at 24 hours: Aromatics (97.45%) >> Alkanes (2.32%) > Cycloalkanes (0.59%) > Isoalkanes (0%). This observation is congruent with a reported result of DTO conversion to hydrocarbon products at a WHSV of 1 h^-1 with increased selectivity to aromatics as the temperatures progresses from 350-450 °C. Similarly, another study reported increased selectivity to aromatics at temperature up to 480 °C but decreased beyond 480 °C for the conversion of Sapium oil over a caged aluminophosphate (AlPO4) catalyst, thus confirming that the effect of temperature on the selectivity to aromatics is negligible when operating within the temperature range between 350 and 480 °C. Anthonykutty et al. (2013) 129529-134 22 reported the optimal conditions for NiMo/Al₂O₃ with WHSV of 1 h^-1 and temperature ranging from 325–400 °C. While these conditions afforded a maximum degree of deoxygenation, the product selectivity shifted from aromatics towards paraffins. Finally, under these conditions (T = 480 °C, P = 580 Psi, and H₂ flow = 60 sccm), DTO was upgraded in the absence of NCSAPO catalyst, to determine the components produced. The results showed that DTO underwent slow pyrolysis, resulting in the production of heavier fraction bio-oil with ~70% selectivity to undesirable polycyclic aromatic hydrocarbons. These products were primarily comprised of naphthalene, anthracene, phenanthrene, pyrene, and others, with naphthalene making up almost 50% of the bio-oil composition. Since naphthalene is considered a hazardous air pollutant (HAP) and a priority pollutant by the US Environmental Protection Agency (EPA), its high concentration in SAF blendstock can have implications for environmental and human health. [00118] Reaction pathways for conversion of DTO to SAK [00119] The nature and composition of aromatics generated from the continuous reactor operating at WHSV of 1 h^-1 and 8 h^-1 are shown in Fig. 6A & 6B. Jet A is mainly composed of substituted monoaromatics, while the products of these reactions are primarily constituted of fused ring and heavier aromatics. The latter are less favorable for use in SAK due to their high tendency toward the formation of soot by secondary aromatization of fused aromatics into PAH via nucleation and subsequent particle growth. Four classes of aromatic are classified in this work as substituted benzene (e.g., toluene, mesitylene, and o-xylene, etc.), substituted indane (e.g., 1- methylindane and 2,3-dihydro-4-methyl-1H-Indene, etc.), substituted naphthalene (e.g., 1,3- dimethylnaphthalene, 1,4,6-trimethylnaphthalene, and 1-methylnaphthalene, etc.), and polycyclic aromatic hydrocarbons (phenanthrene, retene, and anthracene, etc.). The total amount of the classes of aromatics varied depending on the WHSV employed in the reaction. The four classes of aromatics all continue to be present with the substituted benzene remaining at ~30% before and after regeneration as shown in Fig. 6A. This decrease in the amount of total aromatics may be attributed to the deposition, and/or coverage of the acid sites with carbonaceous species as the reaction proceeds. This in turn reduces the acid sites available to facilitate the aromatization reaction. However, when the catalyst is regenerated after the first 72 h, the SAK content increases to nearly the value recorded at 24 h followed by a more gradual decrease in SAK selectivity than observed before regeneration. This improvement may be traced to the re-activation of the catalyst which involves the burn-off of the carbon deposited on the catalyst acid sites. It is also essential to note that the conversion of DTO was 100% at all TOS, which suggests that a WHSV of 1 h^-1 provides sufficient contact time for the feed to be converted. In contrast, at a WHSV of 8 h^-1, the 129529-134 23 conversion varied at different TOS. Although similar percentage distributions to the various aromatic classes were observed during the first 72 h, the SAK selectivity decreased progressively, with a larger amount of substituted naphthalene and/or heavier aromatics present. Similarly, the SAK content improved after the catalyst regeneration. This observation results in an increasing yield of heavier aromatics which deactivate the catalyst and causes pore blockages. Therefore, shorter residence-time is unfavorable for the conversion of DTO to the aromatics useful for SAK such as mono-aromatics (substituted benzene or alkylbenzene, and indane). The liquid product generated from DTO upgrading at 480 °C over NCSAPO and at a WHSV of 1 h^-1 was analyzed. From the GCxGC analyses, the following components and their area percentage were estimated: paraffins (15.7%), iso-paraffins (5.2%), mono-olefins (23%), mononaphthenes (23%), 2 unsaturation (U-S) linear & cyclic hydrocarbons (6.7%), monoaromatics (24.6%), PAHs (17.8%). This result is consistent with Fig. 6A, thus confirming the increased concentrations for both monoaromatics and PAHs. [00120] As shown in Schemes of FIG. 11 and FIG 12, the selectivity to aromatics relative to other hydrocarbons, not only originated from the selective deoxygenation of resins but also the cyclization of long-chain alkenes and the eventual aromatization of cycloalkanes/cycloalkenes. Rosin acid (abietic, dihydroabietic, and dehydroabietic acid) is selectively deoxygenated via decarboxylation/decarbonylation to tricyclic & polycyclic aromatics such as retene or 10,18- bisnorabietane-5,7,9(10),11,13-pentaene, which may further undergo hydrogenation to 18- norabietane. Several reports have shown similar reaction pathways for the thermochemical conversion (mostly under pyrolytic conditions) of biomass to aromatics over acid catalysts. In parallel, fatty acids present in DTO (oleic acid and linoelaidic acid) can also undergo aromatization from long-chain alkanes by the selective deoxygenation of the fatty acids and a long-chain alkane dehydrogenation to a more reactive alkene. Followed by the subsequent cracking of unsaturated long-chain alkenes to shorter ones, which then undergo cyclization to cycloalkanes/cycloalkenes via cycloaddition or Diels Alder reactions, followed by aromatization or hydrogen transfer via dehydrogenation to aromatics (or arenes). Similar observations were noted by others, for the deoxygenation of fatty acids over zeolite catalysts. Their study proposed that under thermal cracking conditions, fatty acid (oleic acid) is converted to long-chain alkanes via McLafferty rearrangements. The unconverted oleic acids or monocarboxylic acids are deoxygenated to yield CO, CO₂, and H₂O, and further undergo cracking over the BrØnsted and Lewis sites of acid catalysts to yield several hydrocarbon pools. These hydrocarbons then eventually yield arenes and heavy aromatics via different reactions like Diels Alder reactions, 129529-134 24 oligomerization, Friedel-Crafts alkylation, etc. It is essential to note that these reactions occur over bifunctional solid acid-supported metal catalysts. However, the preponderance of these reactions and thus the yield of products formed greatly depends on the nature of the feed, the catalyst, and the reaction conditions. [00121] Post Characterization and Surface Analysis of Spent Catalysts [00122] The spent catalyst was analyzed by XPS and regenerated under similar reaction conditions as those used in reactor experiments to observe the different oxide species present on the surface of the spent, calcined, and reduced catalysts. The spent catalyst was regenerated (or calcined) under air at 450 ^oC for 5 h and then reduced under a H₂ atmosphere at 400 ^oC for 3 h. As shown in Table 3, the total amount of nickel detected via XPS varies from the spent to the reduced catalysts following the trend spent (0.03%) << reduced (1.38%) < calcined (2.74%). The Ni concentration is observed to be low on the surface of the spent catalyst due to the coverage of coke deposits on the catalyst surface. The calcined and spent catalysts also show lower concentrations of Ni than the overall bulk material, suggesting Ni particles are segregated away from the catalyst surface. However, the spent catalyst is enriched with Ni concentration upon the combustion of the coke deposit in air during regeneration and during reduction with H₂. A similar trend is observed for copper concentration shown in Table 3. The amount of organic (coke) deposits on the catalysts studied follows the trend spent (60.34%) >> reduced (39.82%) > calcined (30.06%). This is agreeable and consistent with other analyses such as TGA (vide infra) since the coke precursors deposited on the spent catalyst are enough to decrease the catalyst activity, leading to lower conversion and catalyst deactivation. However, when the catalyst is regenerated via combustion in air, the residual coke deposits decrease, which is similar to reported results. Table 3. Surface concentration (at. %) of elements detected via XPS Sample C O Ni Cu P Mg Ca Na Si Al Spent 60.34 17.79 0.03 0.01 2.17 0.01 0.02 0.03 8.78 10.8 Calcined 30.06 26.14 2.74 1.21 2.29 0.02 0 2.74 8.80 28.74 Reduced 39.82 21.32 1.38 0.51 2.68 0.08 0 1.38 10.78 23.29 [00123] Fig.7A shows the Ni 2p X-ray photoelectron spectra of the spent, calcined, and reduced catalysts. Most peaks displayed the Ni 2p_3/2 and 2p_1/2 for the main and satellite peaks, with the following Ni peaks or species observed - metallic nickel (Ni⁰), nickel oxide (NiO), and NiO satellite peak. From Fig. 7A, the spent catalyst showed much lower peak intensity with observed 129529-134 25 Ni⁰ (20.17%), NiO (46.25%), and NiO sat (33.57%) at 852.54 eV, 856 eV, and 862.22eV respectively, indicating the re-oxidation of the NCSAPO catalyst during deoxygenation reaction. Upon calcination, Ni⁰, NiO, and NiO sat were observed to be 30.59%, 40.08%, and 29.33% at 854.05 eV, 855.84eV, and 861.26eV respectively. When calcined or regenerated catalyst is reduced again, the Ni⁰ peak increased to 73.22% at a lower BE of 852.86eV, with the corresponding NiO (21.91%) and NiO sat (4.87%) species at 856.28eV and 859.05eV. The subsequent positive shift of the NiO binding energy (856.28 eV) after reduction indicates a strong interaction between NiO and the support, thus increasing the Ni⁰ concentration relative to the calcined and spent catalyst. Moreover, the large amount of NiO species available for reduction with H2 stems from the calcination of the spent catalyst in air resulting in the removal of coke precursors on the catalyst surface as observed in previous reports. Similar observations have been made by Zhang et al. (2017), where they detected the formation of NiO in air on the surface of both Cu-Ni alloy and Ni at varying Ni 2p3/2 positions of 855.8 eV and 855.9 eV. Additionally, the small peak for the reduced catalyst positioned at 859.05 eV was assigned to Ni²⁺ (NiO) in nickel aluminate spinel which is usually observed at 857.8 eV and 863.0 eV and higher temperatures. This is an additional indication of a strong metal support interaction. This observation agrees with the H2-TPR result, with nickel aluminate spinel reduction occurring at a high temperature of 860 ^oC. [00124] Similarly, Fig.7B displays the Cu 2p X-ray photoelectron spectra of the spent, calcined, and reduced catalyst. The oxide species observed for the Cu 2p peaks include Cu⁰, Cu2O, and CuO species. The spent catalyst showed lower peak intensities for Cu⁰ (24.90%), CuO (34.87%), and Cu₂O (9.52%) species at 933.11 eV, 928.13 eV, and 931.97 eV respectively. However, there is an increase in copper oxide species relative to the spent catalyst after calcination; Cu⁰ (20.56%), CuO (40.08%), and Cu2O (11.12%) at 933.57 eV, 934.17 eV, and 932.76 eV respectively. Finally, upon the reduction of the calcined spent catalyst, all copper oxide species were completely reduced to Cu⁰ (100%) observed at 932.66 eV. This suggests that the catalyst surface is completely enriched with Cu⁰ upon reduction. No additional peaks were observed, which suggests that exposed copper oxide species were completely transferred to metallic copper (Cu⁰) after the reduction. This behavior may be traced to the ability of Cu to suppress coke-induced deactivation and enhance NiO reducibility. [00125] The shifts in BE observed for Ni and Cu may indicate that the transfer of electrons from Cu to Ni changes the electron cloud density of the Ni surface, leading to the formation of intermetallic species. Ultimately, the interaction between nickel and copper species is facilitated 129529-134 26 by the reduction of copper oxide species. Similar observations have been reported by Yang et al. (2017) on different formulations of Ni-Cu/SAPO-11 catalysts. [00126] The transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM- EDS) analysis of spent NCSAPO before and after regeneration (at WHSV of 1h^-1) was performed to acquire insights into the catalyst’s structural changes during aging and regeneration. The TEM- EDS elemental mappings for spent NCSAPO (before regeneration) are shown in Fig.8A-8F. The Ni and Cu present are in close association, and an uneven distribution of the particles on the support is observed to have both spherical and irregular shapes. With an average particle size of 15 nm for the fresh NCSAPO, the particle size distribution (Fig.8G) shows a particle size growth for the spent catalyst (before regeneration) with an average centered around 31.8 nm. This size changes and growth in the crystallites or nanoparticles over time may be traceable to Ostwald ripening. Fig.8H shows that Ni concentration within individual particles is maintained as high as 85%–90% for the spent NCSAPO before regeneration. This confirms that the weight percent of just the metallic phase (80%Ni and 20%Cu) is consistent with the atomic percent of the bulk metal loading for NCSAPO (10%Ni-2.5%Cu). [00127] Similar observations can be highlighted for the spent catalyst (after regeneration), with the TEM-EDS elemental mappings shown in Fig. 9A-9F, having a similar uneven distribution of the particles on the support observed for the spent catalyst before regeneration. However, larger particle sizes, in addition to voids and pores not initially present in the spent catalyst, were observed. The formation of these pores or voids and changes observed particularly at high temperatures is attributed to the Kirkendall effect or porosity. These observations have been reported in Ni-Cu formulations employed for deCOx purposes. Fig.9G also confirms the particle growth of the spent catalyst after regeneration (36.7nm), and Fig. 9H shows that high Ni concentrations within particles were maintained (85%–90%) like the spent NCSAPO catalyst before regeneration. This observation is consistent with other Ni-Cu formulations reported for zeolites and metal oxide (TiO₂) surface enrichments, due to particle sintering and/or metal redistribution. [00128] Coke Characterization Studies [00129] Coke characterization studies of the spent catalysts (NCSAPO) employed for the deCOx reaction of DTO in the continuous reactor at the different WHSV were performed, and the thermogravimetric analysis (TGA) profiles are shown in Fig. 10A and 10B. From the study, all weight loss identified below 400 °C may be attributed to the combustion of residual reactants/products and/or the desorption of physisorbed species on the catalyst surface, while 129529-134 27 temperatures above 400 °C can be likened to hard coke (or graphitic carbon). Fig. 10A shows the extent of weight loss for spent NCSAPO (1 h^-1 WHSV) before and after regeneration, which follows the trend spent NCSAPO after regeneration (4.5%) < spent NCSAPO before regeneration (6%). The decreased coke accumulation after regeneration is likely a result of the ability of Cu addition to suppress cracking and/or decrease the formation of coke. The observed weight gain can also be explained by the oxidation of Ni to NiO as reported elsewhere. This observation is consistent with results observed from XPS (vide supra). It was reported that the anti-coke deposition performance of a Ni-Cu formulation over HZSM-5 support in the conversion of biomass to bio-aromatics. This study showed that the modification of Ni/HZSM-5 using Cu enhanced coking resistance, with a weight loss of 3.72% (Ni-Cu/HZSM-5) as opposed to 6.28% (Ni/HZSM-5) and 6.96% (HZSM-5). It was further reported that the coking resistance is due to the formation of fibrous amorphous coke, the suppression of recalcitrant graphitic coke as a result of high weak (BrØnsted) acidity, and improved carbon deposition resistance. Similar anti-coke deposition performance over a Ni-Cu formulation has been observed in our previous study for the deoxygenation of waste cooking oil and brown grease over 20%Ni-5%Cu/Al₂O₃ which was attributed to the redistribution of Ni and Cu within metal particles during the regeneration process. [00130] Fig.10B also shows the weight loss of spent catalysts at WHSV of 8 h^-1 which follows the trend: NCSAPO before regeneration (19%) < NCSAPO after regeneration (~25%). The profile reveals that the majority of weight loss is situated at temperatures above 400 °C, being indicative of more recalcitrant carbonaceous deposits in the form of graphite or hard coke (or heavier hydrocarbons), thereby leading to excess catalyst deactivation (~25% weight loss during TGA) due to the accumulation or deposition of materials or coke precursors blocking the pores and active sites. The sample analyzed from the deCOx of DTO at WHSV of 8 h^-1 showed that the most abundant products were the heavier aromatics and tricyclic aromatic compounds, these being responsible for coke formation and for excessive deactivation after the 144 h run, which affects the catalyst activity and decreases conversion (<60%). [00131] To assess the leachability of the active metal (Ni) and promoter (Cu) of NCSAPO employed in the continuous reactor, representative product mixtures were filtered off from the solid spent catalyst and analyzed via inductively coupled plasma-mass spectroscopy (ICP-MS). The leaching studies were performed via ICP-MS on the different product samples at the start of the reaction (at t=1 h) and at the end of the reaction (at t=144 h). The result shows that the metals present (Ni and Cu) in the liquid samples were 7.7 ppm and 3.8 ppm for Ni and Cu respectively at t = 1 h, and as low as 0.1 ppm for both Ni and Cu at t = 144 h. This initial loss of Ni may be 129529-134 28 attributed to the formation of volatile Ni carbonyl from the reaction of Ni and CO at elevated temperatures ~75 ^oC as reported elsewhere. Hence, since the deoxygenation reaction of DTO proceeds at a higher temperature (up to 480 ^oC), some Ni leaching is expected, but the low Ni concentration in the products at t=144 h suggests not all Ni species are susceptible to this process. [00132] Swell studies of O-ring seals by aromatic rich SAF blendstock [00133] The presence of aromatic hydrocarbons in jet fuel is critical to swell the seals of the aircraft’s fuel system to avoid leaks. The minimum and maximum concentrations of aromatics in jet fuel are 8 and 25% per ASTM regulations. With this in mind, the liquid products obtained from the continuous upgrading of DTO over NCSAPO, which contains >80% aromatics was diluted in dodecane (a n-alkane that does not contribute to seal-swelling), to obtain a mixture with an aromatic content of 20 vol% (a sample denoted henceforth as 20-A). In addition, the initial tensile properties – namely, type M hardness, tensile strength, and ultimate elongation – of a standard o-ring were determined to be 76 pts, 2328 psi, and 282%, respectively. Following the ASTM D471 standard, the o-ring was immersed for 72 h in sample 20-A at room temperature (23 C), prior to measuring the change in hardness (-1 pts), tensile strength (-9 %), and ultimate elongation (-8 %). After immersion in sample 20-A, the o-ring seal was determined to swell considerably, the volume swell percentage value measured being 2.7±0.2%. This result is closely aligned with the findings of Romanczyk et al. (see Table 4), who demonstrated that the volume swell percentage in ethylbenzene and indane – the most abundant aromatics in Jet A-1 – was 3.1±0.2% and 2.8±0.1%, respectively. Seal swelling potential is determined by both the nature of the aromatic ring(s) as well as by steric effects associated with any alkyl groups attached to the aromatic ring(s). For instance, while anthracene can swell o-ring seals more effectively than naphthalene, indane, and tetralin can swell o-rings 47–50% more than n-propylbenzene. In general, polycyclic aromatics can swell o-rings more effectively than monocyclic aromatics, and the swelling rate depends on both the type of aromatics present in the fuel as well as on their concentration. Finally, the volume swell observed with sample 20-A is higher than that supplied by a mixture of Jet-A and SAF obtained from the hydroprocessing of esters and fatty acids (HEFA) – the main SAF blend currently approved and employed – which showed a volume swell of 2.2±0.2%. This is noteworthy since a previous study concluded that Jet A-1 had a higher swelling rate than other types of SAF including aromatics such as p-xylene, propyl benzene, and tetralin in different concentrations (4, 8, 12.5, and 25%). Table 4. Comparison of the volume swell percentage of aromatic rich SAF blendstock 129529-134 29 N/A Fuel samples Volume swell Reference percent (%) 1 20-A 2.7±0.2 This work 2 Jet A/HEFA 2.2±0.2 Romanczyket al. Fuel 2019, 238, 483-492. DOI: 10.1016/j.fuel.2018.10.103. 3 Ethylbenzene 3.1±0.2 Romanczyket 4 Indane 2.8±0.1 Romanczyket 5 Cycloalkanes (Polysubstituted) 1.81±0.1 Landera, et al. Frontiers in Energy Research 2022, 9, Original Research. DOI: 10.3389/fenrg.2021.771697 6 Naphthalene 1.6±0.2 Romanczyket 7 Synthetic fuel (S-5) (0% 1.7±0.08 Muzzell, et al. Synthetic Aromatics) Fischer-Tropsch (FT) JP- 5/JP-8 Aviation Turbine Fuel Elastomer Compatibility. 2005, 42 8 S-5 + A150 (10% Aromatics) 6.7±0.3 Muzzell 9 S-5 + Decalin (1%) 0.8±0.1 Link, et al. Energy & Fuels 2008, 22 (2), 1115-1120. DOI: 10.1021/ef700569k 10 S-5 + Naphthalene (1%) 1.2±0.5 Link [00134] Variance in Hydrocarbon Production [00135] The following demonstrate the production of useful hydrocarbons for jet fuel applications through contacting the catalyst compositions described herein with various FOGs. In particular, These data show that upgrading pure rosin over two alumina-supported catalysts at temperatures ranging from 260 to 375 °C. Table 5 shows results with distilled tall oil and 25-30 % rosin acid with two alumina-supported catalysts at 350 C°. For Tbale 5, DTO with 25-30% rosin acid was used as feedstock. The catalysts were NCA- 20% Ni-5%Cu/Al₂O₃ or NFA- 20% Ni-5%fe/Al2O3. The conditions were 0.5g catalyst at 350 C for 3hrs. 129529-134 30 Table 5

[00136] Table 6 shows the results of upgrading an isomerized fatty acid feed over the same alumina-supported catalysts at 350 °C, which has afforded a product mixture very similar to jet fuel. The feed was iso-oleic acid ran for 3hrs at 350 C over 0.5 g of catalyst. Upgrading the iso- oleic acid feed using NCA provides a product resembling commercial Jet A-1. Table 6

[00137] Tables 7 and 8 show the results of upgrading DTO over zeotype-supported catalysts (with lower loadings) at 350 °C and 380 °C. In Table 7, DTO with 25-30% rosin acid on zeotype was used with NCSAPO – 10%Ni-2.5%Cu/SAPO-11 or NFSAPO- 10Ni-2.5%Fe/SAPO-11.0.5g catalyst was used at 350 C for 3 hrs. Table 8 is the same at 380 C. Table 7

Table 8 129529-134 31

[00138] Table 9 shows the results of upgrading different feeds over a zeotype-supported catalyst at 375 °C. Table 10 shows the results of upgrading mixtures of two different feeds and rosin over a zeotype-supported catalyst at 375 °C. NCSAPO was used as the catalyst for 3 hrs. Table 9

Table 10

129529-134 32 [00139] This study herein investigated the catalytic conversion of distilled tall oil (DTO) to SAF blendstock via deCOx. The feed was upgraded over a bimetallic Ni-Cu catalyst with SAPO-11 as support. A continuous experiment was conducted in a fixed-bed reactor at a WHSV of h^-1, comprising two 72-hour cycles with an intermediate catalyst regeneration step. The results revealed that DTO conversion remained quantitative throughout the run, and the yield of aromatics was ≥80% regardless of TOS. In addition, 67% of the liquid products fell within the jet fuel range (CN and BP) at all reaction times sampled. This indicates that the NCSAPO catalyst maintained its deoxygenation activity while avoiding excessive cracking. Finally, the synthetic aromatic kerosene blendstock produced showed remarkable potential for swelling the seals used in aircraft fuel systems. [00140] Various modifications of the present disclosure, in addition to those shown and described herein, will be apparent to those skilled in the art of the above description. Such modifications are also intended to fall within the scope of the appended claims. [00141] It is appreciated that all reagents are obtainable by sources known in the art unless otherwise specified. [00142] It is also to be understood that this disclosure is not limited to the specific aspects and methods described herein, as specific components and/or conditions may, of course, vary. Furthermore, the terminology used herein is used only for the purpose of describing particular aspects of the present disclosure and is not intended to be limiting in any way. It will be also understood that, although the terms “first,” “second,” “third” etc. may be used herein to describe various elements, components, regions, layers, and/or sections, these elements, components, regions, layers, and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, “a first element,” “component,” “region,” “layer,” or “section” discussed below could be termed a second (or other) element, component, region, layer, or section without departing from the teachings herein. Similarly, as used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms, including “at least one,” unless the content clearly indicates otherwise. “Or” means “and/or.” As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. It will be further understood that the terms “comprises” and/or “comprising,” or “includes” and/or “including” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, 129529-134 33 elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof. The term “or a combination thereof” means a combination including at least one of the foregoing elements. [00143] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein. [00144] Reference is made in detail to exemplary compositions, aspects, and methods of the present disclosure, which constitute the best modes of practicing the disclosure presently known to the inventors. The Figures are not necessarily to scale. However, it is to be understood that the disclosed aspects are merely exemplary of the disclosure that may be embodied in various and alternative forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for any aspect of the disclosure and/or as a representative basis for teaching one skilled in the art to variously employ the present disclosure. [00145] Patents, publications, and applications mentioned in the specification are indicative of the levels of those skilled in the art to which the disclosure pertains. These patents, publications, and applications are incorporated herein by reference to the same extent as if each individual patent, publication, or application was specifically and individually incorporated herein by reference. [00146] The foregoing description is illustrative of particular embodiments of the disclosure, but is not meant to be a limitation upon the practice thereof. The following claims, including all equivalents thereof, are intended to define the scope of the disclosure. 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Claims

129529-134 43 CLAIMS 1. A system for producing one or more hydrocarbons for sustainable aviation fuel (SAF) comprising: a catalyst composition comprised of 2 to 20 wt.% of a metal on a support; heat energy at a temperature of from about 250 °C to about 500 °C; pressure ranging from 1 to about 40 bar; and a feedstock of one or more fats, oils, and greases (FOGs) comprising mono-, bi-, or tri- glycerides, fatty acids, fatty acid esters, and/or rosin acids, such as yellow grease, brown grease, tall oil, algae oil, rosin, isomerized fatty acids, or any combination thereof. 2. The system of claim 1, wherein the metal is selected from iron, nickel, copper, or a combination thereof. 3. The system of claim 1 or 2, wherein the metal is nickel, copper, or a combination of nickel and copper. 4. The system of claim 3, wherein the metal is a combination of nickel and copper. 5. The system of claim 4, wherein the metal is of a ratio of nickel to copper of about 4:1. 6. The system of claim 1, wherein the support is comprised of an alumina, another oxide, and/or a zeolite or zeotype material. 7. The system of claim 1 or 6, wherein the support comprises SAPO-11. 8. The system of claim 1, wherein the feedstock comprises rosin at an amount of about 20- 50 percent of the content of the feedstock. 9. The system of claim 1, further comprising a steam reforming zone. 10. A method for producing one or more hydrocarbons for sustainable aviation fuel (SAF) comprising preparing a feedstock of one or more FOGs with one or more rosin acids added therein 129529-134 44 and providing heat and a catalyst composition, wherein the catalyst composition comprises a metal and a support. 11. The method of claim 10, wherein the metal is selected from iron, nickel, copper, or a combination thereof. 12. The method of claim 10 or 11, wherein the metal is nickel, copper, or a combination of nickel and copper. 13. The method of claim 12, wherein the metal is a combination of nickel and copper. 14. The method of claim 13, wherein the metal is of a ratio of nickel to copper of about 4:1. 15. The method of claim 10, wherein the support is an alumina, another oxide, and/or a zeolite or zeotype material. 16. The method of claim 10 or 15, wherein the support comprises SAPO-11. 17. The method of claim 10, wherein the feedstock comprises rosin at an amount of about 20- 50 percent of the content of the feedstock. 18. The method of claim 10, wherein the heat is provided at a temperature of about 250 to 500 °C. 19. The method of claim 10, wherein the produced hydrocarbons include one or more of an alkane, an iso-alkane, a cyclo-alkane, and an aromatic. 20. The method of claim 10, further comprising a hydrogenation step of the feedstock with a platinum group metal. 21. The method of claim 20, wherein the platinum metal is selected from ruthenium, platinum, rhodium, palladium, or a combination thereof. 129529-134 45 22. The method of claim 20 or 21, wherein the hydrogenation step is performed with a sulfided catalyst. 23. The method of claim 22, wherein the sulfided catalyst is sulfided NiMo and/or sulfided NiW. 24. The method of claim 20, 21, 22, or 23, wherein the hydrogenation step is performed in the presence of a base metal. 25. The method of claim 24, wherein the base metal is selected from nickel, molybdenum, tungsten, iron, lead, zinc, copper, tin, germanium, titanium, cobalt, rhenium, chromium, uranium, indium, gallium, thallium, dysprosium, or a combination thereof. 26. The method of claim 10 or 20, wherein preparing the feedstock comprises removing contaminants from the feedstock. 27. The method of claim 26, wherein contaminants are removed by providing the feedstock over a guard bed. 28. The method of claim 26, wherein removing the contaminant includes filtration of the feedstock and/or solvent extraction of the feedstock. 29. The method of claim 10 or 20, further comprising processing obtained products through isomerization and/or cyclization.