WO2023184033A1 - Methods of making catalysts, catalysts, and uses thereof - Google Patents

Abstract

A method of preparing a metal oxide-supported catalyst. The method may involve high-energy ball milling a coke-based material and metal oxide nanoparticles; and comminuting and dispersing the metal oxide nanoparticles on the coke-based material; to form the metal oxide-supported catalyst.

Description

METHODS OF MAKING CATALYSTS, CATALYSTS, AND USES THEREOF CROSS REFERENCE TO RELATED APPLICATION [0001] This application claims priority to United States Provisional Patent Application number US 63/325,379, filed 03/30/2022, the entire contents of which are hereby incorporated by reference. FIELD [0002] The present disclosure relates generally to methods of making heterogeneous catalysts useful for processing oil-based materials, such as fossil fuel- based materials. BACKGROUND [0003] Industrial commercialization of high-value potential processes and integrated technology has facilitated the Canadian energy industry’s exploration and production of the world’s third largest estimated proven reserves of oil.^[1] The Alberta Energy Regulator (AER) estimates that of those reserves, crude bitumen accounts for 161 billion barrels,^[2] with 20% accounting for oil sands surface mining reserves and 80% for thermal in-situ extraction.^[3] Steam Assisted Gravity Drainage (SAGD)-produced bitumen contains gas oil and residuum fractions that are highly acidic as identified by Total Acid Number (TAN). Means of attending to, and/or processing highly acidic fossil fuel-based material is desired. SUMMARY [0004] In one or more aspects of the present disclosure, there is provided a method of preparing a metal oxide-supported catalyst, the method comprising: high-energy ball milling a coke-based material and metal oxide nanoparticles; comminuting the metal oxide nanoparticles to a size ≤100 nm; dispersing the metal oxide nanoparticles on the coke- based material; and forming the metal oxide-supported catalyst. [0005] In one or more embodiments of the present disclosure, there is provided a method further comprising pre-treating the coke-based material, wherein pre-treating the coke-based material comprises: grinding the coke-based material, high-energy ball milling the coke-based material in the presence of a base; hydrothermally degassing the coke- based material; and thermally treating the coke-based material at a temperature of at least 300°C. [0006] In one or more embodiments of the present disclosure, there is provided a method wherein the base comprises a hydroxide, such as potassium hydroxide (KOH), calcium hydroxide (Ca(OH)₂), and/or sodium hydroxide (NaOH). [0007] In another embodiment of the present disclosure, there is provided a method wherein high-energy ball milling comprises milling with zirconium oxide balls, stainless steel balls, metal carbide balls, or a combination thereof. [0008] In one or more embodiments of the present disclosure, there is provided a method wherein the high-energy ball milling comprises a ball-to-material mass ratio between about 20:1 to about 100:1. [0009] In one or more embodiments of the present disclosure, there is provided a method wherein the coke-based material comprises coke, petroleum coke, delayed petroleum coke, fluidized petroleum coke, raw petroleum coke, raw live petroleum coke fly ash, or a combination thereof. [0010] In one or more embodiments of the present disclosure, there is provided a method wherein the metal oxide nanoparticles are present at a weight percent between about 1wt% to about 50wt%, between about 10wt% to about 40wt%, or between about 20wt% to about 30 wt%; or about 25 wt%. [0011] In one or more embodiments of the present disclosure, there is provided a method wherein the metal oxide nanoparticles comprise an iron oxide, a magnetite, or a combination thereof. [0012] In one or more embodiments of the present disclosure, there is provided a method wherein the high-energy ball milling occurs at an RPM of at least 500 rpm. [0013] In one or more aspects of the present disclosure, there is provided a metal oxide-supported catalyst formed by one or more of the methods described herein. [0014] In one or more embodiments of the present disclosure, there is provided a catalyst wherein the catalyst is useful for reducing the total acid number (TAN) of acidic oil- based materials from a TAN ≥1 to a TAN <1. [0015] In one or more embodiments of the present disclosure, there is provided a catalyst wherein the catalyst is an esterification catalyst, a transesterification catalyst, a hydrogenation catalyst, or a combination thereof. [0016] In one or more embodiments of the present disclosure, there is provided a catalyst wherein the oil-based material comprises fossil fuel feedstock, such as bitumen, heavy bituminous crude, SAGD-produced bitumen, SAGD-produced diluted bitumen, oil, crude oil, oil sand, pyrolysis oil, scrap tire pyrolysis oil, gas oil, gas residuum, or a combination thereof; renewable feedstock, such as bio-based oil, fatty acid-derived oil, or a combination thereof; or a combination thereof. [0017] In one or more aspects of the present disclosure, there is provided a use of one or more of the metal oxide-supported catalysts described herein, or formed by one or more of the methods described herein, for esterifying an acidic oil-based material in the presence of a lower-molecular weight alcohol; transesterifying an acidic oil-based material in the presence of a lower-molecular weight alcohol; or a combination thereof. [0018] In one or more embodiments of the present disclosure, there is provided a use wherein the acidic oil-based material has a Total Acid Number (TAN) of ≥ 1. [0019] In one or more embodiments of the present disclosure, there is provided a use wherein esterifying and/or transesterifying the acidic oil-based material forms an esterified and/or transesterified oil-based material having a TAN between (0.5 ≤ TAN < 1) or a TAN < 0.5. [0020] In one or more embodiments of the present disclosure, there is provided a use wherein esterifying and/or transesterifying reduces the TAN of the acidic oil-based material by about 50% to about 99%; or about 65% to about 90%; or about 70% to about 90%; or about 85% to about 90%. [0021] In one or more embodiments of the present disclosure, there is provided a use wherein esterifying and/or transesterifying the acidic oil-based material occurs at a temperature between about 40°C to about 400°C; or between about 80°C to about 300°C; or between about 100°C to about 250°C; or between about 150°C to about 250°C; or between about 200°C to about 250°C. [0022] In one or more embodiments of the present disclosure, there is provided a use wherein the acidic oil-based material comprises fossil fuel feedstock, such as bitumen, SAGD-produced bitumen, SAGD-produced diluted bitumen, oil, crude oil, oil sand, pyrolysis oil, scrap tire pyrolysis oil, gas oil, gas residuum, or a combination thereof; renewable feedstock, such as a bio-based oil, a fatty acid-derived oil, or a combination thereof; or a combination thereof. [0023] In one or more embodiments of the present disclosure, there is provided a use wherein the lower-molecular weight alcohol comprises methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, tert-butanol, a glycol, or a combination thereof. BRIEF DESCRIPTION OF THE FIGURES [0024] Embodiments of the present disclosure will now be described, by way of example only, with reference to the attached Figures. [0025] FIG.1 graphically depicts TAN reduction with methanol (2wt%), 1 h hold at set-point temperature e.g., 200ºC), 1:5 mass ratio solid to liquid feed (MCB and methanol) ratio, nitrogen atmosphere initial pressure 1,000 kPa_g. [0026] FIG. 2 graphically depicts TAN reduction comparison (various materials) with bitumen TAN 2.25 mg KOH/g, methanol (20wt%), 1 h hold at set-point temperature 200ºC, 1:5 mass ratio solid to liquid feed (bitumen and methanol) ratio, nitrogen atmosphere initial pressure 1,000 kPa_g. [0027] FIG.3 graphically depicts TAN reduction using Fe₃O₄@MMP catalyst with bitumen TAN 2.25 mg KOH/g, methanol (variable, e.g., 20wt%), 1 h hold at set-point temperature 200ºC, 1:5 mass ratio solid to liquid feed (bitumen and methanol) ratio, nitrogen atmosphere initial pressure 1,000 kPa_g. [0028] FIG.4 graphically depicts TAN reduction reuse testing using Fe₃O₄@PPC catalyst with bitumen TAN 2.25 mg KOH/g, methanol (20wt%), 1 h hold at set-point temperature 200ºC, 1:5 mass ratio solid to liquid feed (bitumen and methanol) ratio, nitrogen atmosphere initial pressure 1,000 kPa_g. [0029] FIG. 5 graphically depicts TAN reduction using Fe₃O₄@PPC catalyst with bitumen TAN 2.25 mg KOH/g, methanol (20wt%), residence time (variable, e.g, 1 h hold) at set-point temperature 200ºC, 1:5 mass ratio solid to liquid feed (bitumen and methanol) ratio, nitrogen atmosphere initial pressure 1,000 kPag. [0030] FIG.6 depicts FTIR spectra of raw petroleum coke (dp < 300 micron) and the difference between samples after pre-treatment steps (HPT – Hydrothermal pre- treatment; TPT – Thermal pre-treatment) obtained by subtraction from the raw petroleum coke spectra. [0031] FIG.7 depicts TGA curves of raw petroleum coke (PC, dp < 300 micron), pretreated petroleum coke (PPC), final catalysts Fe₃O₄PPC and Fe₃O₄PC (100 mL/min air, 10ºC/min ramp). [0032] FIG.8 depicts XRD patterns of raw petroleum coke (PC, dp < 300 micron), pretreated petroleum coke (PPC), and Fe₃O₄@PPC catalyst (25wt% magnetite loading). [0033] FIG.9 depicts XRD patterns of raw magnetite nanoparticles (as received) and final Fe₃O₄@PPC catalyst (25wt% magnetite loading). [0034] FIG. 10A depicts SEM images (a) raw magnetite nanoparticles, (b) Fe₃O₄@PPC, (b’) Fe₃O₄@PPC backscatter electron image, and (c), (d), (e) Fe₃O₄@PPC element mapping images. [0035] FIG.10B depicts SEM images of Fe mapping on (a) raw petroleum coke, (b) pretreated petroleum coke, PPC (c) Fe₃O₄@PPC catalyst. [0036] FIG. 11 depicts a proposed Lewis Acid catalytic esterification with Fe₃O₄@PPC catalyst via Eley-Rideal mechanism. DETAILED DESCRIPTION [0037] Definitions [0038] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood in the art. [0039] As used in the specification and claims, the singular forms "a", "an" and "the" include plural references unless the context clearly dictates otherwise. [0040] The term "comprising" as used herein refers to the list following is non- exhaustive and may or may not include any other additional suitable items, for example one or more further feature(s), component(s) and/or ingredient(s) as appropriate. [0041] Unconventional, or thermal in-situ Steam Assisted Gravity Drainage (SAGD)- produced bitumen contains gas oil and residuum fractions that are highly acidic as identified by Total Acid Number (TAN). TAN is an industry accepted definition for the overall acidity of a petroleum species and is measured by the mass (milligram) of potassium hydroxide (KOH) required to neutralize the acidic components, typically carboxylic and sulfonic functional groups, contained in one gram of oil.^[4] The carboxylic functional group is most commonly connected to naphthenic structures,^[4] which are grouped together and classified as a mixture of monocyclic and polycyclic aliphatic organic carboxylic acids.^[5] These carboxylic acid constituents, naturally present in SAGD bitumen, are broadly generalized as Naphthenic Acids (NAs).^[5] Although NAs are considered to be the largest contributor to acidity,^[5,6] the concentration of NAs is not directly related to the TAN.^[6] Therefore, standardized testing methodology as defined by the American Standard for Testing and Materials (ASTM) D664, which measures all “mobile protons” that can be attributed to various other acidic species contained in the bitumen,^[6] is considered an aggregate index for the overall acidity.^[7] Table 1 below differentiates the TAN of various fractions of SAGD produced diluted bitumen, or dilbit, as an example to illustrate that virgin gas oil and residuum fractions contain the highest acidity.^[8] [0042] Based on industry accepted classifications, TAN can range from highly acidic (TAN ≥ 1), acidic (0.5 ≤ TAN < 1), and not acidic (TAN < 0.5). Highly acidic corrosive crude oils, specifically bitumen produced with high temperature thermal assisted recovery processes, increase the asset integrity risk of upstream production (emulsion gathering pipelines) and downstream (refining and upgrading) equipment at temperatures greater than 200ºC.^{[9, 10]} Current industry practices to manage TAN at downstream operations include dilution of acidic crude via blending with low acidity oil,^[11] chemical injection (corrosion inhibitors),^[12] and advanced material selection.^[13,14] Various studies have also been completed on catalytic^[15-18] and non-catalytic^[19] esterification using lower alcohols, such as methanol, in either sub-critical^[20] or super-critical phases.^{[21, 22]} Other approaches for crude oil TAN reduction are non-catalytic or catalytic thermal decomposition (cracking) and decarboxylation (naphthenic acid decomposition via pyrolysis) and hydrogenation, along with other chemical techniques such as adsorption separation, solvent and ionic liquid extraction, and neutralization.^[5] [0043] Alberta’s oil sand surface mining, located near Fort McMurray, has two major upstream delayed coking carbon rejection upgrading operations that produce solid waste petroleum coke^[23]: i) Canadian Natural Resources Limited (CNRL) Horizon Mine, and ii) Suncor Energy Oil Sands Group (OSG) Base Mine. According to the AER, in 2020 the coke produced between these two operations averaged near 22,900 metric tonnes per day, with year-end closing inventory stockpiles of approximately 72 million metric tonnes.^[24] Delayed petroleum coke, produced from thermal cracking of vacuum distillation tower bottoms resin and asphaltene components, is an amorphous and graphitic - high fixed carbon content - material. The graphitic structure, aromatic hydrogen content (<4wt%),^[25] and low value resulting from abundance are characteristics of delayed petroleum coke that provide a unique opportunity for use in solid-state heterogeneous catalysis. [0044] Various approaches, and resulting materials, have been developed using mechanochemical catalyst synthesis. From nanocomposites^[26] to carbon supported metal or metal oxide nanoparticle catalysts,^[27] high energy ball milling offers a unique approach that may not require the use of liquid solvents or harsh chemicals. These “dry” mechanochemical synthesis approaches are considered a “green” alternative to conventional material and catalyst production as the process may significantly reduce, or eliminate, waste streams. One example is the dispersion, or decoration, of metal oxide particle precursors on a suitable support via high energy, or planetary, milling. The increased ball-to-ball and ball-to-wall collision frequency during milling creates instantaneous localized shear and impact forces necessary for nanoparticle comminution (fragmenting), and resulting higher concentration of surface defects (i.e., oxygen vacancies), associated with the activation of the final catalytic material.^[28] Previous studies using high energy ball milling have also been completed for the decoration and reduction of iron oxide (magnetite) on a graphite support,^[29] production of magnetic biochar for adsorption applications,^[30] and the synthesis of titanium and silicon carbide nanopowders with petroleum coke (sponge) as the carbon source.^[31]. [0045] Generally, the present disclosure describes the development and testing of a metal oxide decorated delayed petroleum coke material. In one or more embodiments, metal oxide decorated delayed petroleum coke material may be used in the catalytic esterification of highly acidic oil. [0046] As described herein, the catalyst was prepared and developed to limit mass transfer limitations (internal diffusion) associated with larger molecular weight, high TAN, constituents present in gas oil and residuum fractions of bituminous crude. A mechanochemical, or mechanical activation, approach was applied using high energy planetary ball milling to produce a supported metal oxide nanocomposite material. The material was tested to determine catalytic performance for TAN reduction of acidic distillate model compound, before testing with a SAGD produced bitumen blend. [0047] In one or more embodiments, ball milling the herein described catalysts may facilitate loading/dispersing/decorating the active site metal oxide at quantities that may be difficult to achieve through traditional equilibrium or wetness impregnation followed by precipitation and/or calcination methodologies. In one or more embodiments, the herein described catalyst synthesis facilitates bringing the catalytic active sites to the reactant molecules (e.g., by external surface dispersion on the petcoke support), and may achieve a 25wt% target loading (and associated dispersion) that may not be achievable using existing traditional methods. In one or more embodiments, the mechanochemical method described herein may induce nanoparticle crystalline domain size reduction smaller than the starting domain size, which may be challenging to achieve with traditional methods. [0048] In one or more examples, there is provided a method of preparing a metal oxide-supported catalyst, the method comprising: high-energy ball milling a coke-based material and metal oxide nanoparticles; comminuting the metal oxide nanoparticles to a size ≤100 nm; dispersing the metal oxide nanoparticles on the coke-based material; and forming the metal oxide-supported catalyst. [0049] In one or more examples, there is provided a method further comprising pre- treating the coke-based material, wherein pre-treating the coke-based material comprises: grinding the coke-based material, high-energy ball milling the coke-based material in the presence of a base; hydrothermally degassing the coke-based material; and thermally treating the coke-based material at a temperature of at least 300°C. [0050] In one or more examples, there is provided a method wherein the base comprises a hydroxide, such as potassium hydroxide (KOH), calcium hydroxide (Ca(OH)₂), and/or sodium hydroxide (NaOH). [0051] In one or more examples, there is provided a method wherein high-energy ball milling comprises milling with zirconium oxide balls, stainless steel balls, metal carbide balls, or a combination thereof. [0052] In one or more examples, there is provided a method wherein the high- energy ball milling comprises a ball-to-material mass ratio between about 20:1 to about 100:1. [0053] In one or more examples, there is provided a method wherein the coke- based material comprises coke, petroleum coke, delayed petroleum coke, fluidized petroleum coke, raw petroleum coke, raw live petroleum coke fly ash, or a combination thereof. [0054] In one or more examples, there is provided a method wherein the metal oxide nanoparticles are present at a weight percent between about 1wt% to about 50wt%, between about 10wt% to about 40wt%, or between about 20wt% to about 30 wt%; or about 25 wt%. [0055] In one or more examples, there is provided a method wherein the metal oxide nanoparticles comprise an iron oxide, a magnetite, or a combination thereof. [0056] In one or more examples, there is provided a method wherein the high- energy ball milling occurs at an RPM of at least 500 rpm. [0057] In one or more examples, there is provided a metal oxide-supported catalyst formed by one or more of the methods described herein. [0058] In one or more examples, there is provided a catalyst wherein the catalyst is useful for reducing the total acid number (TAN) of acidic oil-based materials from a TAN ≥1 to a TAN <1. [0059] In one or more examples, there is provided a catalyst wherein the catalyst is an esterification catalyst, a transesterification catalyst, a hydrogenation catalyst, or a combination thereof. [0060] In one or more examples, there is provided a catalyst wherein the oil-based material comprises fossil fuel feedstock, such as bitumen, heavy bituminous crude, SAGD- produced bitumen, SAGD-produced diluted bitumen, oil, crude oil, oil sand, pyrolysis oil, scrap tire pyrolysis oil, gas oil, gas residuum, or a combination thereof; renewable feedstock, such as bio-based oil, fatty acid-derived oil, or a combination thereof; or a combination thereof. [0061] In one or more examples, there is provided a use of one or more of the metal oxide-supported catalysts described herein, or formed by one or more of the methods described herein, for esterifying an acidic oil-based material in the presence of a lower- molecular weight alcohol; transesterifying an acidic oil-based material in the presence of a lower-molecular weight alcohol; or a combination thereof. [0062] In one or more examples, there is provided a use wherein the acidic oil- based material has a Total Acid Number (TAN) of ≥ 1. [0063] In one or more examples, there is provided a use wherein esterifying and/or transesterifying the acidic oil-based material forms an esterified and/or transesterified oil- based material having a TAN between (0.5 ≤ TAN < 1) or a TAN < 0.5. [0064] In one or more examples, there is provided a use wherein esterifying and/or transesterifying reduces the TAN of the acidic oil-based material by about 50% to about 99%; or about 65% to about 90%; or about 70% to about 90%; or about 85% to about 90%. [0065] In one or more examples, there is provided a use wherein esterifying and/or transesterifying the acidic oil-based material occurs at a temperature between about 40°C to about 400°C; or between about 80°C to about 300°C; or between about 100°C to about 250°C; or between about 150°C to about 250°C; or between about 200°C to about 250°C. [0066] In one or more examples, there is provided a use wherein the acidic oil- based material comprises fossil fuel feedstock, such as bitumen, SAGD-produced bitumen, SAGD-produced diluted bitumen, oil, crude oil, oil sand, pyrolysis oil, scrap tire pyrolysis oil, gas oil, gas residuum, or a combination thereof; renewable feedstock, such as a bio-based oil, a fatty acid-derived oil, or a combination thereof; or a combination thereof. [0067] In one or more examples, there is provided a use wherein the lower- molecular weight alcohol comprises methanol, ethanol, n-propanol, iso-propanol, n- butanol, iso-butanol, tert-butanol, a glycol, or a combination thereof. [0068] In one or more examples, the high-energy ball milling comprises mechanochemical high-energy ball milling. In one or more examples, high-energy ball milling comprises ball milling that may be high energy (impact prominent), of planetary type, and/or having a speed of about >400 rpm. In one or more examples, high-energy ball milling comprises milling with balls at a ball-to-material mass ratio between 20:1 to 100:1. In one or more example, the balls comprise zirconium oxide balls, stainless steel balls, metal carbide balls (e.g., tungsten carbide balls), or a combination thereof. In one or more examples, the ball-to-material mass ratio comprises about 20:1 for pre-treatment ratios. In one or more examples, the ball-to-material mass ratio comprises about 100:1 for nanoparticle-loading catalyst synthesis. [0069] In one or more examples, the coke-based material comprises coke, petroleum coke, delayed petroleum coke, fluidized petroleum coke, raw petroleum coke, raw live petroleum coke fly ash, or a combination thereof. In one or more example, when the coke-based material comprises raw petroleum coke, the method may comprise a one- step catalyst synthesis. In one or more examples, when the coke-based material comprises raw petroleum coke, the one-step catalyst synthesis may provide a catalyst with relatively consistent performance. In one or more examples, when the coke-based material comprises raw petroleum coke, use of the catalyst may result in a relatively higher TAN reduction; for example, about 70% or more. [0070] In one or more examples, the metal oxide nanoparticles are present at a weight percent between about 1wt% to about 50wt%, between about 10wt% to about 40wt%, or between about 20wt% to about 30 wt%. In one or more examples, the amount of metal oxide nanoparticles that are present may be defined by the feed ratio of coke-base material to nanoparticle. In one or more examples, the metal oxide nanoparticles are present at a weight percent of about 25 wt%. In one or more examples, the metal oxide nanoparticles being present at a weight percent of about 25 wt% may allow for magnetically separating or isolating the catalyst from a liquid phase (e.g., a liquid phase of reactants, reagents, solvents, etc.). [0071] In one or more examples, comminuting the metal oxide nanoparticles comprises comminuting to a size ≤100 nm. In one or more examples, comminuting the metal oxide nanoparticles comprises comminuting to a size between about 1 nm to about 100 nm. [0072] In one or more examples, the hydrothermal degassing comprises solution- based degassing. In one or more examples, the hydrothermal degassing comprises removing sulfur-based components or materials, such as H₂S, from the coke-based material. In one or more examples, the hydrothermal degassing comprises removing sulfur- based components or materials, such as H₂S, from the coke-based material in the presence of the base, where the base desulfurizes the off-gas. In one or more examples, desulfurizing off-gas comprises the base reacting with the sulfur-based components or materials, such as H₂S, to form salts, such as sulfate salts. In one or more examples, removing sulfur-based components or materials, such as H₂S, may be beneficial in terms of not increasing sulfur content of resulting product(s), not releasing sulfur products (e.g., H₂S) during a reaction, and/or not deactivating catalysts through sulfur adsorption on active sites. [0073] In one or more examples, thermally treating the coke-based material comprises thermally treating at a temperature of at least 300°C. In one or more examples, thermally treating the coke-based material comprises thermally treating at a temperature of at least 300°C in air. In one or more examples, thermally treating the coke-based material comprises thermally treating at a temperature of at least 300°C in a muffled furnace in air. [0074] In one or more examples, the acidic oil-based material comprises fossil fuel feedstock, such as bitumen, heavy bituminous crude, SAGD-produced bitumen, SAGD- produced diluted bitumen, oil, crude oil, oil sand, pyrolysis oil, scrap tire pyrolysis oil, gas oil, gas residuum, or a combination thereof; renewable feedstock, such as a bio-based oil, a fatty acid-derived oil, or a combination thereof; or a combination thereof. In one or more examples, the acidic oil-based material comprises any acidic oil derived from waste materials (e.g., scrap tire pyrolysis oil), or bio-based oils. [0075] In one or more examples, esterifying and/or transesterifying the acidic oil- based material may occur at a temperature between about 40°C to about 400°C; or between about 80°C to about 300°C; or between about 100°C to about 250°C; or between about 150°C to about 250°C; or between about 200°C to about 250°C. In one or more examples, esterifying and/or transesterifying the acidic oil-based material may occur at a temperature of about 150°C, about 200°C, or about 250°C. In one or more examples, esterifying and/or transesterifying the acidic oil-based material may not occur at a temperature above about 400°C, as naphthenic acids in the acidic oil-based material may start to decompose. In one or more examples, esterifying and/or transesterifying the acidic oil-based material may occur at a temperature of at least about 40°C when the acidic oil- based material comprises a renewable feedstock. [0076] In one or more examples, the method provides a metal oxide-supported catalyst wherein the comminuted metal oxide nanoparticles the fragmented nanoparticles comprise active sites for catalytic reactions to take place. [0077] In one or more examples, when the acidic oil-based material comprises heavy bituminous crude, use of the metal oxide-supported catalyst as prepared by the method described herein may result in a TAN reduction of at least about 70% at about 200°C. In one or more examples, when the acidic oil-based material comprises heavy bituminous crude, use of the metal oxide-supported catalyst as prepared by the method described herein may result in a TAN reduction of at least about 85% at about 250°C. In one or more examples, when the acidic oil-based material comprises Model Compound Blend (MCB) as described herein, use of the metal oxide-supported catalyst as prepared by the method described herein may result in a TAN reduction of at least about 90% at about 200°C. [0078] In one or more examples, there is provided a catalyst material comprising metal oxide nanoparticles dispersed on a coke-based material; the metal oxide nanoparticles having a size less than 100 nm, and/or a dispersion between 20wt% to 30wt%; and the catalyst having a surface area between 5 to 175m²/g, a porosity between 0.02 to 0.11 mL/g, and a total acidity of at least 0.5 mmol/g. [0079] To gain a better understanding of the invention described herein, the following examples are set forth. It should be understood that these examples are for illustrative purposes only. Therefore, they should not limit the scope of this invention in anyway. [0080] EXAMPLES [0081] Example 1 - Total Acid Number (TAN) reduction of highly acidic McMurray formation SAGD bitumen using mechanochemically synthesized solid acid catalyst from petroleum coke [0082] Opportunity crude oils, specifically bitumen produced via Steam Assisted Gravity Drainage (SAGD), are generally considered low quality due to a high Total Acid Number (TAN). Catalytic esterification with methanol can improve the quality of crude oil to meet pipeline specification TAN, potentially minimizing netback penalties subjected to upstream producers, while also reducing the naphthenic acid corrosivity in downstream refining and upgrading. [0083] As described herein, a solid acid catalyst support derived from waste petroleum coke produced from Alberta oil sands mining delayed coking carbon rejection upgrading was developed and tested. The catalyst was a hybrid nanocomposite material produced via top-down mechanochemical synthesis methodology to disperse, or decorate, and activate iron (II,III) oxide magnetite nanoparticles on petroleum coke. It was considered that Lewis acidity was introduced via magnetite nanoparticle comminution, or fracturing, during mechanochemical high energy planetary ball milling, producing an active catalyst for the esterification of highly acidic model compound distillate and SAGD produced bituminous crude from, for example, the Alberta McMurray formation. The acidity of bituminous crude was reduced below pipeline specification (TAN <1) from TAN 2.25 to 0.74 mg KOH/g at 200ºC, 4.8 MPa (gauge), and using the developed catalyst with methanol in a batch reactor. [0084] Materials and Methods [0085] Materials [0086] Delayed petroleum coke (Alberta, Canada) received as raw material from oil sands mining upgrading. Naphthenic acid (technical), dodecane (anhydrous, ≥99%), methanol (ACS reagent, ≥99.8%), toluene (ACS reagent, ≥99.5%), propanol (ACS reagent, ≥99.5%), sodium hydroxide (ACS reagent, ≥97%), potassium hydroxide (≥85%), iron (III) chloride (reagent grade, 97%) and silicon carbide (-400 mesh, ≥97.5%) were purchased from Sigma Aldrich (Darmstadt, Germany). Iron (II,III) oxide (Fe₃O₄) nanopowder (50-100 nm, 20-50 m²/g, 97%) was purchased from Alfa Aesar (Tewksbury, MA, USA) and ferrous sulphate heptahydrate (ACS reagent, ≥99%) was purchased from Anachemia (Quebec, Canada). Gamma-alumina (modified oil drop process, spherical 2.5mm, 210 m²/g, >99%) was supplied by Sasol (Hamburg, Germany). Acid Number Reference Standard (TAN015, 1.54 mg KOH/g) was purchased from Paragon Scientific (Prenton, UK). Compressed nitrogen (99.999%, Alphagaz) was purchased from Air Liquide (Quebec, Canada). McMurray formation SAGD produced semi-diluted sales oil crude (Alberta, Canada) was received as a sample material from thermal in situ oil sands operation storage tanks. Acidic distillate model compound was prepared using a predetermined mass of naphthenic acid blended into a known mass of dodecane to simulate a model compound distillate, and was denoted as Model Compound Blend (MCB). [0087] Pretreated petroleum coke preparation [0088] Delayed petroleum coke was ground by hand using porcelain mortal and pestle followed by mechanical separation with W. S. Tyler No. 50 (300 micron, St. Catharines, ON, Canada) sieve and RX-29 (Mentor, OH, USA) sieve shaker. The prepared raw (green) petroleum coke was denoted as PC. The prepared raw petroleum coke was then mechanochemically pretreated using a Fritsch GmbH (Idar-Oberstein, Germany) Planetary Mono Mill (Pulverisette 6 classic line) with zirconium oxide grinding bowls (2, 80 mL capacity) and balls (5 mm diameter). Each of the two grinding bowls were filled with zirconium oxide balls, 5 g of prepared raw petroleum coke (ball-to-PC mass ratio = 20:1), 0.35 g of NaOH, and 25 mL of deionized water. The grinding bowls were sealed in the presence of atmospheric air, installed in the bowl holder, and the sample was milled at 300 rpm for 5 min. Upon completion, the contents in each grinding bowl were transferred to a 250 mL flat bottom flask via glass funnel for hydrothermal degassing treatment at 150 ºC and -800 mbar (gauge) for 3 h. After hydrothermal degassing, the solution was vacuum filtered using an EZFlow Foxx Nylon Membrane (47 mm diameter, 0.45 micron pore size) and washed using deionized water until the permeate (liquid) stream pH was neutral. The retentate (solids) were washed off the membrane using deionized water and collected in a 250 mL cylindrical beaker and dried in air at 120ºC overnight. After drying, 10 g of the solid was transferred and spread to a thickness of 5-10 mm on a flat ceramic plate (150 mm diameter) and thermally treated at 300ºC (ramp = 10ºC/min) for 12 h using a ventilated Vulcan 3-130 muffle furnace (York, PA, USA) in the presence of air. Yield for the pretreated petroleum coke during the thermal treatment step was >95wt% and the final material was denoted as PPC. [0089] Catalyst preparations [0090] The solid acid catalyst was mechanochemically prepared using the same ball mill as described previously. The grinding bowls were filled with zirconium oxide balls, 1.5 g of PPC (ball-to-PPC mass ratio = 100:1), and 0.5 g of magnetite nanoparticles (Fe₃O₄) to target a 25 wt% loading. The grinding bowls were sealed in the presence of atmospheric air, installed in the bowl holder, and the sample was milled at 500 rpm for 12 h. Upon completion, the contents in each grinding bowl were magnetically separated and transferred to a sealed vial. The prepared catalyst, or mechanochemically modified petroleum coke, was denoted as Fe₃O₄@PPC. [0091] The mechanochemically modified raw petroleum coke (PC) catalyst, denoted as Fe₃O₄@PC, was synthesized using the same procedure as Fe₃O₄@PPC except with PC (dp < 300 µm) instead of pretreated petroleum coke (PPC). Traditional gamma-alumina catalyst support was thermally pretreated at 550ºC^[18] (ramp = 10ºC/min) for 12 h using a ventilated Vulcan 3-130 muffle furnace (York, PA, USA) in the presence of air, and was denoted γ-Al₂O₃. Iron (II,III) loaded (target 25wt%) on gamma-alumina via traditional wetness impregnation of Fe³⁺ and Fe²⁺ (molar ratio 2:1) using FeCl₃ and FeSO₄•7H₂O precursor salts, with a predetermined volume of deionized water, was then calcined at 550ºC (ramp = 10ºC/min) for 4 h in the presence of air, and was denoted as Fe(II,III)/γ-Al₂O₃. [0092] Methods [0093] Analytical methods [0094] American Standard for Testing and Materials (ASTM) Standard Test Method A for Acid Number of Petroleum Products by Potentiometric Titration Designation D664 (ASTM D664) was referred to when performing a manual methodology to measure the TAN of the liquid feed and products. A SCHOTT Instruments Lab 850 Laboratory pH meter (Mainz, Germany) and associated SI Analytics non-aqueous probe (Ag/AgCl reference electrode, ethanol with 1.5M LiCl electrolyte, Weilheim, Germany) were used with the titration solvent and titrant potassium hydroxide standard alcoholic (propanol) solution prepared as per ASTM D664.^[32] The calculation method was defined by the following equation: Total Acid Number, mg KOH/g = (A – B) x M x (56.1 / W) where A is the volume of titration solution required for the oil sample (mL), B is the volume of titration solution required for the blank titration solvent sample (mL), M is the concentration of KOH (MW: 56.1 g/mol) in propanol of the titration solution (mol/L), and W is the mass of oil sample (g). The titration solution was added dropwise to the sample (liquid feed or product) until the end point was reached. The endpoint corresponded to the inflection point closest to the meter reading for the pH 10 aqueous buffer, or in the case of ill-defined, or no inflection point, to the meter reading corresponding to the pH 10 aqueous buffer. [0095] Experimental methods [0096] The reactions were completed using a Parr Instrument Company 5500 Series Compact Reactor (Moline, IL, USA) fitted with a removable glass liner for the stainless steel cylinder (nominal capacity: 300 mL), agitation propeller, and internal cooling loop. The removable glass liner was used to measure a known mass of reactants (solid catalyst, liquid feedstock, and methanol) prior to being installed into the reactor cylinder. Once the reactor flanges and split ring were installed, the reactor was purged with nitrogen to remove any atmospheric gases. The reactor was then placed in the external electric heater assembly with internal thermocouple connected to the controller, coupled to the magnetic drive for internal agitation, and cooling water supply/return connected to the seal flush and internal cooling coil connections. [0097] The internal agitator was started (Speed: 3/7; RPM: ~900), temperature controller was set to ramp and reach the desired set-point temperature (i.e., 200°C) and held for a specified residence time. Once the reaction was completed and the contents cooled to room temperature, the reactor cylinder was depressurized in a ventilated hood, opened, and the liquid products transferred to: i) a glass funnel containing a filter paper (Whatman Grade 42, Buckinghamshire, UK) to separate the solid catalyst from the liquid products (acidic distillate), and ii) a 250 mL flat bottom flask for vacuum distillation at 150ºC and -700 mbar (gauge), corrected to an atmospheric boiling point of 200ºC, to recover any unconsumed methanol, water, and light hydrocarbons. Next, toluene was added to reduce the viscosity facilitating the magnetic separation of the catalyst. An additional vacuum distillation step at the same conditions above was subsequently performed to recovery the toluene and produce the final separated liquid product (crude oil). For both the acidic distillate and crude oil reactions the recovered catalyst was washed with toluene using Soxhlet extraction until the permeate stream was clear and any weakly adsorbed compounds were removed. The recovered catalyst was then dried in a ventilated muffle furnace at 120 ºC (ramp = 10ºC/min) for 30 min to evaporate any excess toluene, transferred to a sealed vial, and used for reuse testing. [0098] Discussion [0099] TAN reduction of model compound distillate [00100] Acidic distillate model compound blends (1.76 and 2.01 mg KOH/g) were used to complete preliminary testing of the TAN reduction performance of the catalyst. First, blank reactions were carried out to determine the thermal effect of using silicon carbide as an unreactive solid with temperatures ranging from 100ºC to 300ºC. From Figure 1, between 200ºC and 250ºC, thermal effects of non-catalytic methanol esterification of the model compound blend distillate were identified. Therefore, 200ºC was selected as a basis to proceed that would limit introduction of thermal effects to quantify the impact of the catalytic performance. [00101] As illustrated in Figure 1, the Fe₃O₄@PPC catalyst improved TAN reduction performance by more than 80% when compared to the blank reactions using no solid (thermal), raw petroleum coke (PC, particle diameters (dP) < 300 µm), and silicon carbide (SiC) at 200ºC. This preliminary testing with the model compound was used to determine if further testing should be completed with a real crude oil feedstock. [00102] TAN reduction of McMurray formation bitumen [00103] The completion of the model compound study promoted the exploration of TAN reduction performance using highly acidic bitumen produced from Steam Assisted Gravity Drainage (SAGD) operations located in Alberta. The sample was a semi-diluted bitumen taken from sales oil storage tanks located upstream of final trim diluent addition. The TAN of the as-received semi-diluted sales oil sample was 1.71±0.03 mg KOH/g, and upon vacuum distillation at 150ºC and -700 mbar (gauge), atmospheric corrected to approximately 200ºC, the TAN of the resulting bitumen was 2.25±0.03 mg KOH/g after removing approximately 12wt% of light hydrocarbons. Since vacuum distillation, at the same conditions, was also part of the reaction liquid product and catalyst recovery process to obtain a final liquid product, the initial TAN of 2.25 mg KOH/g was used as the relative initial acidity of the liquid feed bitumen. [00104] Effect of Catalyst [00105] To understand the impact of the Fe3O4@PPC catalyst, a variety of blank reactions were completed with an increased methanol content (20wt%) as illustrated in Figure 2. Raw (as received) magnetite nanoparticles (normalized mass consistent with that loaded on the Fe₃O₄@PPC catalyst) were used to demonstrate that there is a synergetic effect between the magnetite nanoparticles and the pretreated petroleum coke during the final mechanochemical synthesis to produce the catalyst. The TAN reduction performance with Fe₃O₄@PPC, compared to the raw magnetite nanoparticles, also supported the hypothesis that dispersion, and resulting activation, of the magnetite nanoparticles occurred during the high energy ball milling catalyst synthesis. [00106] The acidic functional groups present on the pretreated petroleum coke (PPC) were presumed to have leached into the product liquid blend resulting in the elevated TAN compared to the non-catalytic thermal blank with no solid. Figure 2 also illustrates that an increased methanol content contributes to an improved TAN reduction and the use of the Fe₃O₄@PPC improves performance by 42% compared to the thermal blank (no solid). [00107] Effect Of Methanol Content [00108] Since the reactions were completed using a fixed volume batch reactor, the impact of methanol content and the associated final hold pressure at the set-point temperature 200ºC was studied. Figure 3 shows that as the methanol content was increased from 2.5wt% to 20wt% the catalytic TAN reduction performance using Fe₃O₄@PPC improved. The hold pressure increased because of the higher content of methanol (phase equilibrium) due to expansion in a fixed volume batch reactor. The appearance of a diminishing return when utilizing a higher initial content of methanol (e.g., 20wt%) may be attributed to the thermodynamic limitations for the conversion of methanol at the reaction temperature of 200ºC. [00109] Preliminary Fe₃o₄@Ppc Catalyst Reuse Testing [00110] An additional basis for testing the catalytic esterification at 200ºC was also to limit the effect of thermal catalytic cracking that would produce light end hydrocarbons and coke production. By limiting the cracking of long chain hydrocarbons and completing the reaction in excess methanol (e.g., 20wt%), the negative impacts associated with catalyst fouling via coking may also be mitigated. Since the intent of the mechanochemical synthesis was to load the metal oxides on the external surface of the pretreated petroleum coke, internal diffusion of heavy molecules into the catalyst pores, and resulting plugging, is mitigated. To perform a preliminary reuse test of the Fe₃O₄@PPC catalyst, multiple reactions were completed. See Figure 4. After the catalyst had been separated from the reaction liquid products, it was washed using toluene Soxhlet extraction methodology, dried in a ventilated muffle furnace at 120ºC for 30 min. This material was then reused in subsequent reactions with a small fraction (5wt%) of make-up fresh catalyst as the catalyst recovery yield was not 100%. [00111] Effect Of Residence Time [00112] Due to the nature of the batch reaction experimental setup, there was a ramp rate from ambient to the set-point hold temperature target of 200ºC. The duration of the ramp from approximately 20ºC to 200ºC was 30 min (i.e., 6ºC/min). The residence time and associated TAN reduction performance using the Fe₃O₄@PPC catalyst is illustrated in Figure 5. A residence time of 0 h was the ramp period only, with no hold duration. Each additional run at the variable residence time was completed separately with a consistent ramp duration to the target set-point of 200ºC. [00113] Catalytic Performance Comparison [00114] Commercial gamma-alumina (γ-Al₂O₃) that has been pretreated via calcination in air at 550ºC contains increased aluminum Lewis acid sites as a result of dehydroxylation.^[33,34] The total acidity of the γ-Al₂O₃, as measured by Boehm titration, was 0.83 mmol/g. Although the performance of the commercial pretreated gamma-alumina had an 18% improvement with consistent catalyst-to-liquid ratio as Fe₃O₄@PPC, the normalized performance associated with the total acidity per gram of metal oxide basis showed that γ-Al₂O₃ achieved a 10.6 % TAN reduction per gram metal oxide per mmol total acidity, versus Fe₃O₄@PPC which was 19.7%. Since the Fe₃O₄@PPC was derived from a waste material support, this material had advantages over the conventional catalyst. See Table 2. [00115] Catalyst Synthesis and Characterization [00116] After completing the preliminary performance tests of the Fe₃O₄@PPC catalyst on a model compound blend (acidic distillate), and a highly acidic bituminous crude oil, further material characterization was completed. The basis for mechanochemical pretreatment of the raw petroleum coke was to establish a reduced particle size with limited milling duration,^[35] coupled with alkaline solution exfoliation and sulphur reduction. The subsequent hydrothermal vacuum degassing at an atmospheric corrected temperature of 200ºC was intended to increase the stability of the petroleum coke while also neutralizing any liberated sulphur species with the aqueous alkaline solution. The final partial oxidation of the dried pretreated petroleum coke at 300ºC was to further stabilize the material while also increasing the concentration of oxygen-containing surface functional groups. Inductive coupled plasma optical emission spectrometry (ICP-OES) was completed on the raw petroleum coke (PC) and pretreated petroleum coke (PTP). Results indicated that the raw petroleum coke sulphur content of 5.4wt% was reduced to 3.1wt%, with the X-ray diffraction (XRD) pattern of the permeate solution evaporation residue indicating the presence of sodium sulphate crystalline structure. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was performed on samples to identify the oxygen containing functional groups produced. Bohem titration was used to determine the approximate strong (H+) and total acidity of the materials. The petroleum coke (PC) had negligible strong acidity (e.g. not detected)^[36] and total acidity between 0.34 mmol/g^[36] and 0.42 mmol/g,^[35] as shown in Table 3. After pretreating the petroleum coke, Boehm titration results indicated an increase in both strong acidity and total acidity. These acid sites may anchor the Fe₃O₄ particles and/or enhance the activity of the catalyst. [00117] As identified in Figure 6, the FTIR spectra for the final pretreated petroleum coke (PPC) contained the presence of increased oxygen functional groups. The generation of a peak at 2992 cm^-1 was consistent with the carboxylic acid (-COOH) O-H stretch, peaks at 1779 cm^-1 and 1843 cm^-1 related to carbonyl groups (ketones and ester, 4 atom ring, respectively) C=O stretch, and a peak at 1275 cm^-1 for ester (acyl) and/or aromatic phenol C-O stretch. The disappearance of peaks associated with aromatic hydrogen at 3050, 870, 805, and 750 cm^-1 were consistent with ball milling and subsequent thermal treatment of petroleum coke.^[37] The formation of a peak at 912 cm^-1 was associated with monosubstituted alkene sp² C-H bending. [00118] Thermogravimetric analysis (TGA) was used to estimate the final loading of magnetite in the Fe₃O₄@PPC catalyst. Figure 7 shows an increased ash content from 7wt% to 36wt% (+29wt%) from the pretreated petroleum coke (PPC). Since the target loading of magnetite was 25 wt%, there may be an increase in ash content as a result from contamination via milling with the zirconia (ZrO₂) milling materials (balls and/or vial) or the non-uniform dispersion of magnetite the sample (12 mg) of material used in the TGA work. [00119] The different TGA profiles for Fe₃O₄@PC and Fe₃O₄@PPC, shown by Figure 7, may indicate different metal and support interactions. [00120] The XRD diffraction patterns of the raw petroleum coke (PC), pretreated petroleum coke (PPC), and Fe₃O₄@PPC catalyst are shown in Figure 8. The effect of alkaline mechanochemical and hydrothermal degassing may have exfoliated the graphitic structure resulting in the change of the peak width between 20-30º 2θ,^[38] for PPC compared to raw PC. The unidentified peaks in the PPC XRD pattern may correspond to exposed metal components after the pretreatment. [00121] Magnetite Nanoparticle Dispersion [00122] The synergy between the pretreated petroleum coke (PPC) support and the dispersed magnetite nanoparticles, leading to improved TAN reduction performance, was considered a result of mechanochemical synthesis. XRD and SEM techniques were used to confirm high energy ball milling facilitates particle comminution, or fragmenting, creating smaller magnetite particles. Figure 9 XRD diffraction patterns for Fe₃O₄@PPC and raw (as received) magnetite nanoparticles identified that peaks associated with magnetite were broadened with reduced intensity for Fe₃O₄@PPC. [00123] The resulting dispersion, or decoration, of the magnetite nanoparticles was confirmed by Scanning Electron Microscope (SEM) and element mapping, Figure 10A and B. [00124] Proposed Catalyst Esterification Mechanism [00125] Catalytic TAN reduction performance using Fe₃O₄@PC, which had no strong (H⁺) surface acidity as measured by Boehm titration, indicated that it was likely the magnetite that was active in the reaction. Therefore, the catalytic activity was proposed to have been created as a result of the highly dispersed iron (magnetite) produced as a result of high energy ball milling. The creation of magnetite nanoparticle surface defects associated with oxygen vacancies may have contributed to increased Lewis acidity. It was proposed that the TAN reduction was predominantly Lewis acid site catalytic esterification, as illustrated by a simplified Eley-Rideal mechanism, shown in Figure 11. [00126] The elevated magnetite loading targeted at 25wt% was an advantage of mechanochemical synthesis for the production of Fe₃O₄@PPC as the basis for the elevated loading to facilitate magnetic separation of the catalytic material from heavy crude. Considering the change in TAN of the bituminous crude for the reactions with a residence time of 1 h, 20 wt% methanol (e.g., 67% reduction in TAN), the estimated Fe₃O₄@PPC Turnover Frequency (TOF) was 2.1x10^-3 h^-1. Total acidity of Fe₃O₄@PPC after multiple reuses (3) was 1.15 mmol/g, a change of 0.12 mmol/g or 9.4% reduction compared to a fresh sample. This may have been caused by deposition, fouling, or adsorption of molecules, or poisoning via sulphur containing species or crude oil heavy metals on acidic sites. [00127] Conclusions [00128] The TAN reduction of highly acidic SAGD produce bitumen was achieved using a metal oxide dispersed on petroleum coke via mechanochemical synthesis with and without alkaline pretreatments. SEM imaging and XRD indicated the dispersion of magnetite nanoparticles created a dispersed nanocomposite material. As described herein, mechanochemical synthesis was found to activate magnetite nanoparticles to increase reactivity, and facilitated the TAN reduction performance below catalytic cracking temperatures at 200°C. Increased Lewis acid sites, that were more stable than Brǿnsted acid sites, promoted catalytic esterification [00129] TABLE 1 TAN of Access Western Blend (AWB) Sour Unconventional Blend (Alberta, Canada) Distillate Gas Oil Naphtha Residuu operty ^Whole C_rude (190^{° °} m Pr C to (343C to (IBP to 190^°C) (527^°C+) 343^°C) 527^°C)

TAN

(_{mg KOH/g)} ^{1.62 - 0.63 3.27 1.33} [00130] TABLE 2 Catalytic TAN reduction comparisons C^{atalyst Reaction Conditions Catalyst-to-} TAN L_{iquid Ratio Reduction} ^Reference S_n/Al2O3 ^{Fixed Bed; T=200°C; 2wt%} m_{ethanol, real crude 1:1 (v/v) 4% [17]} Fixed Bed; T=200°C; 2wt% TPA/γ-Al₂O₃ methanol, simulated acidic 1:5 (v/v) 38% [18] crude F_e3O4@PPC ^{Batch; T=200°C; 2.5wt%} m_{ethanol, real crude 1:5 (w/w) 47%} Present work F_e3O4@PPC ^{Batch; T=200°C; 20wt%} Present m_{ethanol, real crude 1:5 (w/w) 67%} Work F^e ₃ ^O ₄ ^{@PC Batch; T=200°C; 20w} Present m_{ethanol, real crude} ^{1:5 (w/w) 70%} work γ^-Al ₂ ^O ₃ ^{Batch; T=200°C; 20w} Present m_{ethanol, real crude} ^{1:5 (w/w) 88%} work

Fe(II,III)/γ- Batch; T=200°C; 20w Present Al₂O_{3 methanol, real crude} ^{1:5 (w/w) 73%} work

[00131] TABLE 3 Properties of petroleum coke and catalysts Strong Total Acidi ^{2 3 4 1} ty Surface Area Porosity Sample ID Acidity (mmol/g) (m²/g) (mL/g)

PC

0.34-0.42 ~0 PPC 0.19 4.02 2 0.01 Fe₃O₄@PPC 0.14 1.27 9 0.04 Fe₃O₄@PC ~0 1.83 173 0.11 γ-Al₂O₃ Not determined 0.83 208 0.53 ¹Bohem titration with NaCl, ²Bohem titration with HCl, ³BET SA, ⁴BJH Adsorption/Desorption [00132] References [1] Oil Gas J., Worldwide Look at Reserves and Production, 2020, https://www.ogj.com (accessed: January 2022). Oil Gas J., Worldwide Look at Reserves and Production, 2020, https://www.ogj.com (accessed: January 2022). Oil & Gas Journal, Worldwide Look at Reserves and Production, pp.16-17, 2019. [Online]. Available: https://cdn.ogj.com/files/base/ebm/ogj/document/2020/03/191202OGJ_Worldwide Production.5e5ee46e8d9be.pdf [2] Alberta Energy Regulator, Alberta Energy Outlook ST982021 Executive Summary, 2021, https://www.aer.ca (accessed: January 2022). Alberta Energy Regulator, Alberta Energy Outlook ST98 Executive Summary 2019, Table 1 Resources, reserves, and production summary 2018, pp. 9, 2019. [Online]. Available: https://www1.aer.ca/st98-2019-test/data/executive-summary/ST98-2019- Executive-Summary-May-2019.pdf [3] Alberta Energy Regulator Oil Sands web page, https://www.aer.ca (accessed: January 2022). Alberta Energy Regulator, Oil Sands, 2021. [Online]. [Accessed: 05.20.20]. Available: https://www.aer.ca/providing-information/by-topic/oil-sands [4] M. R. Gray, Upgrading Oilsands Bitumen and Heavy Oil, 1st ed., University of Alberta Press, Edmonton, Canada 2015. M. R. Gray, “Chemical Composition: Chemical Structures in Bitumen”, in Upgrading Oilsands Bitumen and Heavy Oil, 1st ed. Edmonton, Canada: University of Alberta Press, 2015, ch.3, sec.5, pp.117. [Online]. Available: https://www-deslibrisca.ezproxy.lib.ucalgary.ca/ID/450794 [5] C. Wu, A. De Visscher, I. D. Gates, Fuel 2019, 253, 1229. C. Wu, A. De Visscher, I. D. Gates, On naphthenic acids removal from crude oil and oil sands process- affected water. Fuel 2019, vol.253, pp.1229-1246. [Online]. Available: https://www- sciencedirect-com.ezproxy.lib.ucalgary.ca/science/article/pii/S0016236119308439 [6] M. M. Ramirez-Corredores, in The Science and Technology of Unconventional Oils: Finding Refining Opportunities, Academic Press Elsevier Inc., London, United Kingdom 2017, Ch.4. M. M. Ramirez-Corredores, “Acidity in Crude Oils: Naphthenic Acids and Naphthenates”, in The Science and Technology of Unconventional Oils: Finding Refining Opportunities, London, United Kingdom: Academic Press Elsevier Inc., 2017, ch. 4, sec. 1, pp. 295-297. [Online]. Available: http://dx.doi.org/ 10.1016/B978-0-12-801225-3.00004-8 [7] R. Bacon, S. Tordo, Crude oil price differentials and differences in oil qualities: a statistical analysis, (WB.34906), 2004, https://openknowledge.worldbank.org (accessed: January 2022). Bacon R, Tordo S. Crude oil price differentials and differences in oil qualities: a statistical analysis. Report No. WB.34906. Technical paper No.81. Washington, DC, USA: ESMAP; October 01, 2004.40 pp. [Online]. Available: http://documents.worldbank.org/curated/en/673981468778803478/pdf/ 30394-Replacement-file-275-BACO.pdf [8] Crude Quality Incorporated, Crude Monitor ASTM D2892 & D5236 TBP Mini-Assay Access Western Blend (April 2015) web page, https://www.crudemonitor.ca (accessed: January 2022). Crude Quality Incorporated, Crude Monitor: ASTM D2892 & D5236 TBP Mini-Assay, Access Western Blend (April 2015), [Accessed: 01.05.2022]. [Online]. Available: https://www.crudemonitor.ca/crudes/assay.php?acr=AWB&crudename=Access% 20Western%20Blend&id=108 [9] CCQTA TAN Project Summary White Paper web page, https://www.ccqta.com (accessed: January 2022). https://www.ccqta.com//whitepapers/CCQTA%20Tan%20Project%20Summary%2 0.pdf [10] E. Slavcheva, B. Shone, A. Turnbull, Brit. Corros. J.1999, 34, 125. Slavcheva E, Shone B, Turnbull A. Review of naphthenic acid corrosion in oil refining. Br Corros J 1999;34:125–31. http://dx.doi.org/10.1179/ 000705999101500761. [11] O. Yepez, Fuel 2005, 84, 97. Omar Yepez. Influence of different sulfur compounds on corrosion due to naphthenic acid. Fuel 84 (2005) 97-104. https://www- sciencedirect-com.ezproxy.lib.ucalgary.ca/science/article/pii/S0016236104002200 [12] S. Dwivedy, R. Navarrete (Baker Hughes), Treatment programme overcomes high TAN problems: Processing high TAN crude with low sulphur shale oil presented challenging corrosion problems for a refiner (101200), 2015, https://www.digitalrefining.com (Accessed: January 2022). SANJAY DWIVEDY and RALPH NAVARRETE. Treatment programme overcomes high TAN problems: Processing high TAN crude with low sulphur shale oil presented challenging corrosion problems for a refiner (Baker Hughes). Digital Refining (2015) Article 101200. https://www.digitalrefining.com/article/1001200/treatment-programme- overcomes-high-tan-problems#.YdcuoGjMLRY [13] W. Qing (CNOOC), Processing high TAN crude: part II (1000427), 2011, https://www.digitalrefining.com (accessed: January 2022). Wu Qing. Processing high TAN crude: part II (CNOOC). Digital Refining (2011) Article 1000427. https://www.digitalrefining.com/article/1000427/processing-high-tan-crude-part- ii#.YdcwMmjMLRY [14] O. P. Alvisi, V. F. C. Lins, Eng. Fail. Anal.2011, 18, 1403. Oaulo P. Alvisi, Vanessa F.C. Lins. An overview of naphthenic acid corrosion in a vacuum distillation plant. Engineering Failure Analysis 18 (2011) 1403-1406. https://www-sciencedirect- com.ezproxy.lib.ucalgary.ca/science/article/pii/S1350630711000720 [15] Y. Z. Wang, Y. P. Liu, C. G. Liu, Pet. Sci. Technol.2008, 26, 1424. Wang YZ, Liu YP, Liu CG. Removal of naphthenic acids of a second vacuum fraction by catalytic esterification. Pet Sci Technol 2008;26:1424–32. http://dx.doi.org/10. 1080/10916460701272229. [16] X. Li et al., Fuel Process. Technol.2013, 111, 68. Li X, Zhu J, Liu Q, Wu B. The removal of naphthenic acids from dewaxed VGO via esterification catalyzed by Mg-Al hydrotalcite. Fuel Process Technol 2013;111:68–77. http://dx.doi.org/10.1016/j.fuproc.2013.01.016. [17] Y. Z. Wang et al., Fuel 2014, 116, 723.Wang YZ, Li JY, Sun XY, Duan HL, Song CM, Zhang MM, et al. Removal of naphthenic acids from crude oils by fixed-bed catalytic esterification. Fuel 2014;116:723–8. http://dx.doi.org/10.1016/j.fuel.2013.08.047. [18] B. S. Rana et al., Fuel 2018, 231, 271. B. S. Rana, D.-W. Cho, K. Cho, J.-N. Kim, Total Acid Number (TAN) reduction of high acidic crude oil by catalytic esterification of naphthenic acids in fixed-bed continuous flow reactor. Fuel 2018, 231, 271-280. [Online]. Available: https://www- sciencedirectcom.ezproxy.lib.ucalgary.ca/science/article/pii/S0016236118308974 [19] G. Sartori et al. (Exxon Research and Engineering Company), U.S. Pat. No. 6251305, 2001. Esterification of acidic crudes. U.S. Pat. No.6251305, 2001. [20] M. K. Khan et al., Fuel Process. Technol.2017, 165, 123. Muhammad Kashif Khan, Asim Riaz, Minhoe Yi, Jaehoon Kim. Removal of naphthenic acids from high acid crude via esterification with methanol. Fuel Processing Technology 165 (2017) 123- 130. https://www-sciencedirect- com.ezproxy.lib.ucalgary.ca/science/article/pii/S0378382016312991 [21] M. K. Khan et al., Fuel 2016, 182, 650. Muhammad Kashif Khan, Rizki Insyani, Jinkee Lee, Minhoe Yi, Jae Woo Lee, Jaehoon Kim. A non-catalytic, supercritical methanol route for effective deacidification of naphthenic acids. Fuel 182 (2016) 650-659. https://www-sciencedirect- com.ezproxy.lib.ucalgary.ca/science/article/pii/S001623611630477X [22] P. C. Mandal et al., Fuel Process Technol 2013, 106, 641. Pradip Chandra Mandal, Wahyudiono, Mitsuru Sasaki, Motonobu Goto. Non-catalytic reduction of total acid number (TAN) of naphthenic acids (NAs) using supercritical methanol. Fuel Processing Technology 106 (2013) 641-644. https://www-sciencedirect- com.ezproxy.lib.ucalgary.ca/science/article/pii/S0378382012003840 [23] Oil Sands Magazine Bitumen Upgrading Explained web page, https://www.oilsandsmagazine.com (accessed: January 2022). https://www.oilsandsmagazine.com/technical/bitumen-upgrading#alberta [24] Alberta Energy Regulator, Alberta Mineable Oil Sands Plant Statistics ST39 Monthly Supplement December 2020, 2020, https://www.aer.ca (accessed: January 2022). Alberta Energy Regulator, Alberta Mineable Oil Sands Plant Statistics ST39 Monthly Supplement December 2020, pp.11 & 432020. [Online]. Available: https://static.aer.ca/prd/documents/sts/ST39-2020.pdf [25] L. D. Virla et al., Micropor. Mesopor. Mat.2016, 234, 239. L. D. Virla, V. Montes, J. Wu, S. F. Ketep, J. M. Hill. Synthesis of porous carbon from petroleum coke using steam, potassium and sodium: Combining treatments to create mesoporosity. Microporous and Mesoporous Materials 2016, 234, 239-247. [Online]. Available: https://www-sciencedirect- com.ezproxy.lib.ucalgary.ca/science/article/pii/S1387181116302773 [26] T. P. Yadav, R. M. Yadav, D. P. Singh, Nanosci. Nanotech.2012, 2, 22. Thakur Prasad Yadav, Ram Manohar Yadav, Dinesh Pratap Singh. Mechanical Milling: a Top Down Approach for the Synthesis of Nanomaterials and Nanocomposites. Nanoscience and Nanotechnology 2012, 2(3): 22-48. [27] C. Xu et al., Chem. Commun.2015, 51, 6698. Chunping Xu, Sudipta De, Alina M. Balu, Manuel Ojedad and Rafael Luque. Mechanochemical synthesis of advanced nanomaterials for catalytic application. Chem. Commun., 2015, 51, 6698-6713 [28] P. Balaz et al., Chem. Soc. Rev.2013, 42, 7571. Peter Balaz et al. Hallmarks of mechanochemistry: from nanoparticles to technology. Chem. Soc. Rev., 2013, 42, 7571-7637 [29] L. H. Moloto, S. S. Manzini, E. D. Dikio, J. Chem. 2013, http//www.doi.org/10.1155/2013/837649 Ledwaba Harry Moloto, Sunnyboy Stanley Manzini, and Ezekiel Dixon Dikio. Reduction of Magnetite in the Presence of Activated Carbon Using Mechanical Alloying. Journal of Chemistry 2013 [30] Y. Li et al., Sci. Total Environ. 2020, 722, 137972. Yanfei Li et al. Solvent-free synthesis of magnetic biochar and activated carbon through ball-mill extrusion with Fe3O4 nanoparticles for enhancing adsorption of methylene blue. Science of the Total Environment 722 (2020) 137972 [31] X. Cui et al., Pet. Sci. Technol.2001, 19, 971. Xiaolong Cui , Yanhua Wang , Lai Wang , Lishan Cui & Min Qi. SYNTHESIS OF NANOMETER-SIZED TiC AND SiC FROM PETROLEUM COKE BY REACTIVE MILLING. Petroleum Science and Technology (2001), 19:7-8, 971-978 [32] ASTM, Standard Test Method for Acid Number of Petroleum Products by Potentiometric Titration (D664-18E2, Active), 2020, https://www.astm.org, (accessed: January 2022) ASTM D664-18E2 Standard Test Method for Acid Number of Petroleum Products by Potentiometric Titration (active): https://www.astm.org/d0664-18e02.html [33] M. R. Gafurov et al., J. Phys. Chem. C 2015, 119, 27410. Quantitative Analysis of Lewis Acid Centers of γ-Alumina by Using EPR of the Adsorbed Anthraquinone as a Probe Molecule: Comparison with the Pyridine, Carbon Monoxide IR, and TPD of Ammonia Marat R. Gafurov,*,† Ildar N. Mukhambetov, Boris V. Yavkin,† Georgy V. Mamin,† Alexander A. Lamberov, and Sergei B. Orlinskii† J. Phys. Chem. C 2015, 119, 27410−27415 [34] A. Kurhade, Ph.D., University of Saskatchewan (Canada) 2019. SYNTHESIS AND CHARACTERIZATION OF SUPPORTED SOLID ACID CATALYSTS FOR CONVERSION OF GREEN SEED CANOLA OIL TO BIODIESEL ANKEETA KURHADE November, 2019 For the Degree of Doctor of Philosophy In the Department of Chemical and Biological Engineering University of Saskatchewan Saskatoon [35] A. C. Baffa Carlotto, M.Sc., University of Calgary (Canada) 2021. Modification of Physicochemical Properties of Petroleum Coke with Ball Milling; Baffa Carlotto, Ana Cristina [36] Q. Huang et al., Catalysts 2020, 10, 259. Nitric Acid Functionalization of Petroleum Coke to Access Inherent Sulfur; Q. Huang et al. [37] Y. Xiao, J. M. Hill, Chemosphere 2020, 248, 125981. Ye Xiao, Josephine M. Hill Solid acid catalysts produced by sulfonation of petroleum coke: Dominant role of aromatic hydrogen Chemosphere Volume 248, June 2020, 125981 [38] F. T. Johra et al., J. Ind. Eng. Chem.2014, 20, 2883. Facile and safe graphene preparation on solution based platform; F.T. Johra et al.. [39] Q. Li et al., Sci. Rep. 2017, 7, 9894. Correlation between particle size domain structure and magnetic properties of highly crystalline Fe3O4 nanoparticles; Qing et al. [00133] Alterations, modifications and variations can be effected by those of skill in the art to particular embodiments described herein. The scope of the claims should not be limited by the particular embodiments set forth herein, but should be construed in a manner consistent with the specification as a whole. [00134] All publications, patents and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication patent, or patent application was specifically and individually indicated to be incorporated by reference.

Claims

WHAT IS CLAIMED IS: 1. A method of preparing a metal oxide-supported catalyst, the method comprising: high-energy ball milling a coke-based material and metal oxide nanoparticles; comminuting the metal oxide nanoparticles to a size ≤100 nm; dispersing the metal oxide nanoparticles on the coke-based material; and forming the metal oxide-supported catalyst.

2. The method of claim 1, further comprising pre-treating the coke-based material, wherein pre-treating the coke-based material comprises: grinding the coke-based material, high-energy ball milling the coke-based material in the presence of a base; hydrothermally degassing the coke-based material; and thermally treating the coke-based material at a temperature of at least 300°C.

3. The method of claim 2, wherein the base comprises a hydroxide, such as potassium hydroxide (KOH), calcium hydroxide (Ca(OH)₂), and/or sodium hydroxide (NaOH).

4. The method of any one of claims 1 to 3, wherein high-energy ball milling comprises milling with zirconium oxide balls, stainless steel balls, metal carbide balls, or a combination thereof.

5. The method of any one of claims 1 to 4, wherein the high-energy ball milling comprises a ball-to-material mass ratio between about 20:1 to about 100:1.

6. The method of any one of claims 1 to 5, wherein the coke-based material comprises coke, petroleum coke, delayed petroleum coke, fluidized petroleum coke, raw petroleum coke, raw live petroleum coke fly ash, or a combination thereof.

7. The method of any one of claims 1 to 6, wherein the metal oxide nanoparticles are present at a weight percent between about 1wt% to about 50wt%, between about 10wt% to about 40wt%, or between about 20wt% to about 30 wt%; or about 25 wt%.

8. The method of any one of claims 1 to 7, wherein the metal oxide nanoparticles comprise an iron oxide, a magnetite, or a combination thereof.

9. The method of any one of claims 1 to 8, wherein the high-energy ball milling occurs at an RPM of at least 500 rpm.

10. A metal oxide-supported catalyst formed by the method of any one of claims 1 to 9.

11. The catalyst of claim 10, wherein the catalyst is useful for reducing the total acid number (TAN) of acidic oil-based materials from a TAN ≥1 to a TAN <1.

12. The catalyst of claim 10 or 11, wherein the catalyst is an esterification catalyst, a transesterification catalyst, a hydrogenation catalyst, or a combination thereof.

13. The catalyst of claim 11 or 12, wherein the oil-based material comprises fossil fuel feedstock, such as bitumen, heavy bituminous crude, SAGD-produced bitumen, SAGD- produced diluted bitumen, oil, crude oil, oil sand, pyrolysis oil, scrap tire pyrolysis oil, gas oil, gas residuum, or a combination thereof; renewable feedstock, such as bio-based oil, fatty acid-derived oil, or a combination thereof; or a combination thereof.

14. Use of the metal oxide-supported catalyst of any one of claims 10 to 13, or formed by the method of any one of claims 1 to 9, for esterifying an acidic oil-based material in the presence of a lower-molecular weight alcohol; transesterifying an acidic oil-based material in the presence of a lower-molecular weight alcohol; or a combination thereof.

15. The use of claim 14, wherein the acidic oil-based material has a Total Acid Number (TAN) of ≥ 1.

16. The use of claim 14 or 15, wherein esterifying and/or transesterifying the acidic oil- based material forms an esterified and/or transesterified oil-based material having a TAN between (0.5 ≤ TAN < 1) or a TAN < 0.5.

17. The use of any one of claims 14 to 16, wherein esterifying and/or transesterifying reduces the TAN of the acidic oil-based material by about 50% to about 99%; or about 65% to about 90%; or about 70% to about 90%; or about 85% to about 90%.

18. The use of any one of claims 14 to 17, wherein esterifying and/or transesterifying the acidic oil-based material occurs at a temperature between about 40°C to about 400°C; or between about 80°C to about 300°C; or between about 100°C to about 250°C; or between about 150°C to about 250°C; or between about 200°C to about 250°C.

19. The use of any one of claims 14 to 18, wherein the acidic oil-based material comprises fossil fuel feedstock, such as bitumen, SAGD-produced bitumen, SAGD- produced diluted bitumen, oil, crude oil, oil sand, pyrolysis oil, scrap tire pyrolysis oil, gas oil, gas residuum, or a combination thereof; renewable feedstock, such as a bio-based oil, a fatty acid-derived oil, or a combination thereof; or a combination thereof.

20. The use of any one of claims 14 to 19, wherein the lower-molecular weight alcohol comprises methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, tert- butanol, a glycol, or a combination thereof.