Coprocessing of bio-olefins

Abstract

The present disclosure relates to coprocessing of bio-olefins using blended renewable feedstocks comprising a first renewable feedstock comprising a precursor of hydroprocessed esters and fatty acids (HEFA) and a second renewable feedstock comprising a bio-olefin. Blended renewable feedstocks for obtaining paraffinic jet and diesel fuels, and renewable paraffinic jet and diesel products obtained therefrom are also provided.

Description

COPROCESSING OF BIO-OLEFINSCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 663,769, filed June 25, 2024, which is incorporated by reference herein in its entirety.BACKGROUND

[0002] Various types of biofuel are being produced to decarbonize the transportation sector, including biodiesel, renewable diesel (RD) and sustainable (or “synthetic”) aviation fuel (SAF). For example, the international aviation industry has set an aspirational goal to reach net zero carbon by 2050. There are significant challenges to overcome to increase the supply of SAF. Producing SAF in standalone plants demands substantial capital and time for constructing new units or revamping units. To cut costs and speed production, co-processing by blending fossil and renewable feedstocks like vegetable oil, animal fat, and used cooking oil (UCO) can be implemented to produce co-hydroprocessed synthesized kerosene, suitable for jet fuel manufacturing. However, in co-processing refinery units, the renewable feedstock’s volume is typically capped at 5%, with the rest being conventionally sourced hydrocarbons. Increasing the co-processing ratio to 10% or higher may require revamps to handle elevated exothermic reactions or address corrosion concerns associated with renewable fats and oils as co-processing feedstock.

[0003] ASTM specification D7566 covers the manufacture of aviation fuel that consists of conventional and synthetic blending components. ASTM has approved 8 pathways to produce synthetic blend components. One of the pathways considered for the production of synthetic paraffinic kerosene (SPK) is the hydroprocessed esters and fatty acids (HEFA) pathway.

[0004] An illustrative example of a HEFA process is shown in FIG. 1. In process 100, a treated HEFA feedstock 102 is hydrodeoxygenated in the presence of a hydrogenation catalyst at block 104. After this first hydrotreatment section, oxygen is completely removed, and a pure paraffinic product is obtained, with typically the same carbon atom distribution as in the starting feedstock. The carbon number range of the deoxygenated HEFA feed molecules is in the Cis to C22 range. Feedstocks rich in lipids (e.g., waste vegetable oils, grease, and animal fats) yield linear paraffins upon deoxygenation. The boiling range of this product exceeds that of typical jet fuels. At block 106, the hydrogenated product is isomerized to produce iso-paraffinic compounds in the presence of an isomerization catalyst, and larger hydrocarbons are cracked into smaller chain molecules in the presence of a hydrocracking catalyst. A HEFA process can produce both jet and diesel range fuel products. While the relative yield of products can depend on the feedstock composition, longer hydrocarbons canbe cracked into shorter chains to produce SPK, if desired. For HEFA-SPK, catalysts must be carefully selected to minimize cracking reactions that result in yield loss from gases and lighter cuts like Naphtha. At block 108, the isomerized and cracked product undergoes a separation process, such as fractionation by distillation. As shown in FIG. 1 , fractionation allows for the separation of SPK, RD, and lighter fractions including Naphtha. This pathway has already gained broader acceptance to produce RD. However, this pathway is faced with several challenges, including feedstock availability, operating costs, requirement for multiple catalysts, and loss of carbon. The production of lighter compounds decreases the overall yield of SAF (per kg of feedstock).

[0005] Feedstock availability - HEFA feeds are composed of non-food vegetable oils, used cooking oil, animal fats, or waste greases. Securing supply of consistent feedstock is challenging and may become increasingly difficult as the demand for sustainable feed increases. Besides the HEFA pathway, other approved pathways also use the same lipid feedstocks.

[0006] Operating costs - The HEFA pathway consists of hydrodeoxygenation of the feed to straight-chain paraffinic hydrocarbons followed by hydro-isomerization to iso-paraffins using an expensive isomerization catalyst. The hydro-isomerization step is necessary to improve the cold flow properties of the final product.

[0007] Multiple Catalysts Required - When the HEFA pathway is used for producing SPK, an additional step of hydrocracking is required due to the larger carbon number chains (C -plus) in the lipid feedstock. Modification of fractionation may also be required to separate the SPK product from the diesel product. Use of multiple catalysts (isomerization and hydrocracking) increases the operating cost of the pathway.

[0008] Loss of Carbon - In the HEFA-to-jet pathway, significant quantities of low-value lighter (Cs-minus) paraffinic hydrocarbons are produced during the hydrocracking step. This reduces the overall yields of SPK in this pathway to 70% and lower (e.g., see FIG. 4). This also results in the loss of renewable carbon.

[0009] In view of the foregoing, there is a need for alternative feedstocks and / or alternative processes to meet the potential for biofuels to contribute to global decarbonization efforts.SUMMARY

[0010] The present disclosure provides materials and processes to address the limitations with feedstock availability, operating costs, catalyst requirements, and carbon loss discussed above.

[0011] In one aspect, the present disclosure provides a blended feedstock for producing a sustainable fuel, the blended feedstock comprising a first renewable feedstock including ahydroprocessed esters and fatty acids (HEFA)-precursor; and a second renewable feedstock including a bio-olefin.

[0012] In one or more embodiments, the HEFA-precursor can include a triglyceride, free fatty acid, vegetable oil, algal oil, bio-oil, animal fat, used cooking oil, non-edible oil, or a combination thereof.

[0013] In one or more embodiments, the second renewable feedstock can be characterized as having a density of 750 - 790 kg / m3, a freezing point of less than -50°C, an iso-paraffin content of at least 95%, a n-paraffin content of less than 5% by wt., optionally less than 2% by wt, a cycloparaffin content of less than 5% by wt., comprising C8-C24 oligomers, comprising mono-olefins, comprising iso-olefins, being substantially free of sulfur, and / or being substantially free of aromatics.

[0014] In one or more embodiments, the second renewable feedstock can be an intermediate of an alcohol-to-jet (ATJ) process. In one or more embodiments, the second renewable feedstock can be obtained by dehydrating and oligomerizing an alcohol. The alcohol can include methanol, ethanol, propanol, iso-propanol, butanol, isobutanol, long-chain fatty alcohols, or combinations thereof. In one or more embodiments, the alcohol can be produced from a feedstock including sugar, corn, grasses, other biomass, or bio-genic CO2. As used herein, “bio-genic CO2” refers to CO2 emissions related to the natural carbon cycle and / or resulting from the combustion, harvest, combustion, digestion, fermentation, decomposition, or processing of biologically based materials. Bio-genic CO2 can include CO2 emissions from the combustion of biogas collected from biological decomposition of waste in landfills, wastewater treatment, or manure management processes, CO2 emissions from combustion of the biological fraction of municipal solid waste or biosolids, and CO2 emissions derived from combustion of biological material, including forest-derived and agriculture- derived feedstocks.

[0015] In one or more embodiments, the first renewable feedstock and second renewable feedstock can be present within a range of about 100:1 to 1 :100 wt / wt.

[0016] In another aspect, the present disclosure provides a process of producing a sustainable fuel comprising hydrodeoxygenating a blended feedstock to form a deoxygenated feed, the blended feedstock comprising: a first renewable feedstock comprising a HEFA- precursor; and a second renewable feedstock comprising a bio-olefin.

[0017] In one or more embodiments, a ratio of iso- to n-paraffins in the deoxygenated feed is increased as compared to a fuel obtained by hydrogenating a feedstock that does not contain the second renewable feedstock.

[0018] In one or more embodiments, the process further includes mixing the first renewable feedstock and the second renewable feedstock.

[0019] In one or more embodiments, the first renewable feedstock comprises one or more of triglycerides, free fatty acids, vegetable oils, algal oils, bio-oils, animal fats, used cooking oils, non-edible oils, and combinations thereof.

[0020] In one or more embodiments, the second renewable feedstock is obtained by dehydrating and oligomerizing an alcohol, optionally obtained from an alcohol-to-jet (ATJ) process. In certain embodiments, dehydrating the alcohol comprises contacting the alcohol with a dehydration catalyst to form an alkene or mixture of alkenes, wherein the dehydration catalyst is selected from the group consisting of supported phosphoric acids, activated alumina, molecular sieves, and heteropoly acid catalysts.

[0021] In one or more embodiments, oligomerizing comprises at least two stages (or steps). In certain embodiments, oligomerizing comprises a first stage that includes contacting the alkene or mixture of alkenes with a first oligomerization catalyst to form a first oligomerate, wherein the first oligomerization catalyst includes nickel on a silico-aluminate support. In certain embodiments, the Ni concentration in the first oligomerization catalyst can be in the range of from 0.1 wt.-% to 10 wt.-%. In certain embodiments, the silico-aluminate support can have a crystalline or amorphous structure. In certain embodiments, the silico-aluminate support comprises beta-zeolite. In certain embodiments, oligomerizing further includes a second stage comprising contacting the first oligomerate with a second oligomerization catalyst to provide the second renewable feedstock, wherein the second oligomerization catalyst comprises a silico-aluminate catalyst or a solid acid catalyst. In certain embodiments, the silico-aluminate catalyst has a crystalline or amorphous structure. In certain embodiments, the silico-aluminate catalyst comprises beta-zeolite or H-ZSM-5 zeolite. The alcohol can include one or more of methanol, ethanol, propanol, iso-propanol, butanol, isobutanol, and long-chain fatty alcohols.

[0022] In one or more embodiments, the second renewable feedstock is obtained by oligomerizing ethylene produced from CO2. In certain embodiments, the ethylene is produced from bio-genic CO2.

[0023] In one or more embodiments, converting CO2to ethylene includes electrocatalytic reduction of CO2 or gas fermentation of CO2. In certain embodiments, CO2 can be converted to ethylene by electrocatalytic reduction using a catalyst selected from the group consisting of pure copper, copper alloys, bimetallic Cu-based catalysts, Cu-based carbonaceous materials, and functionalized variants thereof, and any mixture thereof. In certain embodiments, electrocatalytic reduction includes introducing CO2 to an H-type cell, a gas diffusion cell, a photo or solar cell, a flow-cell, and / or a membrane electrode assembly (MEA) cell. In certain embodiments, the process further includes recovering ethylene by one or more of distillation, simulated moving bed processes, membrane treatment, evaporation, pervaporation, gas stripping, phase separation, ion exchange, and extractive fermentation.

[0024] In In one or more embodiments, converting CO2 to ethylene includes gas fermentation. In certain embodiments, gas fermentation includes passing a gaseous stream including CO2 to a bioreactor containing a culture of microorganism expressing an ethyleneforming enzyme. In certain embodiments, the microorganism expresses an exogenous ethylene-forming enzyme. In certain embodiments, gas fermentation further comprises recovering ethylene by one or more of distillation, simulated moving bed processes, membrane treatment, evaporation, pervaporation, gas stripping, phase separation, ion exchange, and extractive fermentation.

[0025] In one or more embodiments, oligomerizing the ethylene produced by direct conversion of CO2comprises at least two stages (or steps). In certain embodiments, oligomerizing comprises a first stage that includes contacting the ethylene with a first oligomerization catalyst to form a first oligomerate, wherein the first oligomerization catalyst includes nickel on a silico-aluminate support. In certain embodiments, the Ni concentration in the first oligomerization catalyst can be in the range of from 0.1 wt.-% to 10 wt.-%. In certain embodiments, the silico-aluminate support can have a crystalline or amorphous structure. In certain embodiments, the silico-aluminate support comprises beta-zeolite. In certain embodiments, oligomerizing further includes a second stage comprising contacting the first oligomerate with a second oligomerization catalyst to provide the second renewable feedstock, wherein the second oligomerization catalyst comprises a silico-aluminate catalyst or a solid acid catalyst. In certain embodiments, the silico-aluminate catalyst has a crystalline or amorphous structure. In certain embodiments, the silico-aluminate catalyst comprises betazeolite or H-ZSM-5 zeolite.

[0026] In one or more embodiments, the first renewable feedstock and second renewable feedstock are present within a range of about 100:1 to 1 :100 wt / wt.

[0027] In one or more embodiments, the process further includes one or more of hydrogenating the deoxygenated feed, cracking the deoxygenated feed, and isomerizing the deoxygenated feed.

[0028] In one or more embodiments, the process further includes hydrogenating the deoxygenated feed to form a hydrogenated product and fractionating the hydrogenated product. Fractionating can include separating the hydrogenated product into a naphtha boiling point component, an aviation fuel boiling point range component, and a diesel boiling point range component. In some cases, the process can further include blending the aviation fuel boiling point range component with a second fuel to produce a blended fuel. The second fuel can include aromatics.

[0029] In one or more embodiments, the sustainable fuel is selected from the group consisting of synthetic paraffinic kerosene (SPK), sustainable aviation fuel (SAF), and renewable diesel (RD).

[0030] In one or more embodiments, hydrodeoxygenating includes contacting the blended feedstock with a hydrogenation catalyst in the presence of hydrogen. The hydrogenation catalyst can be selected from the group consisting of supported noble metal catalysts, supported nickel catalysts, supported nickel / molybdenum catalysts, and sulfided nickel molybdenum catalysts.

[0031] In one or more embodiments, the blended feedstock further comprises a fossil feedstock. In certain embodiments, the fossil feedstock can include one or more of crude oil, petroleum oil or gas, vacuum gas oil, shale oil or gas, natural gas, and coal deposits. In certain embodiments, the blended feedstock can include about 80% or more fossil feedstock by volume. In certain embodiments, the sustainable fuel includes or retains at least 85% of the14C content of the blended feedstock.

[0032] In another aspect, the present disclosure provides a sustainable fuel produced by one or more embodiments of the above aspect.

[0033] In another aspect, the present disclosure provides a blended aviation fuel comprising a volume of the sustainable fuel of the above aspect and a petroleum-derived jet fuel, wherein the blended fuel has a lower freezing point than a corresponding fuel blend comprising an equivalent volume of a synthetic paraffinic kerosene (SPK) produced by a hydroprocessed esters and fatty acids (HEFA) pathway that does not include a bio-olefin- containing feedstock and under conditions that maximize overall liquid yield.

[0034] In one or more embodiments, the freezing point (of the blended fuel and the corresponding fuel blend) can be determined using a ASTM D2386, ASTM D5972, ASTM D7153, ASTM D7154, or ASTM D7945 test method.

[0035] In one or more embodiments, the blended aviation fuel includes about 5% to about 85%, about 10% to about 75%, about 15% to about 65%, about 20% to about 60%, about 25% to about 55%, or about 30% to about 50% of the sustainable fuel by volume.

[0036] In one or more embodiments, the blended aviation fuel includes about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, or about 75% of the sustainable fuel by volume.

[0037] In one or more embodiments, the blended aviation fuel has a freezing point of less than -40°C or less than -47°C.

[0038] In one or more embodiments, the blended aviation fuel has a freezing point within a range of about -41°C to about -60°C, about 42°C to about 58°C, about 43°C to about 56°C, or about 45°C to about -55°C.

[0039] In one or more embodiments, the blended aviation fuel includes a petroleum- derived jet fuel selected from the group consisting of Jet A fuel, a Jet A-1 fuel, a Jet B fuel, a TS-1 fuel, a Jet Propellant (JP)-5 fuel, and a JP-8 fuel, or a combination thereof.

[0040] In one or more embodiments, the petroleum-derived jet fuel is adapted for use in commercial aircraft or in military aircraft.

[0041] In one or more embodiments, the blended aviation fuel includes at least about 8%, at least about 10%, at least about 12%, at least about 15%, at least about 17%, at least about 19%, at least about 21 %, at least about 23%, or at least about 25% aromatics by volume.

[0042] These and other objects, features and advantages of the present disclosure will become apparent in light of the detailed description of embodiments thereof, and as illustrated in the accompanying drawings.BRIEF DESCRIPTION OF DRAWINGS

[0043] FIG. 1 is a schematic representation of HEFA process 100 for SAF and / or RD production.

[0044] FIG. 2 is a schematic representation of alcohol-to-jet (ATJ) process 200 for production of SAF and / or RD, according to one or more embodiments of the present disclosure.

[0045] FIG. 3 is a schematic representation of process 300 for co-processing of an oligomerate with a HEFA feedstock for production of SAF and / or RD, according to one or more embodiments of the present disclosure.

[0046] FIG. 4 shows the typical impact of cold flow properties on kerosene yield of HEFA (adapted from Figure 4: Oil & Gas Science and Technology - Rev. IFP Energies nouvelles (2016) 71 , page 6 / 13).DETAILED DESCRIPTION

[0047] The explanations and illustrations presented herein are intended to acquaint others skilled in the art with the disclosure, its principles, and its practical application. Those skilled in the art may adapt and apply the disclosure, as may be best suited to the requirements of a particular use. Accordingly, the specific embodiments of the present disclosure are not intended to be exhaustive or limiting. The scope of the disclosure should, therefore, be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled, and not with reference to the descriptions herein. The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. Other combinations are also possible as will be gleaned from the following claims, which are also hereby incorporated by reference into this disclosure.

[0048] The present disclosure describes coprocessing of bio-olefins using a blended feedstock. As used herein, “bio-olefins” refers to olefins that have been directly or indirectly converted from biomass, bio-oil feedstocks, genetically modified microorganisms, or the like, through processes such as fermentation, gasification, electrochemical conversion, crackingand deoxygenation. A blended feedstock of the present disclosure includes renewable feedstocks. As used herein, “renewable feedstock” refers to a material used in a chemical process such as production of another product (e.g., bio-fuel) or in energy production that is or can be obtained from a resource capable of being replenished through a natural process. A blended feedstock can include a first renewable feedstock and a second renewable feedstock.

[0049] First renewable feedstock

[0050] A first renewable feedstock for coprocessing of bio-olefins can include a HEFA- precursor. In the present disclosure, “HEFA-precursor” refers to biologically sourced lipids, such as, edible and non-edible vegetable oils, animal fats, fish oils, microbial oils, algal oils (e.g., microalgal oils), bio-oils, used cooking oil, grease trap waste, and mixtures thereof. Nonlimiting examples of vegetable oils include rapeseed oil, canola oil, colza oil, tall oil, sunflower oil, soybean oil, hemp oil, olive oil, linseed oil, mustard oil, palm oil, arachis oil, castor oil, and coconut oil. Non-limiting examples of animal fats include rendered and / or purified animal fats, suet, tallow, blubber, and recycled alimentary fats. The HEFA-precursor can include triglycerides and / or free fatty acids. The HEFA-precursor can include a feedstock designated for SAF production, and / or exclude one or more of vegetable oil from food or feed crops and palm oil. The HEFA-precursor can include a feedstock eligible for co-processing with a fossil feedstock. The HEFA-precursor can include a feedstock that achieves greenhouse gas (GHG) emission savings, such as a feedstock that achieves 25% or more (e.g., > 65%) GHG emission savings. In one or more embodiments of the present disclosure, two or more HEFA-precursors can be blended to form a first renewable feedstock. A HEFA-precursor can be pre-treated. Pretreatment can include degumming, drying, metal or ion removal, polyethylene removal, clay adsorption, and / or bleaching.

[0051] Second renewable feedstock

[0052] A second renewable feedstock for coprocessing of bio-olefins can include a bioolefin. The bio-olefin can be C4 or longer, such as up to C26. The bio-olefin can be branched. The bio-olefin can be mono-unsaturated or poly-unsaturated. The bio-olefin can be an oligomer of C2-C5 olefins. In one embodiment, the bio-olefin is a Cs to C24 branched monounsaturated hydrocarbon oligomer, such as an oligomer in the Cs to C22 range.

[0053] A second renewable feedstock can include a mixture of bio-olefins of differing lengths, degrees of branching, and degrees of unsaturation, such as a paraffinic mixture. In some cases, a second renewable feedstock can have an iso-paraffin content of at least 95%, a n-paraffin content of less than 5% by wt., or less than 2% by wt., and / or a cycloparaffin content of less than 5% by wt. A second renewable feedstock can have a density of about 750- 790 kg / m3. A second renewable feedstock can be substantially free of sulfur and / or aromatic compounds.

[0054] In one or more embodiments of the present disclosure, a second renewable feedstock includes an intermediate of an alcohol-to jet (ATJ) process. Bio-olefins formed as an intermediate from any of the approved sustainable aviation fuel pathway (for example, ATJ- Synthetic Kerosene with Aromatics (SKA) pathway in ASTM D7566 - 23a) or any bio-fuel intermediates that require hydrogenation and separation as the final steps of the pathway can be used.

[0055] One example of a suitable ATJ process for obtaining a second renewable feedstock is LanzaJet’s ATJ technology, illustrated in FIG. 2. LanzaJet’s ATJ technology is an approved pathway to produce SPK. Although ethanol is exemplified, any renewable alcohol- based fuel can be utilized as ATJ feedstock in process 200. For example, methanol, ethanol, propanol, iso-propanol, butanol, isobutanol and long-chain fatty alcohols can be used as an ATJ feedstock.

[0056] In optional block 202, the ATJ process can include a step of providing the renewable alcohol-based fuel. Suitable methods for obtaining a renewable alcohol-based fuel can include microbial bioreactors to convert carbon-containing gases into ethanol, microbial fermentation of biomass, or the like. In one or more embodiments of the present disclosure, the bio-olefin is converted from ethanol derived from CO, CO2, plant waste materials, or municipal solid waste.

[0057] For example, in optional block 202, the ATJ process includes producing alcohol from sugar, corn, grasses, other biomass, or bio-genic CO2 (e.g., from the harvest, combustion, digestion, fermentation, decomposition, or processing of biologically based materials). In a non-limiting example, the alcohol can be produced from fermentation of industrial waste gases. As used herein, the term “fermentation” refers to a metabolic process that includes producing a product or mixture thereof through utilization of at least one type of microorganism acting upon a substrate. In a non-limiting example, optional block 202 can include producing alcohol via gas fermentation of syngas, or other industrial waste gas, utilizing a C1 fixing microorganism, as described in US Pat. No. 11 ,760,989 B2, the contents of which are incorporated herein by reference.

[0058] At block 204, the ATJ process includes a step of dehydrating ethanol to produce ethylene (or other alkene based on the ATJ feedstock) in the presence of a dehydration catalyst. A suitable dehydration catalyst can be a homogeneous or heterogeneous catalyst. Non-limiting examples of suitable homogeneous acid catalysts include inorganic acids such as sulfuric acid, hydrogen fluoride, fluorosulfonic acid, phosphotungstic acid, phosphomolybdic acid, and phosphoric acid; Lewis acids such as aluminum and boron halides (e.g., AICI3, BF3, etc.); organic sulfonic acids such as trifluoromethanesulfonic acid, p-toluenesulfonic acid and benzenesulfonic acid; heteropolyacids; fluoroalkyl sulfonic acids, metal sulfonates, and metal trifluoroacetates. Combinations of homogeneous acid catalysts can be used. Non-limiting examples of suitable heterogeneous acid catalysts include heterogeneous heteropolyacids (HPAs); solid phosphoric acid; natural clay minerals, such as those containing alumina or silica; cation exchange resins such as sulfonated polystyrene ion exchange resins; metal oxides, such as hydrous zirconium oxide, Fe2Os, Mn2C>3, y-alumina, etc.; mixed metal oxides, such as sulfated zirconia / y-alumina, alumina / magnesium oxide, etc.; metal salts such as metal sulfides, metal sulfates, metal sulfonates, metal nitrates, metal phosphates, metal phosphonates, metal molybdates, metal tungstates, metal borates; zeolites (AKA molecular sieves), such as NaY zeolite, H-ZSM-5, NaA zeolite, etc., and combinations of any of the above. In one or more embodiments, a dehydration catalyst can include supported phosphoric acids (on, e.g., alumina or silica), activated alumina, molecular sieves, and HPA catalysts. In a specific but non-limiting example, ethylene can be produced at 95- 99.6% carbon efficiency (95-99.6% of carbon in ethanol is retained in ethylene).

[0059] At block 206, the ATJ process includes a step of oligomerizing the ethylene to obtain a mixture of Cs to C22 mono-olefins in the presence of an oligomerization catalyst. As used herein, “mono-olefin” refers to an olefin with a single double bond. The mono-olefins can include iso-olefins with varying numbers of carbons and differing degrees of branching.

[0060] A suitable oligomerization catalyst can be a single catalyst or a mixture of different catalysts. A suitable oligomerization catalyst can include an oxide, such as alumina and silica-alumina. In some cases, a suitable oligomerization catalysts includes a zeolite catalyst. Non-limiting examples of suitable zeolites include ZSM-5, ZSM-11 , ZSM-12, ZSM- 23, ZSM-35, ZSM-38, ZSM-48, and zeolites having a structure from one of the following classes: MTT, TON, MFI, MTW, MEL, ITH, IMF, TUN, FER, BEA, FAU, BPH, MEI, MSE, MWW, UZM-8, MOR, OFF, AFO, ATO, and AEL, or a mixture thereof. Three-letter codes indicating a zeotype are defined by the Structure Commission of the International Zeolite Association. For example, BEA refers to zeolite beta. A zeolite oligomerization catalyst can be formed by combining a zeolite with a binder to form a pellet, and then optionally treating the pellet with a phosphorus reagent. The binder can be selected from alumina, aluminum phosphate, silica, silica-alumina, zirconia, titania and combinations of these metal oxides, and other refractory oxides, and clays such as montmorillonite, kaolin, palygorskite, smectite and attapulgite, suitable for conferring hardness and strength to the pellet.

[0061] A suitable oligomerization catalyst can include a solid acid catalyst, such as a solid phosphoric acid (SPA) catalyst. A solid acid catalyst can include a carrier, such as a porous silica-containing materials (e.g., kieselguhr, kaolin, infusorial earth and diatomaceous earth).

[0062] A suitable oligomerization catalyst can include nickel, such as homogeneous and heterogeneous Ni-based catalysts. Non-limiting examples include silica-supported nickel catalyst, nickel phyllosilicates, aluminosilicates (ASA)-supported nickel catalyst, Zeolite- supported nickel catalysts (e.g., Ni precursor Ni(NOs)2 deposited on H-Beta zeolite having a Si to Al ratio of 12 or higher). In a non-limiting example, an aluminosilicate support can have a crystalline structure such as H-Beta zeolite, i.e., the acidic form of zeolite BEA, and similar materials. An aluminosilicate support can be amorphous. Nickel can be incorporated in the support by any method for producing a Ni-based catalyst (e.g., by batch or column ion exchange, impregnation, or similar methods before or after calcination). A suitable Ni-based catalyst can include a concentration of Ni in the range of from 0.1 wt.-% to 10 wt.-%, such as 0.1 wt.-% to 5 wt.-%, or 0.2 wt.-% to 3.0 wt.-%.

[0063] The oligomerization step may be implemented in one step or two steps (or stages). The oligomerization catalyst of the second oligomerization step can be the same or different than the catalyst of the first oligomerization step, and be selected from the oligomerization catalysts above. In a non-limiting example, the first oligomerization step utilizes a first oligomerization catalyst that includes nickel on a silico-aluminate support. The Ni concentration in the first oligomerization catalyst can be within a range of from 0.1 wt.-% to 10 wt.-%, such as 0.2 wt.-% to 3.0 wt.-%. In a non-limiting example, the second oligomerization step utilizes a second oligomerization catalyst that includes a silico-aluminate catalyst or a solid acid catalyst. The silico-aluminate catalyst can be a crystalline structure zeolite such as beta-zeolite (e.g., H-Beta zeolite), H-ZSM-5, etc., or the silico-aluminate support can be amorphous.

[0064] At block 208, the ATJ process includes a step of hydrogenating the mono-olefins to form saturated hydrocarbons in the presence of a hydrogenation catalyst.

[0065] At block 210, the ATJ process includes a step of separating the saturated hydrocarbons into the SPK and RD fractions. Light gases can be fractionated as a by-product. The product composition can be adjusted between the max jet and max diesel mode to produce the desired ratio of the SAF to RD products. In certain embodiments, the LanzaJet ATJ technology can produce 90 mass-% SPK and 10 mass-% RD operating in the max jet mode. In certain embodiments, the product mix can be changed by adjusting only the process conditions to 75 mass-% RD and 25 mass-% SPK in the max diesel mode.

[0066] After step 206, at least a portion of the ATJ intermediate, oligomerate 212, can be diverted to provide the second renewable feedstock for the blended feedstock. Oligomerate 212 can include a mixture of Cs to C22 mono-olefins.

[0067] The second renewable feedstock addresses one or more limitations of conventional HEFA processing to produce bio-fuels. For example, there is an ample supply ofrenewable alcohol-based fuel, such as ethanol, to fill the demands for the lipid feeds used in HEFA processing.

[0068] In certain embodiments, a second renewable feedstock can be obtained from oligomerization of ethylene produced from direct conversion of CO2. The ethylene produced by direct conversion of CO2 can also be referred to as “bio-ethylene”. Direct conversion can include electrochemical conversion of CO2 and / or gas fermentation of CO2. In some cases, a second renewable feedstock can include products derived from both indirect conversion such as an ATJ intermediate as described above, and direct conversion of CO2

[0069] CO2 for direct conversion to ethylene can be captured or extracted from any suitable point source, including sources for indirect production of ethylene as described above. Non-limiting examples include an industrial facility (e.g., a steel mill, cement, glass, paper, or aluminum production facility, chemical production facility, electric power production facility, etc.), natural gas streams, refinery process streams, geological CO2 storage site, ocean, or air. In certain embodiments, the point source is combustion or decomposition of organic material (e.g., bio-genic CO2). In certain embodiments, CO2 extracted from a point source can be purified to remove combustion products such as SOx and NOx, or otherwise treated, scrubbed, or filtered to remove any undesired impurities, such as toxins, undesired components, or dust particles, and / or to increase the concentration of desirable components. In certain embodiments, CO2 capture includes chemisorption using a solvent or sorbent that reacts with the CO2 such as monoethanolamine (MEA), diglycolamine (DGA), diethanolamine (DEA), diisopropanolamine (DIPA) and methyldiethanolamine (MDEA).

[0070] Electrochemical conversion of CO2 can include electrocatalytic reduction of CO2 via surface-catalyzed electro-activation, coordination to the carbon atom to a metal, electrophilic activation of the oxygen or nucleophilic activation of the carbon atom, or CO2 activation by two metal atoms. In some cases, electrochemical conversion of the CO2 can be a tandem process that divides the CO2-to-C2H4pathway into a first stage of CC -to-CO and a second stage of CO-to-C2H4. The catalyst(s) can include copper (Cu) such as pure copper, copper alloys (e.g., CuAg, CuPd, CuAI, CuAu, CuSn, etc.), bimetallic Cu-based catalysts (e.g., Ag-Cu, Sn-Cu, Au-Cu, Pd-Cu, In-Cu, Zn-Cu, Ni-Cu, Bi-Cu and Co-Cu, etc.), Cu-based carbonaceous materials, functionalized variants thereof (e.g., functionalized with organic molecules such as aryl diazonium functionalization, imidazolium functionalization, etc.), functionalized by incorporation of organic polymers such as polyamines, polymethyl acrylates, polymethyl methacrylates, and polymers comprising other functional groups including pendent groups or chains thereof), and any mixture thereof.

[0071] Electrocatalytic reduction of CO2 to ethylene can be implemented in an electrolyzer or other electrochemical system, non-limiting examples of which can include an H-type cell, a gas diffusion cell, a photo or solar cell, a flow-cell, and / or a membrane electrodeassembly (MEA) cell. Suitable electrolyzers can include solid- and liquid-electrolyte electrolyzers. The catalyst and / or electrode incorporating the catalyst can include hierarchical structures that have been or can be tuned to minimize production of one or more of CO, formate, acetate, methane, and / or methanol (i.e., to improve catalytic specificity for ethylene production). The electrode can include catalytic structures such as metallic mesh, molecular- organic frameworks (MOFs), nanosheets, nanotubes, nanowires, nanoparticles, nanocones, nanospheres, nanocubes, nanocrystals, polycrystalline structures, nano- or mesoporous structures, core-shell nanoparticles, etc. Ethylene recovery can be implemented by any suitable separation technique. Non-limiting examples of techniques include distillation, simulated moving bed processes, membrane treatment, evaporation, pervaporation, gas stripping, phase separation, ion exchange, or extractive fermentation, including for example, liquid-liquid extraction and combinations of these techniques.

[0072] The ethylene produced by electrochemical conversion of CO2 can be oligomerized in the presence of an oligomerization catalyst, as described above for block 206. In certain examples, the oligomerization of ethylene from electrochemical conversion of CO2 can provide a mixture of Csto C22 mono-olefins.

[0073] Gas fermentation of CO2 can include the direct conversion of gaseous CO2 to ethylene using a natural or an engineered microorganism. Direct conversion is distinguished from the indirect ethanol pathway of gas fermentation of CO2, whereby ethanol is produced and then converted to ethylene. An engineered microorganism for direct conversion of CO2 to ethylene can include a nucleic acid encoding one or more exogenous enzymes, including an ethylene-forming enzyme. Non-limiting examples of engineered microorganisms for direct conversion of CO2 to ethylene are described in International Patent Application WO2023250392A1 (Applicant: LanzaTech, Inc.), which is incorporated herein in its entirety.

[0074] Gas fermentation can be implemented by passing a gaseous stream of CO2 (e.g., extracted or captured as described above) to a bioreactor containing a culture of a natural or an engineered microorganism capable of producing ethylene, such as a microorganism engineered to express an ethylene-forming enzyme, optionally a heterologous or exogenous ethylene-forming enzyme. One or both of the gaseous stream and the bioreactor can be configured to provide an energy source for the microorganism, such as hydrogen gas. The bioreactor can be configured for introducing the CO2 stream into the culture medium (e.g., as bubbles or dissolved CO2) and / or for recovering ethylene from the bioreactor. Ethylene recovery can be implemented by any suitable separation technique, non-limiting examples of which include distillation, simulated moving bed processes, membrane treatment, evaporation, pervaporation, gas stripping, phase separation, ion exchange, or extractive fermentation, including for example, liquid-liquid extraction and combinations of these techniques.

[0075] The ethylene produced by gas fermentation can be oligomerized over a catalyst to selectively produce an oligomerate, as described above in block 206. In certain examples, the oligomerization of ethylene from gas fermentation of CO2 can provide a mixture of Cs to C22 mono-olefins.

[0076] Coprocessing of bio-olefins

[0077] FIG. 3 illustrates one example of a process for coprocessing of bio-olefins. In process 300, the requirements for hydrocracking and hydro-isomerization associated with a deoxygenated HEFA feed, as described in FIG. 1, can be moderated or reduced significantly because of the complimentary nature of the first and second renewable feedstocks. Coprocessing of the first and second renewable feedstocks can utilize existing HEFA plants.

[0078] In block 310, a first renewable feedstock comprising a pre-treated HEFA- precursor is combined with a second renewable feedstock comprising a bio-olefin to produce a blended feedstock. For example, an oligomerate, such as the iso-mono-olefins formed as an intermediate in ATJ process 200 can be co-processed with the treated HEFA feedstock. The first renewable feedstock and second renewable feedstock can be combined at any ratio. In certain embodiments, the first renewable feedstock and second renewable feedstock are combined at a ratio within the range of about 100:1 to 1 :100 wt / wt.

[0079] In one or more embodiments, the second renewable feedstock can be oligomerate 308 obtained via an optional process that includes step 302 to provide ethanol (or any renewable alcohol-based fuel) for catalytic dehydration at block 304 and catalytic oligomerization at block 306. The resulting oligomerate 308 can be mixed with the first renewable feedstock to provide the blended feedstock. Steps 302-306 can be performed in a separate plant, or in an integrated plant.

[0080] At block 312, the blended feedstock is hydrodeoxygenated in the presence of a hydrogenation catalyst.

[0081] At block 314, a portion of the deoxygenated product is hydrogenated, and can be isomerized (e.g., hydro-isomerized) to produce iso-paraffinic compounds in the presence of an isomerization catalyst, and larger hydrocarbons can be cracked (e.g., hydrocracked) into smaller chain molecules in the presence of a hydrocracking catalyst. Suitable catalysts can be selected based on the chemical properties of the linear paraffins, the necessary cold flow properties, and the selectivity for meeting the specifications of RD and / or SPK. In one or more embodiments of process 300, hydro-isomerization and / or hydrocracking is optional. In some cases, the blended feedstock reduces the need to hydrocrack deoxygenated feed molecules originating from the first renewable feedstock, which improves the overall carbon efficiency of the process, reduces the hydrocracking catalyst severity (reduces the amount of hydrocracking catalyst and / or improves the cycle length), provides more flexibility to changethe jet fuel to diesel ratio, and reduces the overall hydrogen consumption for co-processing compared to separate processing of the HEFA precursor (e.g., as shown in FIG. 1). The combined product will span molecules in the jet and diesel fuel range. The combined product can also have a reduced volume of low-value naphtha and light gases relative to process 100, for example, due to a reduced need for hydrocracking. This also results in a reduced loss of renewable carbon. Thus, process 300 represents an improvement in the overall carbon efficiency of HEFA processing for SAF.

[0082] In one or more embodiments, the isomerization catalyst includes a bifunctional isomerization catalyst, such as a non-sulfided bifunctional hydrocracking catalyst. The bifunctional hydrocracking catalyst can include one or more Group VIII metals, such as a noble Group VIII metal. The bifunctional isomerization catalyst can further include an acidic porous material, such as a zeolite, zeolite-type material, alumina, silica, amorphous silica-alumina, titanium alumina, titania, and / or zirconia.

[0083] In one or more embodiments, hydrocracking catalyst includes a bifunctional hydrocracking catalyst, such as a non-sulfided bifunctional hydrocracking catalyst. The bifunctional hydrocracking catalyst can include one or more Group VIII metals, such as Ni, Co, Pt, and Pd, and / or one or more of Mo, Co and W. The bifunctional hydrocracking catalyst can further include an acidic porous material, such as a zeolite, zeolite-type material, or silica- alumina.

[0084] At block 316, the hydrogenated product undergoes a separation process, such as fractionation by distillation. Process 300 can provide overall yields of SPK of 70% and greater. In certain embodiments, fractionating includes separating the hydrogenated product formed in block 314 into a naphtha boiling point component, an aviation fuel boiling point range component, and a diesel boiling point range component.

[0085] After separation, the fractions can be further processed for use as fuel. For example, a neat fuel of process 300 using ethanol can contain less than 1% of aromatics, whereas jet fuel can contain 8% to 25% aromatics. Therefore, in one or more embodiments, process 300 can further include blending a fraction with a fuel additive or a second fuel, such as an aromatics additive or aromatics-containing fuel.

[0086] A blended feedstock utilizing the molecular composition of an ATJ oligomerate as described above can reduce the hydro-isomerization required to improve the cold flow properties of the jet and diesel products. ATJ oligomerates are iso-olefins and the resulting iso-hydrocarbons (after hydrogenation) has freeze point in the range of -50°C to -75°C for the jet fuel and cloud point of <-15°C for the diesel fuel.

[0087] In one or more embodiments, process 300 can include co-processing of the first and second renewable feedstocks with a fossil feedstock. For example, in block 310 a first renewable feedstock comprising a pre-treated HEFA-precursor, a second renewablefeedstock comprising a bio-olefin, and a fossil feedstock can be combined to produce a blended feedstock. As used herein, the term “fossil” refers to compounds or compositions that are obtainable, derivable, or originating from naturally occurring non-renewable sources, such as crude oil, petroleum oil / gas, shale oil / gas, natural gas, or coal deposits, and the like, and combinations thereof, including any hydrocarbon-rich deposits from ground / underground sources. Compositions obtainable, derivable, or originating from naturally-occurring non- renewable sources can include diesel, kerosene, naphtha, and vacuum gas oil (VGO), and / or an intermediate hydrocarbon product such as a recycle oil. Crude oil can include one or more of unfinished oil, light crude oil, and heavy crude oil. The blended feedstock can include fossil feedstock in major amounts, such as about 80%, 85%, 90%, 91 % 92%, 93%, 94%, 95%, 96%, 97%, 98%, or more fossil feedstock by volume, with the remainder including the first and second renewable feedstocks. The blended feedstock can be processed as described above for blocks 312-316.

[0088] In certain embodiments, process 300 can retain a percentage of the renewable carbon present in the blended feedstock. Renewable carbon content can be assessed by distinguishing between the unstable radiocarbon (14C) atoms present in renewable feedstocks and carbon (12C) atoms of fossil origin. The retention of renewable carbon can be assessed at one or more stages of co-processing from, for example, reaction feeds, reaction effluents, and / or distilled fractions. In some cases, process 300 retains more than 50 wt-%, 60 wt-%, 70 wt-%, 80 wt-%, 90 wt-% or more than 95 wt-% of the renewable carbon present in the blended feedstock in one or more reaction effluents. In some cases, one or more fractions of the sustainable fuel include at least 85-wt% of the14C content of the blended feedstock.

[0089] In one or more embodiments, co-processing of the first and second renewable feedstocks with a fossil feedstock can include introducing the fossil feedstock to the deoxygenated product at block 314, to provide a mixture of renewable and non-renewable components and hydrogenating the mixture. The introduction of fossil feedstock at block 314 can be in addition to or instead of a blended feedstock comprising a pre-treated HEFA- precursor, a second renewable feedstock comprising a bio-olefin, and the fossil feedstock. The fossil feedstock can include diesel, kerosene, naphtha, and vacuum gas oil (VGO), and / or an intermediate hydrocarbon product such as a recycle oil. The mixture of the deoxygenated product and the fossil feedstock can be catalytically isomerized and / or hydrocracked as described above.

[0090] The presence of a second renewable feedstock comprising a bio-olefin in the blended feedstock can ameliorate the effect of a HEFA feedstock on cold flow properties by increasing the proportion of iso-paraffins in the deoxygenated product as compared to coprocessing of fossil and HEFA feedstocks alone. The relative reduction in n-paraffin content reduces the need to isomerize the deoxygenated product. The presence of bio-olefin can alsoimprove retention of bio-genic carbon during co-processing as compared to co-processing of fossil and HEFA feedstocks alone.

[0091] The presence of a second renewable feedstock comprising a bio-olefin in the blended feedstock can also reduce the amount of impurities in the blended feedstock as compared with co-processing of fossil and HEFA feedstocks alone, and thereby mitigate the loss catalytic activity and / or selectivity over time. For example, presence of a second renewable feedstock comprising a bio-olefin can extend catalytic lifetime (activity and / or selectivity) during hydrogenation, hydrocracking, and / or isomerization as compared with coprocessing of fossil and HEFA feedstocks alone.

[0092] Co-processing of bio-olefins, including one or more steps of method 300, can be carried out in a facility for refining renewable fuel. For example, a suitable facility for coprocessing of bio-olefins can be or include a standalone HEFA production facility. In a nonlimiting example, the facility can be a HEFA production facility, such as a HEFA RD and / or SAF production facility, including HEFA RD production facilities that have been retrofitted to maximize SAF production and / or synthetic paraffinic kerosene (SPK).

[0093] A HEFA production facility can include a hydrogenation unit with a catalyst or multiple catalysts. The catalyst(s) can be in a fixed bed reactor or reactors or in a slurry reactor. Suitable catalyst(s) include e.g., a hydrogenation metal selected from a group consisting of Pd, Pt, Ni, Co, Mo, Ru, Rh, W or a combination of these (e.g., a bimetallic catalyst), optionally with an alumina or silica carrier. The catalyst can include supported noble metal catalysts, supported nickel catalysts, supported nickel / molybdenum catalysts, and sulfided nickel molybdenum catalysts. The reactor(s) can be operable at high pressure and temperature. In the hydrogenation unit, the mixture of a first renewable feedstock comprising a pre-treated HEFA-precursor and a second renewable feedstock comprising a bio-olefin can be reacted with hydrogen. The hydrogenation unit can be operable for providing hydrogen to a reactor loop at a make-up rate capable of maintaining the desired hydrogen partial pressure in the reactor(s). The hydrogenation unit can be operable for cooling the reaction products and separating condensed (liquid) products from uncondensed vapor (e.g., with a high-pressure separator). The hydrogenation unit can be operable for purging uncondensed vapor or returning uncondensed vapor to the reactor loop from the separator, and to let down condensed liquids from the separator to a lower pressure. The hydrogenation unit can be operable for transferring the liquid products to a fractionation unit.

[0094] A HEFA production facility can include a deoxygenation unit operable for hydrogenating and deoxygenating one or more components of the first renewable feedstock by oxygen hydrogenolysis, decarboxylation, and decarboxylation. A deoxygenation unit can one or more reactors, each including a catalyst or multiple catalysts. A suitable deoxygenation catalyst can include a Group VIII metal or combinations thereof, and optionally a supportmaterial, such as carbon, a metal oxide, or a metalloid oxide. The reactor can be a fixed bed reactor or a slurry reactor. The reactor(s) can be operable at high temperature. The deoxygenation unit can be operable for recovering the deoxygenated products for further processing. The deoxygenation unit can be operable for transport of the liquid deoxygenated products to a fractionation unit.

[0095] The HEFA production facility can include a hydrocracking / hydrotreating unit The hydrocracking / hydrotreating unit can be a fluid catalytic cracking unit, a diesel hydrotreating unit, or a kerosene hydrotreating unit. The HEFA production facility can include one or more pumps for transporting the low-pressure liquids into the hydrocracking / hydrotreating unit from the fractionation unit or hydrogenation unit. The hydrocracking / hydrotreating unit can be a fixed bed catalytic reactor, including a hydrocracking catalyst, a hydrotreating catalyst, or mixture thereof. The hydrocracking / hydrotreating unit can be operable for transferring the reaction products to a fractionation unit (e.g., the same or different fractionation unit than the fractionation unit above). The fractionation unit can be operable for fractional distillation to meet specifications of the final fuel product.

[0096] The HEFA production facility can include a hydrocracking / isomerization unit. For example, the HEFA production facility can include a hydrodewaxing reactor for isomerization of a portion of the reaction product and / or limited cracking of larger hydrocarbons into smaller chain molecules. The hydrodewaxing reactor can be operable for receiving the low-pressure liquids from the hydrogenation unit. The hydrodewaxing reactor can include an isomerization catalyst ( e.g., a molecular sieve and / or a metal selected from Group VIII of the periodic table and optionally a carrier). The hydrodewaxing reactor can be operable for transporting the isomerized product to the hydrocracking / hydrotreating unit.

[0097] The HEFA production facility can include one or more HEFA feedstock pretreatment units. The pretreatment unit can be operable for compatibility with the hydrocracking catalyst.

[0098] The HEFA production facility can include one or more additional process units such as hydrogen generation equipment, additional reactor loop(s), and compression modifications to address pressure drops therefrom, feedstock receiving and storage units, product (RD and / or SAF) and byproduct (LPG and naphtha) storage, blending and logistics systems, wastewater treatment unit, sour water stripper, sulfur removal unit, utility systems, and controls for other instrumentation and / or structural, mechanical and electrical systems. The HEFA production facility can be configured to utilize a portion of naphtha and LPG byproducts to generate hydrogen, steam and / or power on-site.

[0099] In some cases, co-processing can be implemented in fossil feedstock refinery units configured to (e.g., retrofitted or revamped to) co-process pre-treated HEFA feedstockand fossil feedstock. For example, a fossil feedstock refinery can be modified by changing the fossil feedstock catalyst for renewable feedstock catalyst.

[0100] Optionally, a facility for co-processing of bio-olefins can include one or more units of a HEFA production facility and one or more units operable for generating the second renewable feedstock comprising a bio-olefin. Non-limiting examples include units configured for ATJ production, such as dehydration reactors and oligomerization reactors, and optionally facilities for providing an alcohol feedstock such as a gas fermentation system, which can be integrated into an existing HEFA facility. For example, an existing HEFA facility can include an oligomerization reactor or reactors (e.g., a first stage reactor and a second stage reactor) containing a oligomerization catalyst as described above, or mixture thereof. The oligomerization reactor(s) can be configured to convey the produced second renewable feedstock to the HEFA hydrogenation unit, for example.

[0101] Coprocessing of bio-olefins can leverage considerable synergy between the processing steps required for HEFA feed and the ATJ oligomerate. For example, the ATJ oligomerate, e.g., oligomerate 212 or 308, are mono-olefins that can be saturated by the hydrogenation catalyst used for hydrodeoxygenation of the HEFA precursor components of the blended feedstock. The requirements for hydrocracking and hydro-isomerization of the deoxygenated HEFA precursors can be moderated or reduced significantly because of the complimentary nature of the ATJ oligomerate, e.g., oligomerate 212 or 308, and the deoxygenated HEFA precursor molecules. For example, the carbon number range of the deoxygenated HEFA precursor molecules is in the C to C22 range, while that of the ATJ oligomerate, e.g., oligomerate 212 or 308, is in the Cs to C22 range (i.e. , a mixture comprising a majority of molecules in the jet fuel range with some of the molecules in the diesel range).

[0102] Co-processing of the blended feedstock yields a product with molecules spanning the jet and diesel fuel range with a reduced need for hydrocracking. Thus, coprocessing of bio-olefins improves the overall carbon efficiency of the process, reduces the hydrocracking catalyst severity, provides more flexibility to change the jet fuel to diesel ratio, and reduces the overall hydrogen consumption for co-processing compared to separate processing of the feed. For example, coprocessing provides the flexibility to produce both diesel and jet fuel in an existing HEFA plant, while reducing the need to hydrocrack the diesel molecules from the processing of HEFA precursors of the first renewable feedstock. The reduction in catalyst severity can be utilized to reduce the amount of the catalysts required or increase the utilization of the catalysts by extending the cycle life of these catalysts. For example, coprocessing can reduce the amount of hydrocracking catalyst, hydro-isomerization catalyst, or both, and / or improve the cycle length for these catalysts.

[0103] Co-processing of the blended feedstock also reduces the degree of hydroisomerization required to improve the cold flow properties of the jet and diesel products fromHEFA precursors. For example, iso-olefins of the ATJ oligomerate, e.g., oligomerate 212, result in iso-hydrocarbons (after hydrogenation) having a freeze point in the range of -50°C to -75°C (e.g., for jet fuel) and a cloud point of < -15°C (e.g., for diesel fuel). The deoxygenated HEFA products of process 100 are normal paraffins, which for the diesel range molecules, have a cloud point of >20°C. In contrast, products of the blended feedstock include a mixture of jet and diesel range iso-paraffin molecules, with a reduced need for hydro-isomerization. In one or more embodiments, coprocessing the blended feedstock eliminates the need for hydroisomerization.

[0104] In addition, co-processing of blended feedstock can provide substantial savings in capital costs in comparison to a stand-alone ATJ plant. In some cases, a savings of 10-15% in capital costs can be achieved. Co-processing of blended feedstock can provide additional savings for the outside the battery limit facilities of wastewater processing, hydrogen generation, and other consumable utilities.

[0105] Blended aviation fuels

[0106] Co-processing of blended feedstock expands blending strategies for incorporation of SPK in conventional jet fuel. For example, co-processing of blended feedstock can allow for higher incorporation rates of SPK to meet international targets for reducing CO2 emissions. Accordingly, the present disclosure further provides blended aviation fuels, and methods of preparing blended aviation fuels by incorporation a volume of a sustainable fuel obtained by a co-processing method described above. The blended fuel can include a petroleum-derived jet fuel and a volume of sustainable fuel produced by co-processing the blended feedstock as described above (e.g., hydrodeoxygenating a blended feedstock to form a deoxygenated feed; the blended feedstock comprising: a first renewable feedstock comprising a HEFA-p recursor; and a second renewable feedstock comprising a bio-olefin).

[0107] In certain embodiments, the blended fuel can be characterized by the volume of the sustainable fuel incorporated therein and its freezing point. The blended fuel can incorporate high rates of sustainable fuel while exhibiting excellent cold flow properties. The cold flow properties are conferred by co-processing, as described above.

[0108] At very low temperatures, aviation fuels will develop solid hydrocarbon crystals. Various freezing point tests can be used to determine the temperature at which these crystals completely disappear. In certain embodiments, the blended fuel exhibits a lower freezing point than a corresponding aviation fuel blend prepared by incorporating an equivalent volume of a synthetic paraffinic kerosene (SPK) produced by a hydroprocessed esters and fatty acids (HEFA) pathway that does not include a bio-olefin-containing feedstock of the sustainable fuel and under conditions that maximize overall liquid yield. Conditions that maximize overall liquidyield include conditions that minimize formation of Naphtha, light gases, and / or gasoline cuts, such as incomplete conversion of hydrocarbons from the Diesel range into the jet range.

[0109] The freezing point of the blended fuel (and the corresponding fuel blend) can be determined by a person of ordinary skill in the art using any of these methods. In certain embodiments, the freezing point can be determined using a ASTM D2386, ASTM D5972, ASTM D7153, ASTM D7154, or ASTM D7945 test method. In certain embodiments, the blended aviation fuel has a freezing point of less than -40°C or less than -47°C, such as a freezing point within the range of about -41°C to about -60°C, about 42°C to about 58°C, about 43°C to about 56°C, or about 45°C to about -55°C.

[0110] In certain embodiments, the blended aviation fuel can include any volume of sustainable fuel. In certain embodiments, the blended fuel includes about 5% to about 85%, about 10% to about 75%, about 15% to about 65%, about 20% to about 60%, about 25% to about 55%, or about 30% to about 50% of the sustainable fuel by volume. In certain embodiments, the blended aviation fuel comprises about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, or about 75% of the sustainable fuel by volume.

[0111] The blended aviation fuel can include any suitable petroleum-derived jet fuel. In certain embodiments, the petroleum-derived jet fuel comprises kerosene. In certain embodiments, the petroleum-derived jet fuel is adapted for use in commercial aircraft or in military aircraft (i.e., a commercial jet fuel or a military jet fuel). In certain embodiments, the petroleum-derived jet fuel is selected from the group consisting of a Jet A fuel, a Jet A-1 fuel, a Jet B fuel, a TS-1 fuel, a Jet Propellant (JP)-5 fuel, or a JP-8 fuel. In a particular embodiment, the petroleum-derived jet fuel is Jet A or Jet A-1 .

[0112] The blended aviation fuel can have an aromatics content that allows for compatibility with elastomeric seals in the fuel system of the aircraft, pump lubricity, engine operation, and / or combustion characteristics. In certain embodiments, the blended fuel includes at least 8%, at least 10%, at least 12%, at least 15%, at least 17%, at least 19%, at least 21 %, at least 23%, or at least 25% aromatics by volume.EXAMPLE

[0113] The following example provides a further understanding of the benefits of coprocessing of bio-olefins, as described above.

[0114] ASTM D-7566 permits HEFA-derived SAF to be blended up to 50% with Jet A-1. Targeting SAF from HEFA comes with trade-offs to meet jet fuel specifications. These tradeoffs can impact overall liquid yield and operating costs. One potential strategy to improve liquid product yield is relaxing the freezing point specification: a higher freezing point allows for lesssevere processing of the synthetic paraffinic kerosene (SPK), which should increase overall liquid yield.

[0115] A relevant example this approach is described in Starck, L., et. al. (“Production of Hydroprocessed Esters and Fatty Acids (HEFA) - Optimisation of Process Yields”, Oil & Gas Science and Technology, Rev. IFP Energies nouvelles, 71 (1), 10 (2016)). As reported therein processing that targets a higher freezing point limits the incorporation rate below the ASTM D-7655 target: only about 20% HEFA SAF having a freezing point around -20°C (“HEFA1”) can be blended with Jet A-1 to remain within the freezing point specification of Jet A-1. This is shown in Table 1 from the data extracted from the reference.TABLE 1 : Freezing Point of Jet A-1 / HEFA1 Blends.

[0116] The results with HEFA1 were compared with HEFA SAF having a freezing point below -47°C (“HEFA2”). To increase the amount of HEFA SAF that can be blended with Jet A-1 , an additional hydro-isomerization step is necessary to convert n-paraffins in HEFA SAF to iso-paraffins. The effect of this conversion on the freezing point is shown in Table 2 below. With the lower freezing point HEFA2, full 50% of the HEFA SAF can be blended with the Jet A-1 fuel.TABLE 2: Effect of n-paraffins to iso-paraffins conversion on the freezing point.

[0117] However, production of the lower freezing point HEFA2 SAF necessarily results in an increase in the yields of naphtha and light ends and a reduction in the yields of jet and Diesel range molecules (FIG. 4). In addition, capital-intensive hydroisomerization step, in most cases, uses an expensive noble metal catalyst and adds to the overall capital and operating costs of HEFA SAF production.

[0118] The impact of coprocessing a blended feedstock — comprising a hydroprocessed esters and fatty acids (HEFA)-precursor and a bio-olefin — on the incorporation rate was estimated from insights derived from the Sustainable Aviation Fuel (SAF) produced via the alcohol-to-jet (ATJ) pathway using ethanol as feedstock. The properties of SAF produced by the alcohol-to-jet pathway with ethanol as the feedstock are detailed in ASTM Research Report RR_D02-1884. The freezing point of several ATJ samples is shown below in Table 3.TABLE 3: Freezing Point of SAF derived from various Ethanol Feeds

[0119] The freezing points of the ATJ SAF are significantly better than that of the HEFA1 SAF.

[0120] Estimated SAF freezing points for two different blends of % HEFA1 , ATJ SAF, and Jet Fuel (Freezing Point -49.5°C) are shown in Table 4.TABLE 4: Estimated SAF freezing points

[0121] As shown in Table 4, coprocessing of the bio-olefin containing feedstock (e.g., ATJ oligomerates) with HEFA feedstock improves the freezing point of the blend, allows for more HEFA SAF to be blended with Jet A-1 , and increases the proportion of SAF in the overall blend to the ASTM D7566 allowable limit of 50%. In addition, coprocessing eliminates the need to hydroisomerize HEFA SAF which lowers the cost of producing HEFA SAF. Accordingly, the methods and compositions described in one or more embodiments of the present disclosure offer significant economic and environmental benefits by improving overall yield, lowering processing costs, and potentially expanding sustainable feedstock options for HEFA SAF.

[0122] Terminology used in the present disclosure is for the purpose of describing particular embodiments only and is not intended to limit the scope of the claims of the present invention. Many modifications and variations will be evident to those skilled in the art, that fall within the scope of the following claims:

Claims

WHAT IS CLAIMED IS:1 . A blended feedstock for producing a sustainable fuel, the blended feedstock comprising: a first renewable feedstock comprising a hydroprocessed esters and fatty acids (HEFA)-precursor; and a second renewable feedstock comprising a bio-olefin.

2. The blended feedstock of claim 1 , wherein the HEFA-precursor is selected from the group consisting of triglycerides, free fatty acids, vegetable oils, algal oils, bio-oils, animal fats, used cooking oils, non-edible oils, and combinations thereof.

3. The blended feedstock of claim 1 or 2, wherein the second renewable feedstock comprises an intermediate of an alcohol-to-jet (ATJ) process.

4. The blended feedstock of any one of claims 1-3, wherein the second renewable feedstock is obtained by dehydrating and oligomerizing an alcohol.

5. The blended feedstock of claim 4, wherein the alcohol comprises one or more of methanol, ethanol, propanol, iso-propanol, butanol, isobutanol and long-chain fatty alcohols.

6. The blended feedstock of claim 1 , wherein the second renewable feedstock is characterized as having one or more properties selected from the group consisting of: a density of 750 - 790 kg / m3, a freezing point of less than -50°C, an iso-paraffin content of at least 95%, a n-paraffin content of less than 5% by wt., optionally less than 2% by wt., a cycloparaffin content of less than 5% by wt., comprising C8-C24 oligomers, comprising monoolefins, comprising iso-olefins, being substantially free of sulfur, and being substantially free of aromatics.

7. The blended feedstock of claim 1 , wherein the first renewable feedstock and second renewable feedstock are present within a range of about 100:1 to 1 :100 wt / wt.

8. A process of producing a sustainable fuel comprising: hydrodeoxygenating a blended feedstock to form a deoxygenated feed; the blended feedstock comprising: a first renewable feedstock comprising a HEFA-precursor; and a second renewable feedstock comprising a bio-olefin.

9. The process of claim 8, whereby a ratio of iso- to n-paraffins in the deoxygenated feed is increased as compared to a fuel obtained by hydrogenating a feedstock that does not contain the second renewable feedstock.

10. The process of claim 8, further comprising mixing the first renewable feedstock and the second renewable feedstock.11 . The process of claim 8, wherein the first renewable feedstock comprises one or more of triglycerides, free fatty acids, vegetable oils, algal oils, bio-oils, animal fats, used cooking oils, non-edible oils, and combinations thereof.

12. The process of claim 8, wherein the second renewable feedstock is obtained by dehydrating and oligomerizing an alcohol.

13. The process of claim 12, wherein dehydrating the alcohol comprises contacting the alcohol with a dehydration catalyst to form an alkene or mixture of alkenes, wherein the dehydration catalyst is selected from the group consisting of supported phosphoric acids, activated alumina, molecular sieves, heteropoly acid catalysts, and mixtures thereof.

14. The process of claim 12, wherein oligomerizing comprises two or more two steps.

15. The process of claim 13, wherein oligomerizing comprises a first step comprising contacting the alkene or mixture of alkenes with a first oligomerization catalyst to form a first oligomerate, wherein the first oligomerization catalyst comprises nickel on a silico-aluminate support.

16. The process of claim 15, wherein Ni concentration in the first oligomerization catalyst is in a range of from 0.1 wt.-% to 10 wt.-%.

17. The process of claim 15, wherein the silico-aluminate support has a crystalline or amorphous structure.

18. The process of claim 17, wherein the silico-aluminate support comprises beta-zeolite.

19. The process of claim 15, wherein oligomerizing further comprises a second step comprising contacting the first oligomerate with a second oligomerization catalyst to providethe second renewable feedstock, wherein the second oligomerization catalyst comprises a silico-aluminate catalyst, a solid acid catalyst, or a mixture thereof.

20. The process of claim 19, wherein the silico-aluminate catalyst has a crystalline or amorphous structure.21 . The process of claim 20, wherein the silico-aluminate catalyst comprises beta-zeolite or H-ZSM-5 zeolite.

22. The process of claim 12, wherein the alcohol comprises one or more of methanol, ethanol, propanol, iso-propanol, butanol, isobutanol, and long-chain fatty alcohols.

23. The process of claim 8, wherein the second renewable feedstock is obtained by oligomerizing ethylene produced from direct conversion of CO2, optionally bio-genic CO2.

24. The process of claim 23, wherein direct conversion of CO2 to ethylene comprises electrocatalytic reduction or gas fermentation.

25. The process of claim 24, further comprising converting CO2 to ethylene by electrocatalytic reduction using a catalyst selected from the group consisting of pure copper, copper alloys, bimetallic Cu-based catalysts, Cu-based carbonaceous materials, and functionalized variants thereof, and mixtures thereof.

26. The process of claim 25, wherein electrocatalytic reduction comprises introducing CO2 to an H-type cell, a gas diffusion cell, a photo or solar cell, a flow-cell, and / or a membrane electrode assembly (MEA) cell.

27. The process of claim 24, further comprising converting CO2 to ethylene by gas fermentation.

28. The process of claim 27, wherein gas fermentation comprises passing a gaseous stream comprising CO2 to a bioreactor containing a culture of microorganism expressing an ethylene-forming enzyme.

29. The process of claim 28, wherein the microorganism expresses an exogenous ethylene-forming enzyme.

30. The process of claim 25 or 27, further comprising recovering ethylene by one or more of distillation, simulated moving bed processes, membrane treatment, evaporation, pervaporation, gas stripping, phase separation, ion exchange, and extractive fermentation.31 . The process of claim 26, wherein oligomerizing the ethylene comprises two or more two steps.

32. The process of claim 31 , wherein oligomerizing comprises a first step comprising contacting the ethylene with a first oligomerization catalyst to form a first oligomerate, wherein the first oligomerization catalyst comprises nickel on a silico-aluminate support.

33. The process of claim 32, wherein Ni concentration in the first oligomerization catalyst is in a range of from 0.1 wt.-% to 10 wt.-%.

34. The process of claim 32, wherein the silico-aluminate support has a crystalline or amorphous structure.

35. The process of claim 34, wherein the silico-aluminate support comprises beta-zeolite.

36. The process of claim 32, wherein oligomerizing further comprises a second step comprising contacting the first oligomerate with a second oligomerization catalyst to provide the second renewable feedstock, wherein the second oligomerization catalyst comprises a silico-aluminate catalyst, a solid acid catalyst, or a mixture thereof.

37. The process of claim 36, wherein the silico-aluminate catalyst has a crystalline or amorphous structure.

38. The process of claim 36, wherein the silico-aluminate catalyst comprises beta-zeolite or H-ZSM-5 zeolite.

39. The process of claim 8, wherein the first renewable feedstock and second renewable feedstock are present within a range of about 100:1 to 1 :100 wt / wt.

40. The process of claim 8, further comprising one or more of hydrogenating the deoxygenated feed, hydrocracking the deoxygenated feed, and hydro-isomerizing the deoxygenated feed.41 . The process of claim 8, further comprising hydrogenating the deoxygenated feed to form a hydrogenated product, and fractionating the hydrogenated product.

42. The process of claim 41 , wherein fractionating includes separating the hydrogenated product into a naphtha boiling point component, an aviation fuel boiling point range component, and a diesel boiling point range component.

43. The process of claim 42, further comprising blending the aviation fuel boiling point range component with a second fuel to produce a blended fuel.

44. The process of claim 43, wherein the second fuel comprises aromatics.

45. The process of claim 8, wherein the sustainable fuel is selected from the group consisting of synthetic paraffinic kerosene (SPK), sustainable aviation fuel (SAF), and renewable diesel (RD).

46. The process of claim 8, wherein hydrodeoxygenating comprises contacting the blended feedstock with a hydrogenation catalyst in the presence of hydrogen.

47. The process of claim 46, wherein the hydrogenation catalyst is selected from the group consisting of supported noble metal catalysts, supported nickel catalysts, supported nickel / molybdenum catalysts, and sulfided nickel molybdenum catalysts.

48. The process of claim 8, wherein the blended feedstock further comprises a fossil feedstock.

49. The process of claim 48, wherein the fossil feedstock is selected from the group consisting of crude oil, petroleum oil or gas, vacuum gas oil, shale oil or gas, natural gas, and coal deposits.

50. The process of claim 48, wherein the blended feedstock comprises about 80% or more fossil feedstock by volume.51 . The process of claim 48, whereby the sustainable fuel comprises at least 85% of the14C content of the blended feedstock.

52. A sustainable fuel produced by the process of any one of claims 8-51 .

53. A blended aviation fuel comprising a volume of the sustainable fuel of claim 52 and a petroleum-derived jet fuel, wherein the blended fuel is characterized by a lower freezing point than a corresponding aviation fuel blend comprising an equivalent volume of a synthetic paraffinic kerosene (SPK) produced by a hydroprocessed esters and fatty acids (HEFA) pathway that does not include a bio-olefin-containing feedstock and under conditions that maximize overall liquid yield.

54. The blended aviation fuel of claim 53, wherein the freezing point is determined using a ASTM D2386, ASTM D5972, ASTM D7153, ASTM D7154, or ASTM D7945 test method.

55. The blended aviation fuel of claim 53 or 54, comprising about 5% to about 85%, about 10% to about 75%, about 15% to about 65%, about 20% to about 60%, about 25% to about 55%, or about 30% to about 50% of the sustainable fuel by volume.

56. The blended aviation fuel of any one of claims 53-55, comprising about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, or about 75% of the sustainable fuel by volume.

57. The blended aviation fuel of any one of claims 53-56, having a freezing point of less than -40°C or less than -47°C.

58. The blended aviation fuel of any one of claims 53-57, having a freezing point within a range of about -41 °C to about -60°C, about 42°C to about 58°C, about 43°C to about 56°C, or about 45°C to about -55°C.

59. The blended aviation fuel of any one of claims 53-58, wherein the petroleum-derived jet fuel is a Jet A fuel, a Jet A-1 fuel, a Jet B fuel, a TS-1 fuel, a Jet Propellant (JP)-5 fuel, or a J P-8 fuel.

60. The blended aviation fuel of any one of claims 53-59, wherein the petroleum-derived jet fuel is adapted for use in commercial aircraft or in military aircraft.61 . The blended aviation fuel of any one of claims 53-60, comprising at least 8%, at least 10%, at least 12%, at least 15%, at least 17%, at least 19%, at least 21 %, at least 23%, or at least 25% aromatics by volume.

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