PRODUCE BIOFUELS

FIELD

[0001] The present disclosure relates to processes for producing biofuel compositions wherein a hydrocarbon (petroleum) oil and a hydrothermal liquefaction (HTL) oil(s) are co-processed in a cracking unit. In particular, the disclosure is directed to processes for producing fuel compositions comprising cracking a mixture of hydrocarbon co-feed and an HTL oil derived from cellulose.

BACKGROUND

[0002] With the rising costs and environmental aspects associated with fossil fuels, renewable energy sources have become increasingly important. The development of renewable fuel sources provides a means for reducing the dependence on fossil fuels. Accordingly, many different areas of renewable fuel research are currently being explored and developed.

[0003] To encourage such research efforts, Congress created the renewable fuel standard (also referred to as“RFS”) program to reduce greenhouse gas emissions and expand the nation’s renewable fuels sector while reducing reliance on imported oil. This program was authorized under the Energy Policy Act of 2005 and expanded under the Energy Independence and Security Act of 2007. Examples of such legislation include, but are not limited to, the LTnited States Environmental Protection Agency (also referred to as ΈRA”), the Energy Independence and Security Act (also referred to as“EISA”) and California AB 32 - Global Warming Solutions Act, which respectively established an RFS and a Low Carbon Fuel Standard (also referred to as“LCFS”). For instance, under EISA, the mandated annual targets of renewable content in fuel are implemented through an RFS that uses tradable credits (called Renewable Identification Numbers, referred to herein as “RINs”) to trail and conduct the production, distribution and use of renewable fuels for transportation or other purposes (e.g., pharmaceutical, plastics/resins, etc.). Targets under the LCFS can be met by trading of credits generated from the use of fuels with a lower greenhouse gas emission value than the gasoline baseline. Among such regulations, there are some related to the use of cellulosic containing biomass (cellulosic biomass) that can earn Cellulosic Renewable Identification Numbers (also referred to as“C-RINs”). The use of cellulosic biomass can also support fuel producers in meeting their Renewable Volume Obligations (also referred to as “RVO”).

[0004] With its low cost and wide availability, biomass has increasingly been emphasized as an ideal feedstock in renewable fuel research. Consequently, many different conversion processes have been developed that use biomass as a feedstock to produce useful biofuels and/or specialty chemicals. Existing biomass conversion processes include, for example, combustion, gasification, slow pyrolysis, fast pyrolysis, liquefaction, and enzymatic conversion. One of the useful products that may be derived from the aforementioned biomass conversion processes is a liquid product commonly referred to as "bio-oil." Bio-oil may be processed into transportation fuels, hydrocarbon chemicals, and/or specialty chemicals.

[0005] Despite recent advancements in biomass conversion processes, many of the existing biomass conversion processes produce low-quality bio-oils that are highly unstable and often contain high amounts of oxygen. These bio-oils require extensive secondary upgrading in order to be utilized as transportation fuels and/or as fuel additives due their instability. Furthermore, the transportation fuels and/or fuel additives derived from bio-oil vary in quality depending on factors affecting the stability of the bio-oil, such as the original oxygen content of the bio-oil.

[0006] Bio-oils can be subjected to various upgrading processes in order to process the bio-oil into renewable fuels and/or fuel additives. However, prior upgrading processes have been relatively inefficient and produce renewable fuels and/or fuel additives that have limited use in today's market. Furthermore, only limited amounts of these bio-oil derived transportation fuels and/or fuel additives may be combinable with petroleum-derived gasoline or diesel.

[0007] Accordingly, there is a need for improved processes and systems for producing and using bio-oils to produce renewable fuels.

[0008] References for citing in an Information Disclosure Statement (37 CFR 1.97(h)): U.S. 9, 120,989; U.S. 2013/0118059.

SUMMARY

[0009] The present disclosure relates to processes for producing biofuel compositions by processing hydrocarbon co-feed and a bio-oil obtained via hydrothermal liquifaction (HTL) of a cellulosic biomass to form an HTL oil. The cellulosic mass can be processed at an operating temperature of about 425°C or less, an operating pressure of about 200 atm or less, a residency time of about 5 minutes to about 60 minutes, in the presence of a catalyst. The HTL oil is co- processed with a hydrocarbon co-feed (e.g., petroleum fraction) in a cracking unit, such as an FCC unit, a coker unit or a visbreaking unit, in the presence of a catalyst, at an operating temperature of about 400°C to about 700°C, such as about 545°C to about 585°C, an operating pressure of about 10 psig to about 50 psig, such as about 15 psig (1 bar) to about 30 psig (2 bar), and/or a residency time of about 1 second to about 30 seconds, such as about 2 seconds to about 10 seconds to produce a biofuel.

[0010] In an embodiment, a process for generation of biofuels includes introducing (“feeding”) through separate injection nozzles, an HTL oil and a hydrocarbon (such as Vaccum Gas Oil (VGO) and/or Resid/De-Asphalted Oil (DAO) to a cracker, such as a fluidized catalytic cracking (FCC) unit. [0011] In at least one embodiment, the present disclosure provides a method of processing a hydrocarbon co-feed (e.g., VGO) with an HTL oil in the presence of a cracking catalyst resulting in an improved biofuel product.

[0012] In at least one embodiment, a method of preparing a biofuel includes: i) processing a hydrocarbon co-feed with a HTL oil feedstock in the presence of a cracking catalyst; and ii) optionally, adjusting feed addition rates of the hydrocarbon co-feed, the HTL oil feedstock, or both, to target a desirable biofuel product profile, a riser temperature, or a reaction zone temperature; or iii) optionally, adjusting the amount of cracking catalyst to combined hydrocarbon co-feed/HTL oil ratio (catalyst : oil(s) ratio).

[0013] Further, the present disclosure provides a cracking system wherein the oils are injected separately into the cracker unit so that separation of the final biofuel is not required. For example, the system can include at least two or more feed nozzles coupled with a cracking unit for injection of the oils into the cracking unit.

DETAILED DESCRIPTION

[0014] The present disclosure relates to methods of generating biofuels by co-processing an HTL oil, derived from a cellulosic biomass, with a hydrocarbon oil in a cracking unit. The HTL oil can be derived from cellulosic biomass processed at an operating temperature of about 425°C or less, an operating pressure of about 200 atm or less, a prolonged residency time of about 5 minutes to about 60 minutes, in the presence of a catalyst to form an HTL oil. The HTL oil is co- processed with a hydrocarbon oil (e.g., petroleum fraction) in the presence of a cracking catalyst in cracking unit at an operating temperature of about 400°C to about 700°C, such as about 545°C to about 585°C, an operating pressure of about 10 psig to about 50 psig, such as about 15 psig (1 bar) to about 30 psig (2 bar), and/or a residency time of about 1 second to about 30 seconds, such as about 2 seconds to about 10 seconds, to form a biofuel which may be a cellulosic-renewable identification number-compliant fuel. Processes of the present disclosure provide biofuel compositions without any separation process of the cracked product(s). The cracking process can be performed using a system of at least two or more injection nozzles on the cracking unit, which promotes better blending of the HTL and hydrocarbon oils (and ultimately cracked product(s)) by increasing the dispersion, providing additional time-, energy- and cost-efficiency. In an embodiment, a process for generation of biofuel oils is described that includes introducing (“feeding”), separately or as a mixture, HTL oil and hydrocarbon (such as Vaccum Gas Oil (VGO) and/or Resid/De-Asphalted Oil (DAO) to a cracking unit such as a fluidized catalytic cracking (FCC) unit, such that a portion of the feed HTL oil passes through the FCC (or alternate cracking process like coking or visbreaking) reactor section (with some conversion) and ends up in the product fuel. The bio content of the cracked product provides RIN credits for the cracked product.

[0015] It has been discovered that when HTL oil is the source of the bio-oil and is processed along with a hydrocarbon oil, and the two oils are separately injected into the cracking unit, a useful biofuel is produced directly and a separation step is not required to obtain the biofuel. The present disclosure is directed to a simple, time-effective, energy-effective, and cost-effective environmentally-friendly process that combines HTL technology and cracking technology for conversion of oils into biofuels. In at least one embodiment, the present disclosure advantageously provides a process for meeting renewable fuel targets or mandates established by governments, including legislation and regulations for transportation fuel sold or introduced into commerce in the United States.

[0016] In at least one embodiment, the present disclosure provides a method of processing a hydrocarbon co-feed (e.g., VGO) with a portion thereof blended with an amount of HTL oil. The feeds are processed in the presence of a cracking catalyst resulting in an improved yield of the biogenic carbon, such as an increase of at least 0.5 wt%, such as from about 0.5 wt% to 3 wt%, thus relative to the identical process on an equivalent energy or carbon content basis of the feedstream where the hydrocarbon co-feed is not blended with any other fuel feedstock (such as a HTL oil).

[0017] In at least one embodiment, a method of preparing a biofuel includes: i) processing a hydrocarbon feedstock with an HTL feedstock in the presence of a catalyst; and ii) optionally, adjusting feed addition rates of the hydrocarbon co-feed, the HTL feedstock, or both, to target a desirable biofuel product profile, a riser temperature, or a reaction zone temperature; or iii) optionally, adjusting the cracking catalyst to combined hydrocarbon/HTL feedstock ratio (catalyst : oil(s) ratio).

[0018] Further, the present disclosure provides a system for separately injecting the feedstocks into the cracking unit, for example, by providing at least two or more feed nozzles coupled with an FCC unit for injection into the FCC unit.

[0019] Methods and systems for making compositions of the present disclosure may include renewable fuel (also referred to as HTL oil or renewable oil) as a feedstock in cracking units, such as FCCs, and other refinery systems or field upgrader operations. Renewable fuels may include fuels produced from renewable resources. Suitable HTL oils may include biofuels such as solid biofuels (e.g., wood used as fuel, cellulosic biomass), biodiesel, bio-alcohols (e.g., biomethanol, bio-ethanol, biobutanol) from biomass, and hydrogen fuel (when produced with renewable energy sources), catalytically converted biomass to liquids, and thermochemically produced liquids. In at least one embodiment, the HTL oil is a cellulosic material from biomass. [0020] As used herein, and unless otherwise specified, the term“Cn” means hydrocarbon(s) having n carbon atom(s) per molecule, wherein n is a positive integer.

[0021] As used herein, and unless otherwise specified, the term“hydrocarbon” means a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different values of n. Additionally, the hydrocarbon compound may contain, for example, heteroatoms such as sulphur, oxygen, nitrogen, or any combination thereof. Suitable hydrocarbon compounds may include acetic acid, formic acid, levulinic acid and gamma-valerolactone and/or mixtures thereof.

[0022] The term “hydrocarbon co-feed” refers to a co-feed that contains one or more hydrocarbon compounds.

[0023] The term“fluid hydrocarbon co-feed” refers to a hydrocarbon feed that is not in a solid state. The fluid hydrocarbon co-feed can be a liquid hydrocarbon co-feed, a gaseous hydrocarbon co-feed, or a mixture thereof. Also, the fluid hydrocarbon co-feed can be fed to a catalytic cracking reactor in a liquid state, and/or in a gaseous state, or in a partially liquid-partially gaseous state. When injected into the catalytic cracking reactor in a liquid state, and/or in a gaseous state, or in a partially liquid-partially gaseous state, the fluid hydrocarbon co-feed may be vaporized upon entry, such as the fluid hydrocarbon co-feed may be contacted in the gaseous state with the FCC catalyst. A hydrocarbon co-feed can be a petroleum oil.

[0024] The term“liquefaction”, also referred to as“liquefying”, refers to the conversion of a gas material and/or solid material, such as cellulosic material, into one or more liquid (liquefied) products.

[0025] The term“liquefied product” refers to a product that is liquid at a temperature of about 20°C and a pressure of about 1 bar absolute (0.1 MPa). A“liquefied product” can also refer to a product that can be converted into a liquid by melting (e.g., melting upon heat) or dissolving in a solvent (e.g., an organic solvent). In at least one embodiment, the liquefied product is a liquefied product that is liquid at a temperature of about 80°C and a pressure of about 1 bar absolute (0.1 MPa). Suitable liquefied products may be more or less viscous and with a viscosity that may extensively vary.

[0026] The term“liquid solvent” is herein understood to be a solvent that is liquid at the temperature and pressure at which the liquefaction process is carried out.

[0027] The term“final liquefied product” refers to a liquefied product suitable to be directed to the catalytic cracking process. [0028] The term “cracked product(s)” refers to product(s) obtained after processing/cracking/breaking down heavy hydrocarbon molecules (usually nonvolatile) into lighter molecules (such as light oils (corresponding to gasoline), middle-range oils used in diesel fuel, residual heavy oils, a solid carbonaceous product known as coke, and such gases as methane, ethane, ethylene, propane, propylene, and butylene) by means of heat, pressure, and/or catalysts in a refinery reactor unit, such as an FCC reactor unit. The terms“cracked product” and“final liquefied RINs-product” may be used herein interchangeably.

[0029] The term“visbreaking” refers to the untangling of molecules in fluid during heat treatment and/or to the breaking of large molecules into smaller molecules during heat treatment, which results in a reduction of the viscosity of the fluid.

Hydrothermal Liquefaction

[0030] Hydrothermal liquefaction (HTL) technology produces HTL oil at a lower temperature with much longer residency time as compared to, for example, a fast py-oil process. The HTL process, also called“hydrous pyrolysis”, is used for the reduction of complex organic materials such as biowaste and/or biomass into crude oil and other chemicals. The pathway of HTL can include three major phases, i) depolymerisation, followed by ii) decomposition and iii) recombination/repolymerisation of the reactive fragments. HTL can involve direct liquefaction of biomass, with the presence of water and perhaps some catalysts, to directly convert biomass into liquid oil, at a reaction temperature of less than 400°C. HTL can have different pathways for the biomass feedstock and, unlike biological treatment (e.g., anaerobic digestion), HTL converts feedstock into oil rather than gases or alcohol. There are some unique features of the HTL process and its product compared with other biological processes: 1) the end product is a crude oil (which has much higher energy content of fuels than syngas or alcohol, the energy content being an important property of fuels obtained by the amount of heat produced by the burning of 1 gram of a substance, and is measured in joules per gram); 2) if the feedstock contains a lot of water, HTL does not require drying. As noted above, known processes require extensive separation of products after co-processing in the cracking unit which requires high-energy consumption by large separators, which counteracts the lower greenhouse gas emissions that the obtained biofuels are aiming to achieve. An HTL process of the present disclosure can be performed in any suitable HTL reactor, such as described in U.S. Pat. Pub. No. 2013/0118059, incorporated by reference.

[0031] Suitable biomass, biomass materials, or biomass components, include but are not limited to, wood, wood residues, forest debris, sawdust, slash bark, scrap lumber, manure, thinnings, forest cullings, begasse, corn fiber, corn stover, empty fruit bunches, fronds, palm fronds, flax, straw, low-ash straw, energy crops, palm oil, non-food-based biomass materials, crop residue, slash, pre-commercial thinnings, urban wood and yard wastes, tree residue, annual covercrops, switchgrass, mill residues, miscanthus, animal manure (dry and/or wet), cellulosic containing components, cellulosic components of separated yard waste, cellulosic components of separated food waste, cellulosic components of separated municipal solid waste, or combinations thereof. Suitable cellulosic biomass may include biomass derived from or containing cellulosic materials. For purposes of the present disclosure, the HTL oil can be an oil processed from a cellulosic-containing biomass.

[0032] The biomass can be characterized as being compliant with U. S. renewable fuel standard program (RFS) regulations, or a biomass suitable for preparing a cellulosic-renewable identification number-compliant fuel, for example. Suitable biomass can be characterized as being compliant with those biomass materials specified in the pathways for a D-code 1, 2, 3, 4, 5, 6, or 7-compliant fuel, in accordance with the U.S. renewable fuel standard program (RFS) regulations, such as the biomass can be characterized as being compliant with those biomass materials suitable for preparing a D-code 3 or 7-compliant fuel, in accordance with the U.S. renewable fuel standard program (RFS) regulations or the biomass can be characterized as being composed of only hydrocarbons (or renewable hydrocarbon biofuels, also called“green” hydrocarbons).

[0033] The term“renewable fuel oil” (also referred to as "HTL oil") refers to a biomass-derived fuel oil or a fuel oil produced from the conversion of biomass. The HTL oil used in the process of the present disclosure is a cellulosic renewable fuel oil (also referred to as "cellulosic HTL oil"), and may be derived or prepared from the conversion of cellulosic-containing biomass which is processed via HTL to produce an HTL oil. The HTL-processed HTL oil described herein could also be blended with various non-hydrodeoxygenated, non-deoxygenated, non-hydrotreated, non- upgraded, non-catalytically processed, thermo-mechanically-processed, HTL-processed HTL oil and/or other non-hydrodeoxygenated, non-deoxygenated, non-hydrotreated, non-upgraded, non- catalytically processed, thermo-mechanically-processed, HTL-processed HTL oil that has been derived from other biomass to form blends of non-hydrodeoxygenated, non-deoxygenated, non- hydrotreated, non-upgraded, non-catalytically processed, thermo-mechanically-processed, HTL- process HTL oil.

[0034] In at least one embodiment, the HTL oil is a liquid formed from a biomass including a cellulosic material, wherein the only processing of the biomass is a thermo-mechanical process (specifically including grinding and slow thermal processing (e.g., HTL process), and optionally post-processing or enrichment of the HTL oil liquid prior to introduction into a hydrocarbon conversion unit.

[0035] In particular, the process for making cellulosic RIN-compliant fuel compositions may include a liquefaction process where a cellulosic material is contacted with a liquid solvent to produce a final HTL oil liquefied product. This process may also be referred to as liquefaction or liquefying of the cellulosic material. The liquefaction or liquefying may be carried out by means of a liquefaction or liquefying reaction.

[0036] In at least one embodiment, the liquefaction process is a hydrothermal liquefaction process, meaning that the pyrolysis of a biomass may occur at a reacting (e.g., operating) temperature of less than about 425°C, such as from about 200°C to 425°C, such as from about 250°C to 350°C, and at a residence time of at least 1 minute, such as from about 1 minute to about 2 hours, such as from about 5 minutes to about 1.5 hours, such as from about 10 minutes to about 1 hour, such as from about 15 minutes to about 45 minutes, such as from about 20 minutes to about 30 minutes.

[0037] A cellulosic material can refer to a material containing cellulose. In at least one embodiment, the cellulosic material is a lignocellulosic material. A lignocellulosic material includes lignin, cellulose and optionally hemicellulose. One of the advantages of the liquefaction process is that the process enables liquefaction not only of the cellulose but also the lignin and hemicelluloses.

[0038] For the purposes of this disclosure, any suitable cellulose-containing material can be used as cellulosic material. The cellulosic material for use according to the present disclosure may be obtained from a variety of plants and plant materials including forestry wastes, agricultural wastes, sugar processing residues and/or mixtures thereof. Examples of suitable cellulose- containing materials include, but are not limited to, agricultural wastes such as corn cobs, corn stover, soybean stover, rice straw, rice hulls, oat hulls, corn fibre, cereal straws such as wheat, barley, rye and oat straw; grasses; forestry products such as wood and wood-related materials such as sawdust; waste paper; sugar processing residues such as bagasse and beet pulp; or mixtures thereof.

[0039] The HTL oil formed by liquefaction can be an unenriched liquid (such as an unenriched HTL oil) formed from ground-up biomass by a process, such as a slow thermal processing, wherein the resulting liquid may be at least 50 wt%, such as at least 60 wt%, such as at least 70 wt%, such as at least 75 wt%, such as at 80 wt%, such as at least 85 wt%, such as at least 90 wt% of the total weight of the processed biomass. Namely, the liquid (i.e., the HTL oil) yield from the processed biomass can be at least 50 wt%, such as at least 60 wt%, such as at least 70 wt%, such as at least 75 wt%, such as at least 80 wt%, such as at least 85 wt%, such as at least 90 wt% of the total weight of the ground biomass being processed. The term“unenriched” refers to HTL oil liquid that does not undergo any further pre- or post-processing including, more particularly, no hydrodeoxygenation, no hydrotreating, no catalytic exposure or contact. For example, unenriched HTL oil can be prepared from the ground biomass and then transported and/or stored, and can be even heated or maintained at a given temperature; not exceeding about 65°C, on its way to being introduced into the conversion unit at the refinery (i.e., refinery FCC unit). The mechanical handling associated with transporting, storing, heating, and/or pre-heating of the unenriched HTL oil should not be considered an enriching process. An unenriched HTL oil may include one or more unenriched HTL oils mixed from separate unenriched assortments and/or unenriched assortments generated from different cellulosic biomass (such as assorted varieties of non-food biomass). Additionally, mixed compositions can be blended to purposefully provide or achieve particular characteristics in the combined unenriched HTL oil.

[0040] In at least one embodiment, the HTL oil includes thermally converted biomass or thermo-mechanically converted biomass. Suitable HTL oils may include an HTL liquid (i.e., HTL oil), derived or prepared from the conversion of biomass (e.g., cellulosic biomass). Any suitable HTL oil may include a non-HDO HTL oil, a non-deoxygenated HTL oil, a non-upgraded HTL oil, a thermally-processed cellulosic HTL oil, a thermally-processed, non-upgraded-cellulosic HTL oil, a thermally-processed biomass liquid; a thermally-processed-non-upgraded-biomass liquid, a thermally processed non-food-based biomass liquid, a thermally-processed non-food, cellulosic- based biomass liquid, a thermally-processed non-food-renewable liquid, a thermally-processed cellulosic liquid, a slow thermal-processed cellulosic liquid, a slow thermal-processed bio-oil, a slow thermal processed biomass liquid or thermo-pyrolytic liquid having less than 5 wt% solid content, such as less than 5 wt%, such as less than 4 wt%, such as less than 3 wt%, such as less than 2 wt%, such as less than 1 wt%, such as less than 0.5 wt% solid content. Further examples of suitable HTL oil may include a conditioned HTL oil, a non-hydrotreated-non-upgraded HTL oil, a HTL oil or HTL liquid, a thermo-HTL oil or a thermo-HTL liquid, a bio-oil or a bio-oil liquid, a biocrude oil or biocrude liquid, a thermo-catalytic HTL oil or a thermo-catalytic HTL liquid, a catalytic HTL oil or a catalytic HTL liquid, or any combinations thereof.

[0041] In at least one embodiment, the HTL oil may include one or more of a non-HDO HTL oil, a non-deoxygenated HTL oil, a non-upgraded HTL oil, a thermally-processed cellulosic HTL oil, a slow thermo-mechanically-processed HTL oil, a non-hydrotreated-non-upgraded HTL oil, an HTL oil or HTL liquid; or a thermo-HTL oil or a thermo-HTL liquid.

[0042] Moreover, the liquefaction process may include torrefaction, steam explosion, particle size reduction, densification and/or pelletization of the cellulosic material before the cellulosic material is contacted with the liquid solvent. Such torrefaction, steam explosion, particle size reduction, densification and/or pelletization of the cellulosic material may advantageously allow for improved process operability and economics.

[0043] For example, the cellulosic material can be processed into small particles before being used in the process of the present disclosure, thus in order to promote liquefaction. In at least one embodiment, the cellulosic material is processed into particles having a particle size distribution with an average particle size of about 0.01 millimeter or greater, such as of about 0.05 millimeter or greater, such as of about 0.1 millimeter or greater, such as of about 0.5 millimeter or greater, such as from about 0.01 millimeter to about 30 centimeters, such as from about 1 millimeter to about 20 centimeters, such as from about 2 millimeter to about 10 centimeters, such as from about 5 millimeter to about 5 centimeters. For practical purposes of the present disclosure, the particle size of the cellulosic material in the centimeter and millimeter range can be determined by sieving.

[0044] Particularly, the cellulosic material can be a lignocellulosic material that may involve a pre-treatment in order to remove and/or degrade undesirable lignin and/or hemicellulose. Suitable pre-treatments of lignocellulosic material may include fractionation, pulping and torrefaction processes.

[0045] Suitable HTL oils may have a pH in the range of about 0.5 to about 8, such as of 0.5 to 7, such as of about 0.5 to about 6.5, such as of about 1 to about 6, such as of about 1.5 to about 5, such as of about 1.5 to 4, such as of about 2 to about 3.5. In at least one embodiment, the pH of the HTL oil is less than 8, such as less than 7, such as less than 6.5, such as less than 6, such as less than 5.5, such as less than 5, such as less than 4.5, such as less than 4, such as less than 3.5, such as less than 3, less than 2.5, such as about 2. For example, the pH of the HTL oil may be altered or modified by the addition of an external, non-biomass derived material or pH altering agent. For example, the HTL oil may be acidic. Since the HTL oil is injected in a small quantity into the FCC (as compared to the total weight of the processed biofuel composition), it has been discovered that the risk of corrosion from the acidity generated during the process is limited and the conversion process of hydrocarbons to biofuel in the FCC provides desirable biofuel compositions at pH values of about 5 to 7. Also, the HTL oil may have the pH resulting from the conversion of the biomass from which it may be derived, such as a biomass-derived pH.

[0046] In at least one embodiment, the HTL oil has a solids content from about 0.002 wt% to about 10 wt%, such as from about 0.005 wt% to about 8 wt%, such as from about 0.01 wt% to about 6 wt%, such as from about 0.05 wt% to about 4 wt%, such as from about 0.1 wt% to about 3 wt%, such as from about 0.2 wt% to about 2 wt%, such as from about 0.5 wt% to about 1 wt%, based on the total weight of the HTL oil.

[0047] The term“liquid solvent” refers to a solvent that is liquid at a pressure of about 1 bar atmosphere (0.1 MPa) and at a temperature of about 80°C or higher, such as about 90°C or higher, such as about l00°C or higher, such as about l20°C. In at least one embodiment, the liquid solvent includes or is water.

[0048] In at least one embodiment, the liquid solvent includes or is an organic solvent. Suitable organic solvent can be a solvent including one or more hydrocarbon compounds. Under standard environmental conditions, hydrocarbon compounds are nonpolar hydrophobic.

[0049] Suitable HTL oil may include a solvent content of from 5 wt% to 45 wt%, such as from 10 wt% to 35 wt%, such as from 15 wt% to 30 wt%, such as from 20 wt% to 35 wt%, such as alternatively 20 wt% to 30 wt%, such as alternatively 30 wt% to 35 wt%, such as alternatively 25 wt% to 30 wt% water.

[0050] In at least one embodiment, the HTL oil includes an oxygen content level higher than that of a hydrocarbon co-feed. For example, the HTL oil may have an oxygen content level of greater than 10 wt%, on a dry basis, such as an oxygen content level in the range of about 10 wt% to 50 wt%, such as from about 15 wt% to about 40 wt%, such as from about 20 wt% to about 35 wt%, on a dry basis.

[0051] For example, the HTL oil may include a carbon content of about 30 wt% to 90 wt%, such as of about 35 wt% to 80 wt%, such as of about 40 wt% to 70 wt%, such as of about 50 wt% to 60 wt%, and/or an oxygen content of about 20 wt% to 50 wt% oxygen content, such as of about 30 wt% to 40 wt% oxygen content, on a dry basis.

[0052] In at least one embodiment, the HTL oil includes a carbon content of at least 35 wt% of the carbon content contained in the biomass from which it may be derived. For instance, the HTL oil may include a carbon content level of from about 35 wt% to about 100 wt%, such as about 40 wt% to about 90 wt%, such as about 45 wt% to about 80 wt%, such as about 50 wt% to about 70 wt%, such as about 55 wt% to about 60 wt%, of the carbon content contained in the biomass from which it may be derived. In at least one embodiment, the HTL oil includes a carbon content level lower than that of a hydrocarbon co-feed. For example, the HTL oil may include a carbon content of from about 30 wt% to about 90 wt%, such as about 40 wt% to 80 wt%, such as from 50 wt% to about 60 wt%, on a dry basis.

[0053] The energy content is a property of fuels and is defined as the fuel’s primary energy obtained by the amount of heat produced by the burning of 1 gram of a substance, and is measured in joules per gram. The energy content of a fuel is determined by burning an amount of the fuel and capturing the heat released in a known mass of water in a calorimeter. The energy released can be calculated at initial and final temperatures using the equation

H = At ^» m ^» Cp

where H is the heat energy absorbed (in Joules), At is the change in temperature (in °C), m is the mass (in gram), and Cp is the specific heat capacity (4.18 J/g°C for water). Dividing the resulting energy value by grams of biomass burned gives the energy content (in J/g). The HTL oil may include an energy content level of at least 20% of the energy content contained in the biomass from which it may be derived, such as an energy content level of about 40% to at least 100% of the energy content contained in the biomass from which it may be derived. In at least one embodiment, the HTL oil includes an energy content level of about 50% to about 99% of the energy content contained in the biomass from which it may be derived, such as from about 55% to 90%, such as from about 50% to about 80%, such as from about 60% to about 70%, alternately from about 70% to about 80% of the energy content contained in the biomass from which it may be derived.

[0054] In at least one embodiment, a suitable catalyst for HTL processing is an alkali reagent. Examples of suitable alkali catalyst for HTL can be, but are not limited to, Na2CCh, KOH, K2CO3, FeSCri, Ni(OH) ₂ .

[0055] In at least one embodiment, the organic solvent is partially derived from cellulosic material, such as lignocellulosic material, and/or partially derived from a hydrocarbon source. The organic solvent may include a mixture of a fraction of a hydrocarbon oil and/or one or more hydrocarbon compounds that may be obtained by acid hydrolysis of a cellulosic material, such as a lignocellulosic material.

[0056] In at least one embodiment, the organic solvent includes at least one or more carboxylic acids, for example, such as formic acid, acetic acid, levulinic acid and/or pentanoic acid. Such carboxylic acid(s) can be present before beginning the liquefaction process, that is, which carboxylic acid(s) cannot be in-situ generated and/or derived from the cellulosic material during the reaction.

[0057] The organic solvent may be water-miscible at the reaction temperature of the liquefaction process. The liquefaction process may include contacting the cellulosic material with a solvent mixture including the organic solvent with or without the presence of water.

[0058] During the liquefaction process, water in the solvent mixture may be generated in-situ. In at least one embodiment, the organic solvent is present in an amount of from about 1 wt% to about 99 wt%, such as from about 5 wt% to about 95 wt%, such as from about 10 wt% to about 90 wt%, such as from about 15 wt% to about 85 wt%, such as from about 20 wt% to about 80 wt%, such as from about 25 wt% to about 70 wt%, such as from about 30 wt% to about 70 wt%, such as from about 40 wt% to about 60 wt%, based on the total weight of water and organic solvent.

[0059] A cellulosic material and an organic solvent may be mixed in a solvent mixture at an organic solvent-to-cellulosic material ratio of 0.5: 1 to 50: 1, such as 1 : 1 to 40: 1, such as 2: l to 30: l, such as 3 : 1 to 20: 1, such as 4: 1 to 15: 1, such as 5: 1 to 10: 1, such as 6: 1 to 8: 1 by weight. [0060] In at least one embodiment, the liquefaction process is carried out in the presence of a catalyst. The use of a catalyst advantageously allows one to lower the reaction temperature and speed up the reaction process.

[0061] In at least one embodiment, an HTL process is conducted in an aqueous condensed phase. The HTL may be conducted at an operating temperature of from about 200 °C to 425 °C, such as from about 250 °C to 400 °C, such as from 275 °C to 375 °C, such as from about 300 °C to 350 °C, alternatively from about 250 °C to 350 °C. In at least one embodiment, the HTL is conducted at an operating pressure of from about 50 atm to about 400 atm, such as from about 100 atm to about 300 atm, such as from about 150 atm to about 275 atm, such as at 200 atm.

[0062] An HTL process may be conducted at a residence time of from about 1 minute to about 2 hours, such as from about 5 minutes to about 1 hour, alternatively from about 5 minutes to about 30 minutes. In at least one embodiment, a processed HTL oil is produced at a carbon yield to biofuel of about 10% to about 60%, such as from about 15% to about 50%, such as from about 20% to about 40%. The present disclosure provides a processed HTL oil having a low heating value of about 20 MJ/kg to 60 MJ/kg, such as about 25 MJ/kg to about 50 MJ/kg.

[0063] In at least one embodiment, an HTL oil is produced via HTL with an oxygenates content of about 15% or lower, such as about 12% or lower, such as about 10% or lower, and a water content of about 8% or lower, such as about 5% or lower, such as about 3% or lower. Without being bound by theory, the low contents of water and oxygenates can promote a greater thermal stability of the HTL oil formed via HTL.

[0064] Kinematic Viscosity at 40 °C (KV40) of the HTL oil after HTL can be at least 500 cSt or greater, such as 1,000 cSt or greater, such as 1,500 cSt or greater, such as 2,000 cSt or greater, such as 2,500 cSt or greater, such as 3,000 cSt or greater, such as 3,500 cSt or greater, such as at least 4,000 cSt or greater.

Fluid Catalytic Cracking

[0065] In at least one embodiment, the present disclosure also provides a process for conversion of a cellulosic material including: i) a liquefaction process, including contacting a cellulosic material with or without an organic solvent at a temperature of from about 200°C to about 425°C, optionally in the presence of a catalyst, where the organic solvent includes a fraction of one or more hydrocarbon oil(s), to produce an HTL oil (e.g., a final liquefied product); ii) a catalytic cracking process, including contacting a mixture of at least part of the HTL oil and the organic solvent (fraction of one or more hydrocarbon oil(s)) with an FCC catalyst in an FCC reactor at a temperature of from about 400°C to about 700°C, such as about 545°C to about 585°C, thus to produce one or more cracked product(s). In at least one embodiment, the final cracked product of stage ii) may suitably be the biofuel composition or any part thereof. For example, the final cracked product of stage ii) can be introduced to (e.g., blended with) one or more additional components to form a biofuel composition. The final cracked product, with or without blending to one or more additional components to form a biofuel composition, is not fractionated after an FCC process. Moreover, after an FCC process, the final cracked product, with or without blending to one or more additional components to form a biofuel composition, is not further separated and/or distilled (e.g., for additional purification processes) from all the reaction mixture(s) formed during the cracking process, with the exception of optionally removing water. The final cracked product, with or without blending to one or more additional components to form a biofuel composition, may be stored, manufactured, commercialized and/or employed as is, after an FCC process. Alternatively, the final cracked product can be blended with one or more additional components to form a biofuel composition.

[0066] In at least one embodiment, a refinery method and system may include an assembly for introducing the HTL oil, such as an HTL-processed oil, in an amount of at least about 1 wt% of the HTL oil, such as about 1 wt% to about 20 wt% of the HTL oil, into an FCC unit or field upgrader operation with the contact time of the cracking catalyst being for a period of about 0.5 seconds to about 40 minutes, such as from about 1 second to about 30 minutes, such as from about 30 seconds to about 15 minutes, such as from about 1 minute to about 5 minutes, alternately from about 5 minutes to about 40 minutes.

[0067] Furthermore, the HTL oil can be conditioned prior to introduction into the refinery process (e.g., FCC reactor unit) and can be made from several compositions as discussed above. In at least one embodiment, an HTL oil is produced from the HTL conversion of biomass under the conditions of 200 °C to 425 °C (e.g., 350 °C), at a processing residence time of at least 1 minute, such as from 1 minutes to 2h, such as from 5 minutes to 30 minutes, either with or without a catalyst. An example of a catalyst used for the cracking process may be Y-Zeolite, ZSM-5 or other FCC catalyst, or mixtures thereof (further details will be provided below). A catalyst additive can be added to optimize the performance of the FCC catalyst when processing HTL oil.

[0068] In at least one embodiment, a hydrocarbon co-feed, for example derived from upgrading petroleum, includes a gas oil (GO) feedstock, a vacuum gas oil (VGO) feedstock, a heavy gas oil (HGO) feedstock, LPG, a middle distillate feedstock, a heavy-middle distillate feedstock, a hydrocarbon-based feedstock, Resid/De-Asphalted Oil (DAO) or combinations thereof. The hydrocarbon co-feed may be gasoline or diesel. Where a catalyst is used, the catalyst/oil ratio can be in the range of about 2/1 to 10/1, such as about 3/1 to 9/1, 4/1 to 8/1, or 5/1 to 7/1, where oil in this ratio is the total amount of oil feedstock introduced (e.g., hydrocarbon co- feed and the HTL oil feedstock).

[0069] In at least one embodiment, the amount of the HTL oil feedstock that may be introduced into a refinery for co-processing with a hydrocarbon co-feed, is in the range of from about 1 wt% to about 20 wt%, such as from about 2 wt% to about 15 wt%, such as from about 3% to about 10%, such as from about 4% to about 8%, relative to the total amount of feedstock introduced into the refinery for processing (e.g., hydrocarbon co-feed and the HTL oil feedstock). For example, the amount of HTL oil feedstock introduced into the cracking conversion unit for co- processing with a hydrocarbon co-feed, may be 1 wt%, relative to the total amount of feedstock introduced into the refinery for processing, such as 2 wt%, such as 3 wt%, such as 4 wt%, such as 5 wt%, such as 6 wt%, such as 7 wt%, such as 8 wt%, such as 9 wt%, such as 10 wt%, such as 11 wt%, such as 12 wt%, such as 13 wt%, such as 14 wt%, such as 15 wt%, such as 16 wt%, such as 17 wt%, such as 18 wt%, such as 19 wt%, such as 20 wt%, relative to the total amount of feedstock introduced into the refinery for processing.

Injection System coupled to the Cracking unit

[0070] In at least one embodiment, an HTL oil is fed to a cracking reactor in a liquid state and/or in a gaseous state, or in a partially liquid-partially gaseous state. When injected into the reactor in a liquid state, and/or in a gaseous state, or in a partially liquid-partially gaseous state, the HTL oil can be vaporized upon entry, such that the HTL oil can be contacted in the gaseous state with the cracking catalyst.

[0071] Furthermore, a catalytic cracking process may include contacting the HTL oil and a fluid hydrocarbon co-feed (e.g., petroleum oil) with a cracking catalyst, such as in an FCC reactor with an FCC catalyst, at a temperature of about 400°C to about 700°C, such as about 545°C to about 585°C, to produce one or more cracked products.

[0072] In at least one embodiment, the fluid hydrocarbon co-feed is any non-solid hydrocarbon co-feed suitable as a co-feed for a catalytic cracking unit. For example, the fluid hydrocarbon co- feed can be obtained from a conventional crude oil (also sometimes referred to as a petroleum oil or mineral oil), an unconventional crude oil (that is, oil produced or extracted using techniques other than the traditional oil well method) or a Fisher Tropsch oil, and/or any hydrocarbon listed above, and/or a mixture thereof.

[0073] In at least one embodiment, the fluid hydrocarbon co-feed is a fluid hydrocarbon co- feed from a renewable source, such as a vegetable oil.

[0074] Furthermore, the fluid hydrocarbon co-feed may include a fraction of a renewable oil and/or crude oil, such as straight run (atmospheric) gas oils, flashed distillate, vacuum gas oils (VGO), light cycle oil, heavy cycle oil, hydrowax, coker gas oils, diesel, gasoline, kerosene, naphtha, liquefied petroleum gases, atmospheric residue ("long residue") and vacuum residue ("short residue") and/or mixtures thereof. The fluid hydrocarbon co-feed may include paraffins, olefins and aromatics, and/or mixtures thereof.

[0075] In a at least one embodiment, the fluid hydrocarbon co-feed includes at least about 5 wt% elemental hydrogen (i.e., hydrogen atoms) or greater, such as about 10 wt% elemental hydrogen or greater, such as from about 5 wt% to about 20 wt% elemental hydrogen based on the total fluid hydrocarbon co-feed on a wet biomass basis. A high content of elemental hydrogen, such as a content of at least 5 wt%, allows the hydrocarbon feed to act as an inexpensive hydrogen donor in the catalytic cracking process.

[0076] In at least one embodiment, a fluid hydrocarbon co-feed is present at a weight ratio of fluid hydrocarbon co-feed to the HTL oil of 4:6, such as 4.5:5.5, such as 5:5, such as 5.5:4.5, such as 6:4, such as 6.5:3.5:, such as 7:3, such as 7.5:2.5, such as 8:2, such as 8.5: 1.5, such as 9: 1, such as 9.5:0.5, such as 9.8:0.2, such as 9.9:0.1. The fluid hydrocarbon co-feed and the HTL oil can be fed to an FCC reactor in a weight ratio within the above ranges.

[0077] The amount of the HTL oil, based on the total weight of the HTL oil and fluid hydrocarbon co-feed supplied to an FCC reactor, can be from about 65 wt% to about 0.05 wt%, such as from about 60 wt% to about 0.1 wt%, such as from about 55 wt% to about 1 wt%, such as from about 50 wt% to about 2.5 wt%, such as from about 45 wt% to about 5 wt%, such as from about 10 wt% to about 40 wt%.

[0078] The catalytic cracking process can be carried out in an FCC reactor. An FCC reactor is part of an FCC unit. Suitable FCC reactors can be, for example, a fixed bed reactor, a circulating fluidized bed reactor, a fluid bed reactor (such as a fluidized dense bed reactor), a moving bed reactor, an FCC riser reactor, a multiple FCC riser reactor, and/or a hybrid reactor such as one or more of these cited reactors can be coupled together, and the like. In at least one embodiment, the catalytic cracking process is carried out in an FCC riser reactor, such as the FCC reactor is the FCC riser reactor. The fluid hydrocarbon co-feed can be supplied to such FCC riser reactor downstream of the location where one or more liquefied product(s) can be supplied to the FCC riser reactor.

[0079] In at least one embodiment, a mixture of one or more liquefied product(s) with a first hydrocarbon co-feed is supplied to a cracking reactor, such as an FCC riser reactor, at a first location and a second fluid hydrocarbon co-feed is supplied to the cracking reactor, such as the FCC riser reactor, at a second location downstream of the first location. The HTL oil and the hydrocarbon co-feed are injected into the cracking reactor through separate injection nozzles.

[0080] In at least one embodiment, a mixture of one or more HTL oil(s) and a first hydrocarbon co-feed, such as an organic solvent when the organic solvent is chosen from the described fluid hydrocarbon co-feeds, is supplied to an FCC reactor, such as an FCC riser reactor, at a first location and a second fluid hydrocarbon co-feed is supplied to the FCC reactor, such as the FCC riser reactor, at a second location downstream of the first location.

[0081] Suitable conventional reactor types are described in for example U.S. Pat. No. 4,076,796; U.S. Pat. No. 6,287,522 (dual riser); Fluidization Engineering , D. Kunii and O. Levenspiel, Robert E. Krieger Publishing Company, New York, N.Y. 1977; Fluid Catalytic Cracking technology and operations , Joseph W. Wilson, PennWell Publishing Company, 1997, chapter 3, pages 101 to 112; Riser Reactor, Fluidization and Fluid-Particle Systems , pages 48 to 59, F. A. Zenz and D. F. Othmo, Reinhold Publishing Corporation, New York, 1960; U.S. Pat. No. 6,166,282 (fast-fluidized bed reactor); U.S. patent application Ser. No. 09/564,613 filed May 4, 2000 (multiple riser reactor), the disclosures of which are incorporated herein by reference.

[0082] For purposes of the present disclosure, the FCC riser reactor can be an elongated tube- shaped reactor suitable for carrying out any catalytic cracking reactions. The elongated tube-shaped FCC riser reactor can be oriented in a vertical manner.

[0083] The FCC riser reactor may be an“internal” FCC riser reactor or an“external” FCC riser reactor, such as the FCC riser reactor is an internal FCC riser reactor that is a vertical tube-shaped reactor, which may have a vertical upstream end located outside a vessel and a vertical downstream end located inside the vessel. The vessel can be a reaction vessel suitable for catalytic cracking reactions and/or a vessel that may include one or more cyclone separators and/or swirl tubes to separate catalyst from cracked product. Usage of an internal riser reactor may advantageously prevent from any potential clogging and/or fouling that may occur during the FCC process.

[0084] The length of the riser reactor may vary widely. For purposes of the present disclosure, the FCC riser reactor may have a length in the range of from about 1 meter (3.28 feet) to about 100 meters (328 feet), such as from about 5 meters (16.4 feet) to about 75 meters (246 feet), such as from about 10 meters (32.8 feet) to about 60 meters (196.8 feet), such as from about 15 meters (49.2 feet) to about 50 meters (164 feet).

[0085] In at least one embodiment, the HTL oil produced in the HTL process is supplied to an FCC riser reactor, at the bottom of the FCC riser reactor. This may advantageously result in an in- situ water formation at the bottom of the reactor. The in-situ water formation may lower the hydrocarbon partial pressure and reduce second order hydrogen transfer reactions, thereby resulting in higher olefin yields. In at least one embodiment, the hydrocarbon partial pressure is lowered to a pressure in the range of from about 0.01 to 0.50 MPa, such as from 0.05 to 0.45 MPa, such as from 0.1 to 0.40 MPa, such as from 0.15 to 0.35 MPa, such as from 0.10 to 0.30 MPa.

[0086] A number of riser designs use a lift gas as a further means of providing a uniform catalyst flow. Lift gas is used to accelerate the catalyst in a first section of the riser before introduction of the feed and thereby reduces the turbulence which can vary the contact time between the catalyst and hydrocarbons. Hence, there is better catalyst/oil contacting when a lift gas is used, and, without being bond by theory, it is believed that the lift gas can "condition" the FCC catalyst, so that its performance increases in the cracking reactor. Therefore, adding a lift gas at the bottom of the FCC riser reactor could be beneficial for the process.

[0087] Suitable lift gas may include, but are not limited to, steam, vaporized oil and/or oil fractions, and/or mixtures thereof. However, the use of a vaporized oil and/or oil fraction (such as vaporized liquefied petroleum gas, gasoline, diesel, kerosene or naphtha) as a lift gas may have the advantage that the lift gas can simultaneously act as a hydrogen donor and may prevent or reduce coke formation. Further, if a fluid hydrocarbon co-feed is used as an organic solvent in the FCC process, also vaporized organic solvent may be used as a lift gas. Alternatively, a heavy feed such as a gas oil, a VGO, may be added to the FCC riser reactor via feed injection nozzles. The catalyst is pre-accelerated up the FCC riser upstream of the feed by injection of lift gas to the base of the riser.

[0088] One or more HTL oil(s) and/or any fluid hydrocarbon feed may flow co-currently in the same direction. The FCC catalyst can be contacted in a concurrent-flow, countercurrent-flow or cross-flow configuration with such a flow of the HTL oil(s) and optionally the fluid hydrocarbon feed. In at least one embodiment, the FCC is contacted in a concurrent-flow configuration with a concurrent-flow of the HTL oil(s) and optionally the fluid hydrocarbon feed.

[0089] Potential contaminants present in a hydrocarbons feedstock fed to an FCC reactor, can be vanadium, nickel, sodium, and iron. The catalyst used in the FCC unit may favor the absorption of these contaminants which may then have unfavorable effects on the hydrocarbons conversion into a biofuel in the FCC reactor. The main advantage of co-feeding an HTL oil with one or more hydrocarbon(s) to an FCC reactor can be that the renewable oil contains little or none of these contaminants, thus beneficially extending the life of the catalyst, and enabling to maintain greater catalyst activity while improving the magnitude of the conversion into biofuel(s).

[0090] In at least one embodiment, a system (also referred to as an apparatus) used for processing or co-processing a hydrocarbons feedstock, an HTL oil, or combinations thereof, includes a refinery system, such as a conversion unit, such as an FCC unit, a coker, a coking unit, a field upgrader unit, a hydrotreater, a hydrotreatment unit, a hydrocracker, a hydrocracking unit, and/or a desulfurization unit. For instance, the system used for the hydrocarbons conversion into a biofuel may be or include an FCC unit operation; may be or include a coker; may be or include a hydrotreater; may be or include a hydrocracker. A conversion system of hydrocarbons into biofuel used for processing or co-processing a hydrocarbon co-feed, an HTL oil, or combinations thereof, may include a retrofitted refinery system, such as a refinery system including a retrofitted port for the introduction of an HTL oil. For example, the conversion system of hydrocarbons into biofuel used for processing or co-processing a hydrocarbon co-feed, an HTL oil, or combinations thereof, may include a retrofitted FCC refinery system having at least two or more retrofitted port(s) for introducing an HTL oil. For example, a retrofitted port may be a stainless steel port, a titanium or some other alloy or a combination thereof of high durability, high corrosive environment material.

[0091] In at least one embodiment, a refinery system used for processing a hydrocarbon co- feed with an HTL oil includes a retrofitted refinery system, a FCC, a retrofitted FCC, a coker, a retrofitted coker, a field upgrader unit, a hydrotreater, a retrofitted hydrotreater, a hydrocracker, or a retrofitted hydrocracker.

[0092] In at least one embodiment, the process of the present disclosure for converting hydrocarbons into biofuel(s) includes introducing, injecting, feeding, co-feeding, an HTL oil into a refinery system via a mixing zone, at least two or more nozzles, at least two or more retrofitted ports, at least two or more retrofitted nozzles, one or more velocity steam line, or a live-tap. For example, the process of the present disclosure for converting hydrocarbons into biofuel(s) may include processing a hydrocarbon co-feed with an HTL oil. In at least one embodiment, the process may include co-injecting a hydrocarbon co-feed and an HTL oil, such as co-feeding, independently or separately introducing, injecting, feeding, or co-feeding, a hydrocarbon co-feed and an HTL oil into a refinery system. For example, a hydrocarbon co-feed and an HTL oil may be provided, introduced, injected, fed, or co-fed at a close distance from each other into the FCC reactor, the reaction zone, the FCC reaction riser of the refinery system. Furthermore, the HTL oil may be introduced, injected, fed, co-fed into the FCC reactor, the reaction zone, or the FCC reaction riser of the refinery system near, upstream, and/or downstream to the delivery or injection point of the hydrocarbon co-feed. The hydrocarbon co-feed and the HTL oil can be contacted with each other upon introduction, delivery, injection, feeding, co-feeding into the refinery system, into the reactor, into the reaction zone, or into the FCC reaction riser. In at least one embodiment, the hydrocarbon co-feed and the HTL oil are contacted with each other subsequent to entering the refinery system, the reactor, the reaction zone, or the FCC reaction riser. The hydrocarbon co-feed and the HTL oil may be first contacted with each other subsequent to entering into, introduction into, injection into, feeding into, or co-feeding into the refinery system, the reactor, the reaction zone, or the FCC reaction riser. In at least one embodiment, the hydrocarbon co-feed and the HTL oil are co-blended prior to injection into the refinery system.

[0093] The hydrocarbon co-feed and the HTL oil may be introduced, injected, fed, co-fed into the refinery system through different or similar delivery systems. For example, the hydrocarbon co-feed and the HTL oil may be introduced into the refinery system through at least two or more independent or separate injection nozzles. The hydrocarbon co-feed and the HTL oil may be introduced into the refinery system near to each other in a FCC reactor riser in the refinery system. The HTL oil may be introduced, injected, fed, co-fed into the refinery system above, below, near the introduction point of the hydrocarbon fuel feedstock in the refinery system. In at least one embodiment, at least two or more injection nozzles are located in a FCC reactor riser in the refinery system suitable for introducing the hydrocarbon fuel feedstock and/or the HTL oil. The HTL oil may be introduced into the refinery system through a lift steam line located at the bottom of the FCC reactor riser. The hydrocarbon co-feed may be introduced into the refinery system at a first injection point and the renewable fuel oil may be introduced into the refinery system at a second injection point. The first injection point can be, for example, upstream of the second injection point, alternatively, and/or downstream of the second injection point, and/or near to the second injection point, and/or the first injection point and the second injection point may be located in a reactor riser, such as an FCC reactor riser. In at least one embodiment, an HTL oil may be introduced below an FCC reactor riser during the conversion process of the hydrocarbon co-feed. Additionally, an HTL oil may be injected via a quench riser system upstream, downstream, or near, from the introduction point of the hydrocarbon co-feed. In at least one embodiment, an HTL oil is injected via a quench riser system located above, below, or near, a petroleum fraction feedstock injection nozzle.

[0094] In at least one embodiment, the processing of the hydrocarbon co-feed with the HTL oil has a substantially equivalent or greater performance in preparing the biofuel product, relative to processing solely the hydrocarbon co-feed in the absence of the HTL oil. In at least one embodiment, processing an amount of up to 30 wt%, such as up to 20 wt%, of HTL oil with the remainder hydrocarbon co-feed, for instance 0.05:99.95, such as 1 :99, such as 2:98, such as 3 :97, such as 4:96, such as 5:95, such as 10:90, such as 20:80 weight ratio of HTL oil to the hydrocarbon co-feed may have a substantially equivalent or greater performance in the resulting fuel products, relative to processing solely the hydrocarbon co-feed in the absence of the HTL oil. In at least one embodiment, processing in the range of from 20:80 to 0.05:99.95 weight ratio of an HTL oil with a hydrocarbon co-feed results in a weight percent increase in gasoline or diesel of more than 0.05 wt%, such as 0.5 wt% or greater, such as 1 wt% or greater, such as 1.5 wt% or greater, such as 2 wt% or greater, such as 5 wt% or greater, such as 10 wt% or greater, such as 20 wt% or greater, relative to processing solely the hydrocarbon co-feed in the absence of the HTL oil.

[0095] In at least one embodiment, a suitable amount of one or more HTL oil(s) (such as from 2 wt% to 20 wt% relative to the total weight of feedstock fed) of one or more HTL oil(s), is blended with one or more variety of hydrocarbon oils and/or blends of hydrocarbon oils including HGO (Heavy Gas Oil), LGO (Light Gas Oil), VGO (Vacuum Gas Oil), and other petroleum fractions and blends.

[0096] For example, an HGO may be a lighter feedstock that can be combined with one or more hydrocarbon oil(s), as in a mixed feed stream or as a separate feed stream, either before, or after, alternatively before and after, the introduction of one or more hydrocarbon oil(s). In at least one embodiment, an HGO is directed to a refinery FCC unit. In an alternate embodiment, a hydrocarbon oil is introduced jointly with an HTL oil, before, or after, alternatively before and after the introduction of the HTL oil. Either the HTL oil or the hydrocarbon oil, or both, may be alternatively fed in a pulse manner. In at least one embodiment, a hydrocarbon oil is introduced jointly with an HTL oil (e.g., a cellulosic RIN-compliant fuel) in the feed of a refinery FCC unit.

[0097] A suitable amount of an HTL oil, such as a cellulosic RIN-compliant fuel, may be blended with a VGO. VGO can be a feedstock fed to a refinery FCC unit. In at least one embodiment, a blend of HTL oil, such as a cellulosic RIN-compliant fuel, and VGO targets a final measured TAN (also referred to as“Total Acid Number”) of the cracked product(s) of less than 4, such as less than 2, such as less than 1, such as in a range of from 0.05 to 1, such as from 0.05 to 0.5, such as from 0.05 to 0.25.

[0098] In at least one embodiment, a suitable amount of HTL oil is blended (e.g., by co- feeding) with an HGO (e.g., a lighter feedstock) that can be directed to a refinery FCC unit, thus either in combination with a VGO or as a separate feed.

[0099] In at least one embodiment, a suitable amount of HTL oil is blended (e.g., by co- feeding) with lighter hydrocarbon co-feeds such as a light cycle oil (LCO), or gasoline, or diesel, with or without a surfactant, alternatively with or without any additive(s). The content of LCO, and/or gasoline, and/or diesel blended with an HTL oil may be of about 0.005 wt% to about 98 wt%, such as from about 0.005 wt% to about 90 wt%, such as from about 0.005 wt% to about 80 wt%, such as from about 0.005 wt% to about 70 wt%, such as from about 0.005 wt% to about 60 wt%, such as from about 0.005 wt% to about 50 wt%, such as from about 0.005 wt% to about 40 wt%.

[0100] Suitable HTL oil may include all of the whole fuel produced from the thermal or catalytic conversion of biomass, such as a whole fuel produced from the thermal or catalytic conversion of biomass with a low water content (e.g., at least less than 15%).

[0101] In at least one embodiment, the flash point of an HTL oil is increased in order to reduce the volatile content of the liquid and subsequently co-processed in an FCC with a hydrocarbon feedstock. The flash point may be increased, for example, from 50°C to 70°C, or greater and can be measured by the Pensky-Martens closed cup flash point tester (e.g. ASTM D-93). However, various methods and apparatus can be used to effectively reduce the volatile components, such as flash column, falling film evaporator, devolatilization vessel or tank. If present, reduction of some of the volatile components of the HTL oil may improve the reduction of undesirable components such as phenols from passing through the FCC reactor and ending up in the collected water stream.

[0102] Not only do biofuel feedstocks like corn, switchgrass, and agricultural residues need water for growth and conversion to bioethanol, but petroleum feedstocks like crude oil and oil sands also require large volumes of water for drilling, extraction and conversion into petroleum products. Hence, the initial HTL process of the HTL oil before introduction to the FCC unit is advantageous since only less than about 12% of water and less than about 5% of oxygenates are present, preventing undesirable components to interfere with the HTL oil, the hydrocarbon, and the catalyst during the conversion process to biofuel. For example, the water content of an HTL oil feedstock that may be introduced into a refinery FCC unit for co-processing with a hydrocarbon co-feed (e.g., VGO), may be less than about 12%, such as in the range of about 0.01 wt% to about 12 wt%, such as from about 1 wt% to about 10 wt%, such as from about 1.5 wt% to 5 wt%. In at least one embodiment, the water content of the HTL oil feedstock introduced into the refinery FCC unit for co-processing with a hydrocarbon co-feed (e.g., VGO) is less than about 12%, such as in the range of about 0.01 wt% to about 12 wt%, such as from about 1 wt% to about 10 wt%, such as from about 1.5 wt% to 5 wt%.

[0103] For purposes of the present disclosure, a hydrocarbon co-feed can be or include an organic solvent which may include a polar and/or a non-polar hydrocarbon compounds (e.g., LCO). In at least one embodiment, the organic solvent includes at least one or more polar hydrocarbon compounds, such as the organic solvent includes more than one, such as more than two, such as more than three different polar hydrocarbon compounds.

[0104] In at least one embodiment, the organic solvent includes one or more carboxylic acids. A carboxylic acid refers to a hydrocarbon compound including at least one carboxyl (-COOH) group, such as the carboxylic acids can be polar hydrocarbon compounds. The organic solvent includes equal to or more than about 1 wt% carboxylic acids, such as equal to or more than about 3 wt% carboxylic acids, such as equal to or more than about 5 wt% of carboxylic acids, such as equal to or more than about 10 wt% of carboxylic acids, such as equal to or more than about 15 wt% of carboxylic acids, such as equal to or more than about 20 wt% of carboxylic acids, such as equal to or more than about 25 wt% of carboxylic acids, such as equal to or more than about 30 wt% of carboxylic acids, such as equal to or less than about 95 wt% of carboxylic acids, such as equal to or less than about 90 wt% of carboxylic acids, such as equal to or less than about 85 wt% of carboxylic acids, such as equal to or less than about 80 wt% of carboxylic acids, such as equal to or less than about 70 wt% of carboxylic acids, based on the total weight of organic solvent.

[0105] Suitable organic solvents, including one or more carboxylic acids, can be, but are not limited to, formic acid, acetic acid, propionic acid, butyric acid, 4-oxopentanoic acid acid (also called“levulinic acid”), pentanoic acid (also called“valeric acid”), caproic acid, and/or benzoic acid. In at least one embodiment, the carboxylic acid solvent included in the organic solvent is acetic acid. Acetic acid can be simultaneously used as part of the organic solvent and/or used as an acid catalyst.

[0106] In an alternate embodiment, an organic solvent includes paraffinic compounds, naphthenic compounds, olefmic compounds and/or aromatic compounds. Such compounds may be present in refinery streams such as gas oil, fuel oil and/or residue oil. These refinery streams may therefore also be suitable as organic solvent in the cracking process.

[0107] In at least one embodiment, a hydrocarbon co-feed includes at least a portion of cracked product(s), such as a portion of the cracked product(s) may be recycled to the cracking process and further used as organic solvent. In at least one embodiment, equal to or more than about 5 wt%, such as equal to or more than about 10 wt%, such as equal to or more than about 15 wt%, such as equal to or more than about 20 wt%, such as equal to or more than about 25 wt%, such as equal to or more than about 30 wt% of the organic solvent is obtained from an intermediate and/or a final cracked product.

[0108] In at least one embodiment, any recycle of cracked product(s) includes a weight amount of cracked product(s) of 1 to 150 times the weight of the HTL oil, such as 2 to 100 times the weight of the HTL oil, such as 5 to 50 times the weight of the HTL oil, such as 10 to 20 times the weight of the HTL oil.

[0109] In at least one embodiment, at least part of the hydrocarbon co-feed is derived from a cellulosic material, such as a lignocellulosic material and/or a hemicellulosic material, such as a lignocellulosic material. For example, at least part of the hydrocarbon co-feed may be generated in-situ during liquefaction of the cellulosic material, such as a lignocellulosic material and/or a hemicellulosic material, such as a lignocellulosic material. In another example, at least part of the hydrocarbon co-feed may be obtained by acid hydrolysis of a cellulosic material, such as a lignocellulosic material and/or a hemicellulosic material, such as a lignocellulosic material, such as a lignocellulosic material. Examples of possible hydrocarbon compounds in the hydrocarbon co-feed that may be obtained by acid hydrolysis of a cellulosic material, such as a lignocellulosic material and/or a hemicellulosic material, such as a lignocellulosic material, may include formic acid, acetic acid, and levulinic acid.

[0110] Further, suitable hydrocarbon compounds attainable from such acid hydrolysis products by hydrogenation may also be used. Examples of such hydrogenated hydrocarbon compounds may include, but are not limited to, tetrahydrofufuryl compounds (derived from furfural via hydrogenation), tetrahydropyranyl compounds (derived from hydroxymethylfurfural), gamma- valerolactone (derived from levulinic acid via hydrogenation), ketones, mono- and di-alcohols (derived from sugars) and guaiacol and syringol compounds (derived from lignin). In at least one embodiment, the hydrocarbon co-feed includes one or more of such hydrocarbon compounds. Such hydrocarbon compounds may also be included in the final cracked product. Accordingly, in at least one embodiment, the final cracked product or part thereof includes one or more of the hydrocarbon compounds listed, optionally hydrogenated, compounds such as guaiacol and/or syringol compounds, which can be derived from lignin.

[0111] One or more hydrocarbon compounds in the hydrocarbon co-feed may advantageously be obtainable from the HTL oil cracked in the cracking process. The hydrocarbon compound(s) may for example be generated in-situ and/or recycled and/or used as a make-up hydrocarbon co- feed, affording significant economic and processing advantages.

[0112] During FCC, in at least one embodiment, the hydrocarbon co-feed includes one or more hydrocarbon compounds that may be suitable to act as a fluid hydrocarbon co-feed in the catalytic cracking phase. The hydrocarbon co-feed used during cracking may include, one or more hydrocarbon compounds obtained from, for example, a crude oil (e.g., a petroleum oil or mineral oil), a renewable source (e.g., HTL oil), and/or a mixture thereof, such as the hydrocarbon co-feed used during cracking may include a fraction of a petroleum oil or renewable oil. Suitable hydrocarbon co-feed may include, but are not limited to, diesel, gasoline, kerosene, naphtha, liquefied petroleum gases, VGO, a straight run (atmospheric) gas oils, atmospheric residue ("long residue") and vacuum residue ("short residue"), flashed distillate, light cycle oil, heavy cycle oil, hydrowax, coker gas oils, and/or mixtures thereof. In at least one embodiment, hydrocarbon co- feed include(s) diesel, gasoline, VGO and/or mixtures thereof.

[0113] A co-solvent may be used in addition to the hydrocarbon co-feed already available in the FCC in order 1) to enhance the solvent power; and 2) to increase the solubility of poorly-soluble components present during the cracking process. Suitable co-solvent can be an organic solvent that includes hydrocarbons, such as a petroleum oil or a fraction thereof. Such hydrocarbon co-feed or organic co-solvent may be a suitable feed to the catalytic cracking phase. Furthermore, no separation of the hydrocarbon co-feed or organic co-solvent may be required.

[0114] Optionally, one or more cracked product(s) can be subsequently hydrotreated with a source of hydrogen, such as in the presence of a hydrotreatment catalyst to produce a hydrotreated cracked product. For instance, a hydrotreatment process may include hydrodeoxygenation, hydrodenitrogenation and/or hydrodesulphurization. One or more hydrotreated product(s) derived therefrom can conveniently be used as a biofuel composition. Such biofuel composition may conveniently be blended with one or more other components (e.g., additives) to produce a biofuel composition. Examples of such components may include, but are not limited to, anti-oxidants, corrosion inhibitors, ashless detergents, dehazers, dyes, lubricity improvers and/or mineral fuel components, conventional petroleum derived gasoline, diesel and/or kerosene fractions.

[0115] In at least one embodiment, the FCC process includes contacting an HTL oil (e.g., a cellulosic material) concurrently with the fraction of a hydrocarbon (e.g., petroleum oil), with a source of hydrogen, with a hydrogenation catalyst, and optionally with an acid catalyst, at a temperature of equal to or more than about l00°C to produce a cracked product (e.g., final (RINs)biofuel product(s)). In the FCC unit, cracking and hydrogenation of the HTL oil and hydrocarbons may be carried out simultaneously or hydrogenation may be carried out subsequent to the cracking.

[0116] In at least one embodiment, a mixture of one or more liquefied product(s) with a first hydrocarbon co-feed is supplied to an FCC reactor, such as an FCC riser reactor, at a first location and a second fluid hydrocarbon co-feed is supplied to the FCC reactor, such as the FCC riser reactor, at a second location downstream of the first location. In at least one embodiment, a mixture of one or more HTL oil(s) and a first hydrocarbon co-feed, such as an organic solvent when the organic solvent is chosen from the described fluid hydrocarbon co-feeds, is supplied to an FCC reactor, such as an FCC riser reactor, at a first location and a second fluid hydrocarbon co-feed is supplied to the FCC reactor, such as the FCC riser reactor, at a second location downstream of the first location.

[0117] In at least one embodiment, the FCC unit is designed to have at least two feedstock injection points, such as two or more feedstock injection points, such as at least one injection point for a petroleum oil co-feed and at least one injection point for an HTL oil feedstock. For example, an FCC unit has at least two injection points for co-injection of a mixture of a petroleum fraction feedstock and an HTL oil feedstock (both petroleum fraction feedstock and HTL oil feedstock can be mixed upstream of the injection point) or the system could be fitted with multiple points of injection for either, both or mixtures of the feedstock. In an alternate embodiment, the FCC unit is retrofitted to include a way of introducing the HTL oil, for example, by adding an injection point close to the FCC riser or at some point in the process where the catalyst may be upflowing. A suitable FCC unit fitted with at least two feedstock injection points is described in U.S. Patent No. 9, 129,989 which is incorporated herein by reference.

[0118] Processes of the present disclosure can provide biofuel compositions (e.g., biolfuel compositions having RIN credits) without any separation process of the cracked product(s) after FCC providing additional time-, energy- and cost-efficiency. Furthermore, an FCC unit fitted with two or more feedstock injection points where the FCC unit is located downstream from a hydrothermal liquefaction unit provides biofuel compositions with a total acid number (TAN) of about 3 mg or greater KOH/g, such as about 6 mg or greater KOH/g, The FCC process can be performed using a system of at least two or more inj ection nozzles on the FCC unit, which promotes better blending of the HTL and hydrocarbon oils (and ultimately cracked product(s)) by increasing the gas/oil dispersion, providing additional time-, energy- and cost-efficiency.

[0119] In at least one embodiment, processed and/or unprocessed HTL oil is fed upstream and/or downstream of a hydrocarbon (e.g., gas oil (GO); VGO) feed inlet. The HTL oil can be introduced in an upstream and/or a downstream section of the FCC riser onto the FCC catalyst, thus enabling the hydrocarbons conversion into a biofuel, such as the HTL oil can be introduced downstream of the FCC riser. Introduction of the HTL oil in upstream and/or downstream section of the FCC riser may thereby imparting properties of the renewable oil (e.g., viscosity of the oil; acid nature; oxidation stability; etc.) In an alternate embodiment, an HTL oil is introduced downstream of the hydrocarbons fresh feed injection nozzles. Optionally, a retrofitted riser with a retrofitted renewable oil feedstock injection port(s) can be added to the present system. The term “retrofitting” refers to the addition of new technology or features to older systems, such as to install new or modified parts or equipment in something previously manufactured or constructed. The FCC riser may be adapted to include multiple renewable oil feedstock injection port(s) both before and after the introduction of the hydrocarbons. Furthermore, The FCC riser may be retrofitted to have only one additional renewable oil feedstock injection port positioned either before or after the hydrocarbons injection point, alternatively retrofitted to have one or more renewable oil feedstock injection(s) port along the hydrocarbons feedstock feed line.

[0120] The FCC unit may include a riser quench system which may inject vaporizable quench oil into the FCC riser above the hydrocarbons feed injection nozzles. Introduction of a quench oil, such as vegetable oil, may increase the temperature in the mix zone and lower section of the FCC riser. In at least one embodiment, the HTL oil feedstock may be injected into the quench line of the FCC riser.

[0121] In at least one embodiment, the FCC process includes contacting an HTL oil with an organic solvent, optionally in the presence of an acid catalyst, at a temperature of at least about 90°C, such as from about 90 °C to about 700 °C, such as from about 400°C to about 700 °C, such as from about 545°C to about 585°C.

[0122] In at least one embodiment, the catalyst is an acid catalyst suitable for cracking of the HTL oil and/or hydrocarbon co-feed, sufficiently strong to enable cleavage of the covalent linkages and dehydration of the HTL oil and hydrocarbons. Suitable acid catalysts can be, but are not limited to, a Bronsted acid or a Lewis acid. The acid catalyst of the process of the present disclosure may be a homogeneous catalyst or a heterogeneous catalyst, such as the acid catalyst can be a homogeneous or a finely dispersed heterogeneous catalyst, such as the acid catalyst is a homogeneous catalyst. Furthermore, the acid catalyst can be maintained as a stable liquid under the cracking conditions used during the process.

[0123] The acid catalyst can be a Bruns ted acid, such as a mineral or an organic acid, such as a mineral or an organic acid having a pKa value of from about 2 to 6, such as from about 2.2 and 4, such as from 2.5 and 3. Suitable mineral acids may include, but are not limited to, hydrochloric acid (HC1), nitric acid (HNCh), sulphuric acid (H2SO4), Boric acid (H3BO3), para-toluene sulphonic acid, phosphoric acid (H3PO4), Hydrobromic acid (HBr), and mixtures thereof. In at least one embodiment, the acid catalyst used in the cracking process is sulphuric acid or phosphoric acid. Suitable organic acids for the FCC process may include, but are not limited to, formic acid, acetic acid, oxalic acid, lactic acid, levulinic acid, citric acid, trichloracetic acid and mixtures thereof.

[0124] The acid catalyst can be present in an amount of from about 0.005 wt% to about 50 wt%, such as from about 0.01 wt% to about 45 wt%, such as from about 0.05 wt% to about 40 wt%, such as from about 0.1 wt% to about 35 wt%, such as from about 0.5 wt% to about 30 wt%, such as from about 0.75 wt% to about 25 wt%, such as from about 1 wt% to about 20 wt%, such as from about 2 wt% to about 15 wt%, such as from about 5 wt% to about 15 wt%, based on the total weight of the organic solvent and/or solvent mixture, and the acid catalyst.

[0125] Strongly acidic catalyst sites on the catalyst promote cracking. Hence, the hydrogen forms of zeolites used in FCC unit systems are powerful solid-based acids, promoting various acid- catalyzed based reactions (e.g., cracking, isomerisation, alkylation, dehydration of alcohols, hydrogenation of the polyaromatics ). The hydrogen forms of zeolites can effectively promote hydrogen transfer, thus with longer reactor residence times. The present FCC unit system benefits from the characteristics of renewable oil, namely its TAN or acidic nature, that can lead to an improvement in cracking or the conversion of, for example, VGO (i.e., a synergistic effect) in FCC operations. Consequently, such procedure advantageously promotes the production of desirable products by reducing unwanted products by way of heavy cycle oil and clarified slurry oil. Further, additives, such as sulfur-reducing additives, may be added to the catalyst. It is anticipated that such additives may experience enhanced effectiveness.

[0126] The FCC catalyst can be any suitable catalyst for use in a cracking process. In at least on embodiment, the FCC catalyst includes any suitable zeolitic component for the FCC. Also, the FCC catalyst may contain an amorphous binder compound and/or a filler. Examples of the amorphous binder component may include quartz, zirconia, silica, alumina, magnesium oxide, calcium carbonate, and/or titania, and/or a mixture thereof of at least two or more of these components. Suitable fillers may include clays (such as hydrated aluminum silicate, also called “kaolin”) and/or silica. For purpose of the present disclosure, the zeolitic component can be a large, a medium, and/or a mixture thereof of large and medium pore zeolite which may include a porous, crystalline aluminosilicate structure.

[0127] In at least one embodiment, a porous, crystalline aluminosilicate structure has a porous internal cell structure on which the major axis of the pores can be from about 0.4 nanometer to about 0.65 nanometer, alternatively in the range of from about 0.65 nanometer to about 0.9 nanometer. Examples of large pore zeolites may include, but are not limited to, faujasite, zeolite Y or X, ultra-stable zeolite Y, Rare Earth zeolite Y and Rare Earth ultra-stable zeolite Y. Examples of medium pore zeolites may include, but are not limited to, the Modernite Framework Inverted (MFI) structural type (e.g., ZSM-5), the MTW type (e.g., ZSM-12), the TON structural type (e.g., theta) and the FER structural type (e.g., ferrierite).

[0128] In at least one embodiment, a hydrogenation catalyst for the FCC process is a hydrogenation catalyst that is resistant to the combination of the organic solvent and/or the solvent mixture and, if present, the acid catalyst. For example, a hydrogenation catalyst may include a heterogeneous and/or homogeneous catalyst, such as the hydrogenation catalyst is a homogeneous catalyst, alternatively a heterogeneous catalyst. The hydrogenation catalyst may include a hydrogenation metal known to be suitable for hydrogenation reactions, such as for example nickel, iron, palladium, ruthenium, rhodium, molybdenum, cobalt, copper, iridium, platinum and gold, or mixtures thereof.

[0129] The hydrogenation catalyst including such a hydrogenation metal may be sulfided. Further, sulfided hydrogenation catalysts may be used such as, for example, a catalyst based on Molybdenum sulfide, potentially including Cobalt and/or Nickel as a promotor, such as sulfided MM0/AI2O3 catalyst.

[0130] With respect to the hydrogenation catalyst being a heterogeneous catalyst, the catalyst may include a hydrogenation metal supported on a carrier. Suitable carriers include for example carbon, alumina, titanium dioxide, zirconium dioxide, silicon dioxide and mixtures thereof. Examples of suitable heterogeneous hydrogenation catalysts may include, but are not limited to, ruthenium, platinum or palladium supported on a carbon carrier, such as ruthenium supported on zirconium dioxide or titanium dioxide. Any suitable form of the heterogeneous catalyst and/or carrier used for the present process may be a mesoporous powder, granules, pellets, tablets or any extrudates, megaporous structure (e.g., honeycomb, cloth, foam, and/or mesh). The heterogeneous catalyst may be present in a FCC reactor included in a fixed bed reactor or ebullated slurry bed reactor, such as in a fixed bed reactor.

[0131] With respect to the hydrogenation catalyst being a homogeneous hydrogenation catalyst, the catalyst may include an organic or inorganic salt of a hydrogenation metal. Suitable examples of organic or inorganic salt of a hydrogenation metal can be, but are not limited to, acetate-, acetyl acetonate-, nitrate-, sulphate- or chloride-salt of palladium, platinum, nickel, cobalt, rhodium or ruthenium, such as, in at least one embodiment, the homogeneous catalyst is an organic or inorganic acid salt of a hydrogenation metal, where the acid is an acid already present in the process as the acid catalyst (described above).

[0132] In at least one embodiment, a source of hydrogen may be any source of hydrogen known to be suitable for hydrogenation purposes, which may include hydrogen gas and/or hydrogen-donor (e.g., formic acid), such as the source of hydrogen is a hydrogen gas. Hence, such hydrogen gas introduced to the FCC reactor at a partial hydrogen pressure that can be in the range of from about 0.01 MPa to 30 MPa, such as from about 0.05 MPa to about 28 MPa, such as from about 0.1 MPa to about 26 MPa, such as from about 0.5 MPa to about 24 MPa, such as from about 1 MPa to about 22 MPa, such as from about 2 MPa to about 20 MPa, such as from about 3 MPa to about 18 MPa, such as from about 4 MPa to about 16 MPa. A hydrogen gas can be supplied to an FCC reactor co-currently, cross-currently or counter-currently to the HTL oil, such as the hydrogen gas is supplied counter-currently to the HTL oil.

[0133] In the FCC unit, the cracking process can be carried out at any total pressure known to be suitable for cracking processes, such as the cracking process can be carried out under a total pressure value of from about 10 psig to about 50 psig, such as about 15 psig (1 bar) to about 30 psig (2 bar).

[0134] Additionally, during the cracking process in the FCC unit, the HTL oil and one or more hydrocarbon(s) are cracked, namely the HTL oil and one or more hydrocarbon(s) may be converted into one or more cracked product(s), to produce cracked product(s), such as a biofuel product. In at least one embodiment, the final biofuel product is either hydrogenated or not. Furthermore, the final cracked product can be contacted/blended with one or more component(s), such as any fuel additives (e.g., metal deactivators, corrosion inhibitors, lead scavengers, fuel dyes, and antioxidant stabilizers), to form a biofuel composition. Methods of the present disclosure (e.g., HTL oil + dual nozzle system) can provide improved final cracked products that do not need to be fractionated before blending with one or more components, saving energy, time, and cost in product of biofuels. The one or more components can be selected from an anti-oxidant, a corrosion inhibitor, an ashless detergent, a dehazer, a dye, a lubricity improver, a mineral fuel component, a petroleum derived gasoline, a diesel, and a kerosene.

[0135] The reaction effluent produced in the cracking process in the FCC unit may include insoluble solid materials such as humins (also referred to as“char”) and the cracked product(s), including the processed-HTL oil and hydrocarbon(s). Moreover, the reaction effluent may include, for example, water (expected to be in much lower amount when compare to the water formed during fast pyrolysis), co-solvent, acid catalyst and/or hydrogenation catalyst, and/or gaseous products (e.g., hydrogen, nitrogen). In at least one embodiment, the cracking process of the present disclosure does not include any separation of the final cracked product from a reaction effluent produced in the cracking process. Hence, the reaction effluent is not forwarded to a separation section. In at least one embodiment, the final cracked product is the RIN-biofuel product(s).

[0136] The water produced during the cracking process may be removed by distillation, pervaporation and/or reversed osmosis. The final cracked product may include hydrocarbon compounds and/or a small amount of oxygenates, such as for example alcohols (e.g., mono- and/or di-alcohols) and/or ketones (mono- and/or di-ketones).

[0137] In at least one embodiment, the present disclosure provides a method of processing a hydrocarbons fraction (e.g., VGO) with a substituted amount of a processed-HTL oil in the presence of a catalyst resulting in a sustaining and/or increasing or improving the yield of a transportation fuel, such as an increase of at least 0.2 wt% or at least 0.5 wt%, relative to the identical process on an equivalent energy or carbon content basis of the feedstream where the petroleum fraction is not substituted to any other fuel feedstock. Examples of transportation fuel yield may be, but are not limited to, a LPG, a gasoline, a diesel fuel, a jet fuel, an LCO, a heating oil, a transportation fuel, and/or a power fuel.

[0138] In at least one embodiment, the present disclosure provides a method of processing a hydrocarbon fraction (e.g., VGO) with a substituted amount of a processed-HTL oil in the presence of a catalyst resulting in an increased or improved yield of the biogenic carbon, such as an increase of at least 0.5 wt%, such as an increased or improved yield of the biogenic carbon of from about 0.5 wt% to 3 wt%, thus relative to the identical process on an equivalent energy or carbon content basis of the feedstream where the petroleum fraction is not substituted to any other fuel feedstock. Examples of transportation fuel yield may be, but are not limited to, an LPG, a gasoline, a diesel fuel, a jet fuel, an LCO, a heating oil, a transportation fuel, and/or a power fuel. [0139] In at least one embodiment, a method of preparing a biofuel includes processing a hydrocarbon co-feed with a processed-HTL oil feedstock in the presence of a catalyst. For example, a method of preparing a biofuel may include providing a processed-HTL oil feedstock for processing with a hydrocarbon co-feed in the presence of a catalyst. In at least one embodiment, a method of preparing a biofuel includes: i) processing a hydrocarbon co-feed with a processed-HTL oil feedstock in the presence of a catalyst; and ii) optionally, adjusting/catering feed addition rates of a hydrocarbon co-feed, a processed-HTL oil feedstock, or both, to target a desirable biofuel product profile, a riser temperature, or a reaction zone temperature; or iii) optionally, adjusting the FCC catalyst to combined hydrocarbon co-feed and processed-HTL oil feedstock ratio (catalyst : oil(s) ratio) to target a particular biofuel product profile, a riser temperature, or a reaction zone temperature; where the catalyst : oil(s) ratio can be a weight ratio or a volume ratio.

[0140] In at least one embodiment, feed nozzles that are modified for the properties of conditioned renewable fuel feedstock and any suitable nozzles of the FCC are converted into stainless steel, or other suitable metallurgy, and adjusted to inject HTL oil to provide an upgrade to the traditional systems.

[0141] In at least one embodiment, the addition rate value of the HTL oil in a refinery FCC unit that may be processing a hydrocarbon fraction is sufficient to provide mixing of the HTL oil with co-feed. Additionally or alternatively, the contact time of the FCC catalyst and the HTL oil is about 1 second to about 30 seconds, such as about 2 seconds to about 10 seconds.

[0142] FCC units may use steam to lift the catalyst. The steam can be used for dilution of the reaction media at a residence time control. The lift steam can enter the FCC reactor riser from the bottom of the unit and/or through at least one or more nozzles on the side of the reactor. These nozzles may be located below, above or co-located with the feedstock (either the HTL oil feed, hydrocarbon feed or both HTL oil and hydrocarbon feed) injection point.

[0143] In at least one embodiment, a delivery system of the processed-HTL oil separated from the hydrocarbon feedstock feed port (or assembly) for introducing the processed-HTL oil material into an FCC unit is used. The separate delivery system may include transfer from storage, preheat and deliver the processed-HTL oil to an appropriate injection point on the FCC. To ensure contact between the processed-HTL oil and the hydrocarbon feedstock the point of introduction may be near to the hydrocarbon feedstock injection nozzles which may be located in the downward section of the FCC reactor riser.

[0144] In at least one embodiment, the processed-HTL oil is introduced through one or more atomizing nozzle(s) that may be inserted into one or multiple steam lines and/or may be introduced into one or more recycle lift vapor line(s). [0145] The addition rate of the processed-HTL oil may be controlled by a separate delivery system (i.e., separate from the hydrocarbon delivery system) into the downward section of the FCC reactor riser. In an alternate embodiment, the addition rate of the processed-HTL oil is controlled by a separate delivery system into one or multiple lift steam line(s). The addition rate of the processed-HTL oil may be controlled by a separate delivery system into an available port in the downward section of the FCC reactor riser. In a further alternate embodiment, the addition rate of the processed-HTL oil is controlled by a separate delivery system and introduced into one of the hydrocarbon nozzles or injectors either separately or with the hydrocarbon feedstock, such as separately of the hydrocarbon feedstock.

[0146] In at least one embodiment, a method of the present disclosure includes: i) producing a processed-HTL oil based feedstock; ii) introducing the processed-HTL oil based feedstock into a refinery system, where the refinery system conversion unit may be selected from a group including an FCC, a coker, a field upgrader system, a lube oil refinery facility, a hydrocracker, and a hydrotreating unit; iii) and co-processing the processed-HTL oil based feedstock with a hydrocarbon feedstock (e.g., VGO). For example, the method may include (i) producing the processed-HTL oil based feedstock, which includes a hydrothermal liquefaction conversion of biomass, and (ii) conditioning the processed-HTL oil based feedstock to provide introduction into the FCC refinery system. Hence, the conditioning of the processed-HTL oil based feedstock may include controlling an ash content to be in a range of between 0.001 wt% and 1 wt%; controlling a pH to be in a range of from about 5 to about 7, such as from about 5 to 6; and controlling a water content to be in a range between 0.05 wt% and 0.2 wt%. In at least one embodiment, the hydrocarbon feedstock used is a VGO.

[0147] The conversion method of the present disclosure may include injecting the processed- HTL oil feedstock into a catalytic riser of a FCC unit. For example, the processed-HTL oil feedstock may be injected upstream of a VGO inlet port of a FCC unit, such as the processed-HTL oil feedstock may be injected downstream of a VGO inlet port of a FCC unit, such as the processed- HTL oil feedstock may be injected into a riser quench line of a FCC unit, such as the processed- HTL oil feedstock may be injected into a second riser of a two riser FCC unit, such as the processed-HTL oil feedstock may be injected into a third riser of a three riser FCC unit.

[0148] In at least one embodiment, the system used for the conversion process includes a production facility for producing a processed-HTL oil based feedstock and a refinery system, where the refinery system may be selected from a conversion unit including a FCC, a coker, a field upgrader system, a lube oil refinery facility, a hydrocracker, and a hydrotreating unit, where the processed-HTL oil based feedstock may be introduced into the refinery system, and theHTL oil based feedstock may be co-processed with a hydrocarbon feedstock in the refinery system.

Regenerating Catalyst

[0149] In at least one embodiment, the catalytic cracking process includes: i) an FCC process including contacting the HTL oil, the hydrocarbons, and an FCC catalyst at a temperature of from about 400°C to about 700°C, to produce one or more cracked products and a spent (“deactivated”) FCC catalyst; ii) a separation process including separating one or more of the cracked products from the spent FCC catalyst; iii) a regeneration process including regenerating spent FCC catalyst to produce a regenerated FCC catalyst, heat and carbon dioxide; and a recycling process including recycling the regenerated FCC catalyst to the FCC process.

[0150] The separation process including separating one or more of the cracked products from the spent FCC catalyst can be carried out using one or more cyclone separators and/or one or more swirl tubes. Suitable methods of carrying out the separation process are described in Fluid Catalytic Cracking; Design, Operation, and Troubleshooting of FCC Facilities by Reza Sadeghbeigi, published by Gulf Publishing Company, Houston Texas, 1995, pages 219 to 223, and Fluid Catalytic Cracking technology and operations , by Joseph W. Wilson, published by PennWell Publishing Company, 1997, chapter 3, pages 104 to 120, and chapter 6, pages 186 to 194, incorporated herein by reference.

[0151] Furthermore, the separation process may include a stripping process such as the spent FCC catalyst may be stripped to recover the products absorbed on the spent FCC catalyst before the regeneration process. The recovered products may be recycled and added to a stream including one or more cracked products obtained from the catalytic cracking process.

[0152] In at least one embodiment, the regeneration process includes contacting the spent FCC catalyst with an oxygen containing gas in a regenerator, in order to produce a regenerated FCC catalyst, heat and carbon dioxide. The catalyst activity can be restored during the regeneration coke process where the coke that can be deposited on the catalyst, as a result of the FCC reaction, is burned off.

[0153] Additionally, the oxygen containing gas may be any suitable oxygen containing gas for use in a regenerator, such as air or oxygen-enriched air (OEA). The term“oxygen enriched air” refers to air including about 20 vol% oxygen or greater, such as air including about 25 vol% oxygen or greater, such as air including about 30 vol% oxygen or greater, based on the total volume of air.

[0154] The heat produced in the exothermic regeneration process can be used to supply energy for the endothermic catalytic cracking process. Moreover, the heat produced in the exothermic regeneration process can be used to heat water and/or generate steam. The steam can be used elsewhere in the FCC refinery, such as a lift gas in a riser reactor. [0155] The regenerated FCC catalyst can be recycled back to the FCC process. In at least one embodiment, a side stream of make-up FCC catalyst is added to the recycle stream to make-up for loss of FCC catalyst in the reaction zone and regenerator.

Cracked Products and Compositions

[0156] The process of the present disclosure provides one or more cracked product(s). At this point of the process, there is no fractionation of any of the cracked product(s) produced. Hence, there is no separation process of the cracked product(s) with the blend components (RFOs and hydrocarbons) if present. Such simplified, environmentally-friendly, time- and cost-efficient FCC process enables access to the desirable biofuel with RIN credits, yet with grade quality (e.g., low concentration of sulfur content of from about 0.1 wt% to 2.5 wt% and heavy metals) . Hence, the one or more cracked product(s) derived therefrom can conveniently be used directly as a biofuel component. As used herein“grade quality” refers to a low to moderate level of sulfur (e.g., from 0.5 wt% to 2.5 wt%) and low to moderate level of heavy metals (e.g., vanadium and nickel).

[0157] In at least one embodiment, a cracked product may conveniently be blended with one or more other components to produce a biofuel composition. Examples of such one or more other components may include any additives such as anti-oxidants, corrosion inhibitors, ashless detergents, dehazers, dyes, lubricity improvers and/or mineral fuel components, but also conventional petroleum derived gasoline, diesel and/or kerosene. A biofuel composition can include one or more other components at an additive content of from about 0.001 wt% to about 30 wt% of any additives, such as from about 0.01 wt% to about 10 wt%, such as from about 0.1 wt% to about 3wt%, based on the weight of the biofuel composition.

[0158] In at least one embodiment, a biofuel formed after an FCC process includes an FCC product composition derived from catalytic contact of a feedstock including an HTL oil, such as a biofuel derived from a hydrocarbon co-feed and an HTL oil feedstock, such as a biofuel derived from about 50 wt% to about 99.99 wt%, such as from about 55 wt% to about 99.5 wt%, such as from about 60 wt% to about 99 wt%, such as from about 65 wt% to about 90 wt%, such as from about 70 wt% to about 90 wt% of a hydrocarbon co-feed, and from about 0.01 wt% to about 50 wt%, such as from about 0.5 wt% to about 45 wt%, such as from about 1 wt% to about 40 wt%, such as from about 10 wt% to about 35 wt%, such as such as from about 10 wt% to about 30 wt% of an HTL oil feedstock, or a biofuel derived from 50 vol% to about 99.99 vol%, such as from about 55 vol% to about 99.5 vol%, such as from about 60 vol% to about 99 vol%, such as from about 65 vol% to about 90 vol%, such as from about 70 vol% to about 90 vol% of a hydrocarbon co-feed, and from about 0.01 vol% to about 50 vol%, such as from about 0.5 vol% to about 45 vol%, such as from about 1 vol% to about 40 vol%, such as from about 10 vol% to about 35 vol%, such as from about 10 vol% to about 30 vol% of an HTL oil feedstock.

EXAMPLES

[0159] Table 1 illustrates comparative results obtained from conventional data for fast pyrolysis versus HTL of cellulosic material. When pyrolysis of biomass was performed by fast pyrolysis at an operating temperature of from 450°C to 500°C, an operating pressure of 1 atm, and at a very short residence time (of less than a second), without the presence of catalyst, a thermally unstable oil was produced with high contents of water (25%) and oxygenates (38%). Fast pyrolysis produced an oil containing very reactive species (e.g., oxygenates), which is an issue for fuel storage and transportation. However, with HTL that required lower operating temperature (350 °C), longer residence time (5 minutes to 30 minutes), and higher pressure (150 atm to 250 atm, such as 200 atm), produced an oil that was more thermally stable, with less water and oxygenates contents (5% and 12%, respectively). This comparative experiment and the associated comparative data in Table 1 were provided in Elliott, D.C., et al. (September 2, 2014), Comparative Analysis of Fast Pyrolysis and Hydrothermal Liquefaction as Routes for Biomass Conversion to Liquid Hydrocarbon Fuels , PowerPoint slides presented at the Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products, TCS 2014 (Denver, Colorado).

Table 1.

[0160] Table 2 illustrates prophetic yields developed for the use of HTL oil blended with hydrocarbon feedstock (e.g., gasoline, diesel) in the FCC unit. When a petroleum fraction of VGO is mixed with a substituted amount of an HTL oil (5%) in the presence of a catalyst, the quality of the gasoline or the diesel fuel is not negatively affected. The yield of gasoline (and diesel) remains overall the same. The gasoline (or diesel) yield can also be represented in terms of the amount of carbon in the feedstock that may be converted to gasoline (or diesel). Surprisingly, the yields of biogenic carbon of gasoline and diesel increase (2% and 1%, respectively). These yields suggest that more carbon in the VGO may be going to gasoline (and diesel) production than would otherwise be the case without the addition of the HTL oil in the blend. HTL oil may be synergistically affecting either the cracking chemistry or catalyst activity in favor of the gasoline (or diesel) product. These prophetic results demonstrate that combining a hydrocarbon fuel with an HTL oil via a simple process for the production of cost- and time-efficient generation of biofuels having RIN credits, i.e., the cellulosic RIN credits.

Table 2

[0161] Subsequent to the above prophetic example, actual experiments were run on an HTL sample. Table 3 below summarizes two data sets comparing VGO only and VGO + 5% HTL. The two data sets have different operating conditions. Results are similar to those predicted in the prophetic example. Note that biogenic carbon was not measured, but the assumptions of the biogenic carbon shown in Table 2 would be expected to apply to the experimental data. Also, water and CO/CO2 results in the actual experiments were unavailable.

Table 3

[0162] Overall, processes of the present disclosure can provide thermally stable biofuel compositions providing conversion of a hydrocarbon feedstock using an HTL oil, thus with less water and oxygenates content. Processes of the present disclosure can provide biofuel compositions without any separation (e.g., fractionation) of the cracked product(s) after FCC providing additional time-, energy- and cost-efficiency. The FCC process can be performed using a system of at least two or more injection nozzles coupled with the FCC unit, which promotes better blending of the HTL and hydrocarbon oils (and ultimately cracked product(s)) by increasing the gas/oil dispersion, providing additional time-, energy- and cost-efficiency.

[0163] The phrases, unless otherwise specified, "consists essentially of and "consisting essentially of do not exclude the presence of other processes, elements, or materials, whether or not, specifically mentioned in this specification, so long as such processes, elements, or materials, do not affect the basic and novel characteristics of the present disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.

[0164] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

[0165] All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term“comprising” is considered synonymous with the term“including”. Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase“comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases“consisting essentially of,”“consisting of,”“selected from the group of consisting of,” or“is” preceding the recitation of the composition, element, or elements and vice versa.

[0166] While the present disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the present disclosure.