Processing solid biomass feedstock to produce renewable fuels

Abstract

A process includes processing a slurry feed comprising a solid biomass feedstock containing a lignocellulosic material and a liquid carrier under solvent liquefaction conditions to produce a solvent liquefaction effluent including a liquefied biomass and unconverted solid biomass feedstock, processing, in a slurry hydroconversion reactor, the solvent liquefaction effluent comprising the liquefied biomass including the lignocellulosic material and unconverted solid biomass feedstock in the presence of a slurry hydroconversion catalyst and hydrogen in a slurry hydroconversion zone and under slurry hydroconversion conditions to produce a slurry hydroconversion effluent, and processing the slurry hydroconversion effluent by subjecting the slurry hydroconversion effluent to a hydrodeoxygenation catalyst and under hydrodeoxygenation reaction conditions to produce a hydrodeoxygenated liquid effluent, and subjecting the hydrodeoxygenated liquid effluent to a hydrogenation catalyst and under hydrogenation reaction conditions to produce a liquid hydrocarbon product.

Description

T-12604-W001 (538-356 PCT)PROCESSING SOLID BIOMASS FEEDSTOCK TO PRODUCE RENEWABLE FUELSPRIORITY CLAIM

[0001] The present application claims priority to U.S. Patent Application No. 63 / 721,695, entitled “Processing Solid Biomass Feedstock to Produce Renewable Fuels,” fded November 18, 2024, the content of which is incorporated by reference herein in its entirety.BACKGROUND

[0002] With increasing demand for liquid transportation fuels, decreasing reserves of ‘easy oil’ (crude petroleum oil that can be accessed and recovered easily) and increasing constraints on carbon footprints of such fuels, it is becoming increasingly important to develop routes to produce liquid transportation fuels from biomass in an efficient manner. Such liquid transportation fuels produced from biomass are sometimes also referred to as biofuels. Biomass offers a source of renewable carbon. Therefore, when using such biofuels, it may be possible to achieve more sustainable CO2 emissions over petroleum-derived fuels.

[0003] Solid feedstocks such as feedstocks containing lignocellulose (e.g., woody biomass, agricultural residues, forestry residues, residues from the wood products and pulp & paper industries) and municipal solid waste are important feedstocks for biomass-to-fuel processes due to their availability on a large scale.

[0004] A two-step process is generally adopted for upgrading solid feedstocks to transportation fuels. The solid feedstock is first liquefied by pyrolysis, hydrolysis, hydrothermal liquefaction, etc. to produce bio-crude. The bio-crude is subsequently hydrotreated to reduce the viscosity and oxygen content to produce transportation fuel. Without hydrogenation, the liquefied bio-crude products have low quality (e.g., in terms of contaminants, stability, homogeneity, etc.) which can pose significant challenges for further upgrading at a downstream hydrotreating unit. Therefore, it is desirable to have high quality biocrude from liquefaction which can be directly upgraded in a hydrotreating unit.T-12604-W001 (538-356 PCT)SUMMARY

[0005] In accordance with an illustrative embodiment, a process for upgrading a solid biomass feedstock comprises:

[0006] processing, in a solvent liquefaction reactor, a slurry feed comprising a solid biomass feedstock comprising a lignocellulosic material and a liquid carrier under solvent liquefaction conditions to produce a solvent liquefaction effluent comprising a liquefied biomass comprising the lignocellulosic material and unconverted solid biomass feedstock,

[0007] processing, in a slurry hydroconversion reactor, the solvent liquefaction effluent comprising the liquefied biomass comprising the lignocellulosic material and unconverted solid biomass feedstock in the presence of a slurry hydroconversion catalyst and hydrogen in a slurry hydroconversion zone and under slurry hydroconversion conditions to produce a slurry hydroconversion effluent, and

[0008] processing, in a hydrotreating reactor, the slurry hydroconversion effluent by subjecting the slurry hydroconversion effluent to a hydrodeoxygenation catalyst and under hydrodeoxygenation reaction conditions to produce a hydrodeoxygenated liquid effluent, and subjecting the hydrodeoxygenated liquid effluent to a hydrogenation catalyst and under hydrogenation reaction conditions to produce a liquid hydrocarbon product.

[0009] In accordance with another illustrative embodiment, a system comprises:

[0010] a solvent liquefaction reactor configured to process a slurry feed comprising a solid biomass feedstock comprising a lignocellulosic material and a liquid carrier to produce a solvent liquefaction effluent comprising a liquefied biomass comprising the lignocellulosic material and unconverted solid biomass,

[0011] a slurry hydroconversion reactor configured to process the solvent liquefaction effluent comprising the liquefied biomass comprising the lignocellulosic material and unconverted solid biomass in the presence of a slurry hydroconversion catalyst and hydrogen in a slurry hydroconversion zone and under slurry hydroconversion conditions to produce a slurry hydroconversion effluent, and

[0012] a hydrotreating reactor configured to process the slurry hydroconversion effluent by subjecting the slurry hydroconversion effluent to a hydrodeoxygenation catalyst and under hydrodeoxygenation reaction conditions to produce a hydrodeoxygenated liquid effluent, andT-12604-W001 (538-356 PCT)subject the hydrodeoxygenated liquid effluent to a hydrogenation catalyst and under hydrogenation reaction conditions to produce a liquid hydrocarbon product.BRIEF DESCRIPTION OF THE DRAWING

[0013] In combination with the accompanying drawing and with reference to the following detailed description, the features, advantages, and other aspects of the implementations of the present disclosure will become more apparent, and several implementations of the present disclosure are illustrated herein by way of example but not limitation. The principles illustrated in the example embodiments of the drawing can be applied to alternate processes and apparatus. Additionally, the elements and features shown in the drawing are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the example embodiments. Certain dimensions or positions may be exaggerated to help visually convey such principles. In the drawings, the same reference numerals used in different embodiments designate like or corresponding, but not necessarily identical, elements. In the accompanying drawing:

[0014] FIG. 1 illustrates a process and system for upgrading a solid biomass feedstock comprising a lignocellulosic material to a renewable fuel, according to an illustrative embodiment.DETAILED DESCRIPTION

[0015] Various illustrative embodiments described herein are directed to processes and systems for upgrading a solid biomass feedstock comprising a lignocellulosic material to, for example, a renewable fuel such as diesel fuel, jet fuel, gasoline and sustainable aviation fuels (SAF). The processing of a solid biomass feedstock comprising a lignocellulosic material into, for example, value added fuels, offers one alternative to crude.

[0016] DEFINITIONS

[0017] To define more clearly the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions are applicable to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition from the IUPAC Compendium of Chemical Terminology can be applied, as long as that definition does not conflict with any other disclosure or definition applied herein or render indefinite or non-enabled any claim to which that definition is applied. To the extent that any definition or usage providedT-12604-W001 (538-356 PCT)by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein controls.

[0018] While systems and processes are described in terms of “comprising” various components or steps, the systems and processes can also “consist essentially of’ or “consist of’ the various components or steps, unless stated otherwise.

[0019] The terms “a,” “an,” and “the” are intended to include plural alternatives, e.g., at least one. The terms “including,” “with,” and “having,” as used herein, are defined as comprising (i.e., open language), unless specified otherwise.

[0020] Various numerical ranges are disclosed herein. When Applicant discloses or claims a range of any type, Applicant’s intent is to disclose or claim individually each possible number that such a range could reasonably encompass, including end points of the range as well as any sub-ranges and combinations of sub-ranges encompassed therein, unless otherwise specified. For example, all numerical end points of ranges disclosed herein are approximate, unless excluded by proviso.

[0021] Values or ranges may be expressed herein as “about,” from “about” one particular value, and / or to “about” another particular value. When such values or ranges are expressed, other embodiments disclosed include the specific value recited, from the one particular value, and / or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that there are a number of values disclosed therein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. In another aspect, use of the term “about” means ±20% of the stated value, ±15% of the stated value, ±10% of the stated value, ±5% of the stated value, ±3% of the stated value, or ±1% of the stated value.

[0022] Applicant reserves the right to proviso out or exclude any individual members of any such group of values or ranges, including any sub-ranges or combinations of sub-ranges within the group, that can be claimed according to a range or in any similar manner, if for any reason Applicant chooses to claim less than the full measure of the disclosure, for example, to account for a reference that Applicant may be unaware of at the time of the filing of the application. Further, Applicant reserves the right to proviso out or exclude any members of a claimed group.T-12604-W001 (538-356 PCT)

[0023] The term “hydroconverting” or “hydroconversion,” as used herein refers to any process in which hydrocarbons are processed or treated in the presence of a hydrogen stream and a catalyst under hydroconverting conditions, typically, at elevated temperature and elevated pressure. Hydroconverting includes, for example, hydrocracking, hydrotreating, hydrogenation, deoxygenation, desulfurization, denitrogenation, demetallization, dechlorination, decarboxylation, decarbonylation, dearomatization or a combination thereof.

[0024] The term “hydrotreating” refers to processes wherein a hydrogen-containing treat gas is used in the presence of suitable catalysts which are primarily active for the removal of heteroatoms, such as sulfur, nitrogen, oxygen and metals from the hydrocarbon feedstock. In hydrotreating, hydrocarbons with double and triple bonds such as olefins may be saturated. Some hydrotreating processes are specifically designed to saturate aromatics. In hydrotreating, a feed derived from a biological source is subjected to hydrodeoxygenation, hydrogenation, decarboxylation and / or decarbonylation.

[0025] The term “renewable” refers to a material that is produced from a renewable resource, which is a resource produced via a natural process at a rate comparable to its rate of consumption (e.g., within a 100-year time frame). The renewable resource can be replenished naturally or via agricultural techniques. Non-limiting examples of renewable resources include plants, animals, fish, bacteria, fungi, and forestry products. These resources can be naturally occurring, hybrids, or genetically engineered organisms. Natural resources such as crude oil (petroleum), natural gas, coal, peat, etc. take longer than 100 years to form and thus they are not considered renewable resources.

[0026] The term “biocrude” refers to oils produced from biomass by employing any liquefaction process such as a hydrothermal liquefaction, pyrolysis and hydropyrolysis, or processed oils which contain 20 % or more of water.

[0027] The term “Cn hydrocarbons” or “Cn,” is used herein having its well-known meaning, that is, wherein “n” is an integer value, and means hydrocarbons having that value of carbon atoms. The term “Cn+ hydrocarbons” or “Cn+” refers to hydrocarbons having that value or more carbon atoms. The term “Cn- hydrocarbons” or “Cn-” refers to hydrocarbons having that value or less carbon atoms.T-12604-W001 (538-356 PCT)

[0028] The term “hydrocarbon” is used in the conventional sense to refer to a compound containing only carbon and hydrogen atoms.

[0029] The term “hydrocarbonaceous” can be used to refer to compounds, mixtures, and / or other fractions that are substantially composed of hydrocarbons or hydrocarbon-like compounds, but that may also include heteroatoms (i.e., not carbon or hydrogen). Examples of such heteroatoms include sulfur, nitrogen, oxygen, phosphorus and various trace metals such as alkali metals, alkaline earth metals and transition metals (e.g., iron). For a mixture or fraction, the combined carbon and hydrogen content of a hydrocarbonaceous mixture or fraction can correspond to at least 80 wt. % of the total weight of a mixture or fraction, or at least 90 wt. %, or at least 95 wt. %, or at least 98 wt. %, such as up to 100 wt. % (i.e., a hydrocarbon mixture or fraction is included within the definition for a hydrocarbonaceous fraction). It is noted that a hydrocarbonaceous sample can correspond to a portion of one or more hydrocarbonaceous compounds, mixtures, and / or fractions.

[0030] The term “continuous” means a system that operates without interruption or cessation for a period of time, such as where reactants are continually fed into a reaction zone and products are continually or regularly withdrawn without stopping the reaction in the reaction zone.

[0031] The term “biomass” refers to, without limitation, organic material originating from plants, animals, or micro-organisms (e.g., including plants, agricultural crops or residues, municipal wastes, and algae).

[0032] The terms “upgrade,” “upgrading” and “upgraded,” when used to describe a feedstock that is being or has been subjected to hydroprocessing, or a resulting material or product, refer to one or more of a reduction in molecular weight of the feedstock, a reduction in boiling point range of the feedstock, a reduction in concentration of hydrocarbon free radicals, and / or a reduction in quantity of impurities, such as sulfur, nitrogen, oxygen, halides, and metals.

[0033] The term “zone” can refer to an area including one or more equipment items and / or one or more sub-zones. Equipment items can include one or more reactors or reactor vessels, separation vessels, distillation towers, heaters, exchangers, pipes, pumps, compressors, and controllers. Additionally, an equipment item, such as a reactor, dryer, or vessel, can further include one or more zones or sub-zones.T-12604-W001 (538-356 PCT)

[0034] The term “effluent” refers to a stream that is passed out of a reactor, a reaction zone, or a separator following a particular reaction or separation. Generally, an effluent has a different composition than the stream that entered the reactor, reaction zone, or separator. It should be understood that when an effluent is passed to another component or system, only a portion of that effluent may be passed. For example, a slipstream may carry some of the effluent away, meaning that only a portion of the effluent may enter the downstream component or system.

[0035] The terms “separation unit” and “separator” refer to any separation device(s) that at least partially separates one or more chemical constituents in a mixture from one another. For example, a separation system may selectively separate different chemical constituents from one another, forming one or more chemical fractions. Examples of separation systems include, without limitation, distillation columns, fractionators, flash drums, knock-out drums, knock-out pots, centrifuges, filtration devices, traps, scrubbers, expansion devices, membranes, solvent extraction devices, high-pressure separators, low-pressure separators, or combinations or these. The separation processes described in the present disclosure may not completely separate all of one chemical constituent from all of another chemical constituent. Instead, the separation processes described in the present disclosure “at least partially” separate different chemical constituents from one another and, even if not explicitly stated, separation may include only partial separation.

[0036] It should further be understood that streams may be named for the components of the stream, and the component for which the stream is named may be the major component of the stream (such as comprising from 50 wt. %, from 70 wt. %, from 90 wt. %, from 95 wt. %, from 99 wt. %, from 99.5 wt. %, or from 99.9 wt. % of the contents of the stream to 100 wt. % of the contents of the stream). It should also be understood that components of a stream are disclosed as passing from one system component to another when a stream comprising that component is disclosed as passing from that system component to another. For example, a disclosed “hydrogen stream” passing to a first system component or from a first system component to a second system component should be understood to equivalently disclose “hydrogen” passing to the first system component or passing from a first system component to a second system component.

[0037] The term “boiling point temperature” means atmospheric equivalent boiling point (AEBP) as calculated from the observed boiling temperature and the distillation pressure, asT-12604-W001 (538-356 PCT)calculated using the equations furnished in ASTM DI 160 appendix A7 entitled “Practice for Converting Observed Vapor Temperatures to Atmospheric Equivalent Temperatures”.

[0038] The term “T5” or “T95” means the temperature at which 5 volume percent or 95 volume percent, as the case may be, respectively, of the sample boils using ASTM D86.

[0039] The term “initial boiling point” (IBP) means the temperature at which the sample begins to boil using ASTM D86.

[0040] The term “end point” (EBP) means the temperature at which the sample has all boiled off using ASTM D86.

[0041] The term “True Boiling Point” (TBP) means a test method for determining the boiling point of a material which corresponds to ASTM D2892 for the production of a liquefied gas, distillate fractions, and residuum of standardized quality on which analytical data can be obtained, and the determination of yields of the above fractions by both mass and volume from which a graph of temperature versus mass % distilled is produced using fifteen theoretical plates in a column with a 5: 1 reflux ratio.

[0042] The term “naphtha” or “naphtha boiling range” means hydrocarbons boiling in the range of an IBP between about 0°C and 100°C or a T5 between 15°C and 100°C and the “naphtha cut point” comprising a T95 between 150°C and 200°C using the TBP distillation method.

[0043] The term “kerosene” or “kerosene boiling range” means hydrocarbons boiling in the range of from 132°C to 300°C, using the TBP distillation method. Further, a kerosene stream may be defined as having T5 boiling point from 120°C to 200°C and T95 boiling point from 270°C to 300°C or a T10 boiling of no more than 205°C and a final boiling point of no greater than 300°C using ASTM D86. Furthermore, the flash point must be greater than about 38°C using ASTM D56.

[0044] The term “diesel” or “diesel boiling range” means hydrocarbons having a T5 boiling point between 150°C and 200°C and a T95 boiling point between 343°C and 399°C using the TBP distillation method.

[0045] The term “vacuum gas oil” (VGO) as used herein refer to hydrocarbons boiling in the range of about 343°C to 550°C.

[0046] The term “light vacuum gas oil” (LVGO) refers to hydrocarbons boiling in the range of about 343°C to 425°C.T-12604-W001 (538-356 PCT)

[0047] The term “heavy vacuum gas oil” (HVGO) refers to hydrocarbons boiling in the range of about 425°C to 550°C.

[0048] The terms “wt. %,” “vol. %” or “mol. %” refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component. In a non-limiting example, 10 moles of component in 100 moles of the material are 10 mol. % of component.

[0049] The non-limiting illustrative embodiments described herein overcome the drawbacks discussed above by providing systems and processes for processing a liquid feedstock comprising a lignocellulosic material to provide, for example, renewable fuels such as diesel fuel, gasoline and sustainable aviation fuels.

[0050] The non-limiting illustrative embodiments of the present disclosure will be specifically described below with reference to the accompanying drawing. For the purpose of clarity, some steps leading up to the production of a renewable fuel as illustrated in FIG. 1 may be omitted. In other words, one or more well-known processing steps which are not illustrated but are well-known to those of ordinary skill in the art have not been included in the figure. This is not intended to be interpreted as a limitation of any particular embodiment, or illustration, or scope of the claims.

[0051] FIG. 1 shows a system 100 including a mixing unit 102 for receiving a solid biomass feedstock 104 and a liquid carrier 101 to produce a slurry feed 106. Liquid carrier 101 can be an external liquid carrier 103 and / or an internal recycle stream including one or more of a recycled stream 114 from a solvent liquefaction in a solvent liquefaction reactor 108 as discussed below, and / or a recycled bottom liquid stream 128 from a slurry hydroconverson process in a slurry hydroconversion reactor 118 as discussed below, and / or a recycled upgraded stream 142 from a hydrotreating process in a hydrotreating reactor 134 as discussed below. The term “external liquid carrier” refers to a liquid carrier that does not originate from each of the solvent liquefaction, slurry hydroconverson and hydrotreating processes themselves but rather is added to the mixing unit from another source. Recycled stream 114, recycled bottom liquid stream 128 and recycled upgraded stream 142 are liquid carriers produced exclusively in situ and are an internal recycle stream such that the process of the present disclosure can operate in a continuous manner.T-12604-W001 (538-356 PCT)

[0052] In operation, one or more of external liquid carrier 103, recycled stream 114, recycled bottom liquid stream 128 and recycled upgraded stream 142 can be used to form slurry feed 106 with solid biomass feedstock 104. For example, as one skilled in the art will readily appreciate, solid biomass feedstock 104 can initially be combined with external liquid carrier 103 to form slurry feed 106. As the process continues, recycled stream 114, recycled bottom liquid stream 128 and recycled upgraded stream 142 are continuously produced exclusively in situ, and one or more of recycled stream 114, recycled bottom liquid stream 128 and recycled upgraded stream 142 can be recycled back to mixing unit 102 to form slurry feed 106 with solid biomass feedstock 104 as part of a continuous process. In the case where there is an insufficient amount of any one or all of recycled stream 114, recycled bottom liquid stream 128 and recycled upgraded stream 142 for forming slurry feed 106 with solid biomass feedstock 104, then an additional amount of external liquid carrier 103 can be sent to mixing unit 102 to assist in forming slurry feed 106.

[0053] Although external liquid carrier 103, recycled stream 114, recycled bottom liquid stream 128 and recycled upgraded stream 142 are shown entering mixing unit 102 as liquid carrier 101, this is merely illustrative and any points of entry into mixing unit 102 for external liquid carrier 103, recycled stream 114, recycled bottom liquid stream 128 and recycled upgraded stream 142 are contemplated herein.

[0054] In some embodiments, external liquid carrier 103 can be any hydrocarbon solvent that has appropriate physical properties (viscosity, flashpoint) for forming slurry feed 106. Suitable hydrocarbon solvents include, for example, mineral oil, kerosene, jet-fuel, white oils, diesel oil, olefins (PAO or polyalpha olefins), organic esters, synthetic fluids, and mixtures thereof. In some embodiments, a suitable hydrocarbon solvent is an ester-based oil or mixtures thereof, e.g., bio-derived oil such as vegetable derived oil, liquid at ambient temperature such as tallow oil.

[0055] In some embodiments, external liquid carrier 103 can be any oxygenated hydrocarbon that has appropriate physical properties (viscosity, flashpoint) for forming slurry feed 106. Suitable oxygenated hydrocarbon includes, for example, alcohols, ethers, esters, ketones, aldehydes, carboxylic acids and their derivatives, and oxygen containing heterocyclic compounds. Suitable alcohols include, for example, methanol, ethanol, propanol, 2-propanol, butanol, tertbutanol, iso-butanol and 2-butanol. Suitable ethers include, for example, ethers containing 5 orT-12604-W001 (538-356 PCT)more carbon atoms per molecule such as methyl tert-butyl ether and ethyl tert-butyl ether. Suitable esters include, for example, esters containing 5 or more carbon atoms per molecule.

[0056] In some embodiments, external liquid carrier 103 can be a liquid carrier in which at least 50 wt. %, based on the total weight of the liquid carrier, has a boiling point greater than or equal to about 300°F.

[0057] In some embodiments, external liquid carrier 103 can be one or more biocrudes such as, for example, tall oil products. Suitable tall oil products include, for example, crude tall oil, tall oil fatty acid, distilled tall oil and tall oil pitch. The term “tall oil pitch (TOP)” refers to residual bottom fraction from tall oil distillation processes. In some embodiments, tall oil pitch comprises from about 34 wt. % to about 51 wt. % free acids, from about 23 wt. % to about 37 wt. % esterified acids, and from about 25 wt. % to about 34 wt. % unsaponifiable neutral compounds of the total weight of the tall oil pitch. The free acids include, for example, dehydroabietic acid, abietic and other resin acids. The esterified acids include, for example, oleic and linoleic acids. The unsaponifiable neutral compounds include, for example, diterpene sterols, fatty alcohols, sterols, and dehydrated sterols.

[0058] In some embodiments, external liquid carrier 103 can be an unconverted heavy oil (UCO) fraction processed from a heavy oil feedstock in a slurry hydroconversion reactor not in system 100 of the present disclosure.

[0059] In some embodiments, solid biomass feedstock 104 to be employed includes, for example, one or more of a residual waste feedstock and a biomass feedstock containing lignocellulosic material. Lignocellulosic material includes three main components, namely, cellulose, hemicellulose and lignin. In some embodiments, cellulose is the primary structural component of lignocellulose and provides rigidity and forms the framework of plant cell walls. Cellulose can consist of a beta (l-4)-linked chain of glucose molecules. Hydrogen bonds between different layers of cellulose contribute to its resistance to degradation. In some embodiments, hemicellulose is usually the second most abundant component in lignocellulose and contributes to the overall structure and flexibility of the plant cell wall. Hemicelluloses are a group of polysaccharides made up of various sugars. For example, hemicellulose can be composed of various 5- and 6-carbon sugars, including arabinose, galactose, glucose, mannose and xylose. In some embodiments, lignin is the most complex constituent and provides additional strength,T-12604-W001 (538-356 PCT)protection, and resistance to decay. Lignin is a polymer structure of three major phenolic components, including p-coumaryl alcohol (H), coniferyl alcohol (G) and sinapyl alcohol (S).

[0060] Lignocellulosic material may include a mixture of lignin, cellulose and hemicelluloses in any proportion. Such material can be more difficult to convert into fungible liquid hydrocarbon products than cellulosic and hemicellulosic material. Suitable lignocellulosecontaining biomass includes woody biomass and agricultural and forestry products and residues (e g., whole harvest energy crops, round wood, forest slash, bamboo, sawdust, bagasse, sugarcane tops and trash, cotton stalks, com stover, com cobs, castor stalks, Jatropha whole harvest, Jatropha trimmings, de-oiled cakes of palm, castor and Jatropha, coconut shells, residues derived from edible nut production and mixtures thereof), and municipal solid wastes containing lignocellulosic material. The municipal solid waste may include, for example, any combination of lignocellulosic material (yard trimmings, pressure- treated wood such as fence posts, plywood), discarded paper and cardboard and waste plastics, along with refractories such as glass, and metal.

[0061] In some embodiments, a solid form of solid biomass feedstock 104 includes, for example, particles, pellets, shavings, fibers, needles and / or other geometries. The solid form does not necessarily have to have a homogeneous configuration. Instead, the configuration may be regular or irregular. For example, in the case of the solid form comprising particles, the particles can be, for example, virtually spherical particles, and likewise particles having an irregular and / or angular outward shape. In addition, the surface of the particles may be smooth, but it is also possible that the surface of the material is rough and / or has unevenness and / or depressions and / or elevations. In an illustrative embodiment, a solid form can contain particles of solid biomass feedstock 104 having a particle size of about 1 millimeter (mm) to about 3.5 mm.

[0062] Mixing unit 102 includes a first inlet for receiving liquid carrier 101 and a second inlet for receiving solid biomass feedstock 104. However, it is also contemplated that liquid carrier 101 can be co-fed with solid biomass feedstock 104 to mixing unit 102. Mixing unit 102 can be any conventional mixing unit known in the art for combining liquid carrier 101 with solid biomass feedstock 104 to form slurry feed 106.

[0063] In some embodiments, slurry feed 106 can contain liquid carrier 101 in an amount ranging from about two times to about eight times the amount of solid biomass feedstock 104.T-12604-W001 (538-356 PCT)

[0064] In some embodiments, slurry feed 106 can contain from about 65 wt. % to about 95 wt. % of liquid carrier 101 from about 5 wt. % to about 35 wt. % of solid biomass feedstock 104.

[0065] Stage 1 : Solvent Liquefaction Process

[0066] System 100 further includes solvent liquefaction reactor 108 for receiving slurry feed 106. The solvent liquefaction process of solid biomass feedstock 104 in slurry feed 106 can be carried out in a variety of solvent liquefaction reactors. Suitable solvent liquefaction reactors include, for example, continuous stirred tank reactors, bubble column reactors, liquid recirculation reactors, and combinations thereof. Solvent liquefaction reactor 108 may be a single-stage or multi-stage and may be comprised of a single reactor or multiple reactors. In one embodiment, solvent liquefaction reactor 108 is an up-flow reactor.

[0067] In some embodiments, solvent liquefaction reactor 108 is configured for sufficient backmixing of slurry feed 106. In non-limiting illustrative embodiments, backmixing is provided by, for example, mechanical mixers such as top-mounted, side-mounted, or bottom-mounted agitators; rapid movement of slurry feed 106 pumped into or through solvent liquefaction reactor 108; and / or introducing or generating gases or vapors such as gas bubbles from one or more gas spargers in solvent liquefaction reactor 108.

[0068] The slurry feed 106 is held in solvent liquefaction reactor 108 and heated to a temperature to produce a solvent liquefaction effluent 112 comprising a liquefied biomass and unconverted solid biomass feedstock 104 with liquid carrier 101. In some embodiments, the solvent liquefaction process in solvent liquefaction reactor 108 can be operated under solvent liquefaction conditions including, for example, a pressure in a range of from about 20 bar to about 200 bar, and a reactor temperature in a range from about 500°F to about 750°F. The process does not include hydrogen or carbon monoxide as an input, and may be done with or without a catalyst.

[0069] In some embodiments, the operating temperature and pressure provide efficient liquefaction, converting from about 50% to about 70%, of solid biomass feedstock 104 (on a dry weight basis) into liquid and / or gaseous products. As a result of the solvent liquefaction condition selections described herein, high efficiency can be obtained.

[0070] In some embodiments, solvent liquefaction effluent 112 contains, for example, a liquefied biomass comprising the lignocellulosic material, light liquid hydrocarbonaceousT-12604-W001 (538-356 PCT)products such as a light (C2 to C5) hydrocarbon product, a heavy liquid bottom product including, for example, a naphtha steam, a diesel stream, a light vacuum gas oil (LVGO) stream and a heavy vacuum gas oil (HVGO) stream, and unconverted solid biomass feedstock. In some embodiments, the liquefied biomass may be cooled using, for example, a heat exchanger, to allow for oligomerization to occur to convert a portion of the light liquid hydrocarbonaceous products into heavier hydrocarbons for an improved yield in the diesel range, i.e., the liquefied biomass is cooled to allow for oligomerization to occur to convert a portion of light liquid hydrocarbonaceous products into heavy hydrocarbons in the diesel range.

[0071] Following liquefication of solid biomass feedstock 104, any by-products such as carbon monoxide, carbon dioxide, water, etc., exit solvent liquefaction reactor 108 as a by-product stream 110 for further use or processing. In some embodiments, solvent liquefaction effluent 112 is sent directly to slurry hydroconversion reactor 118 as is. In some embodiments, a portion of the heavy bottom product including, for example, one or more of naphtha steam, diesel stream, light vacuum gas oil (LVGO) stream and heavy vacuum gas oil (HVGO) stream liquid product can be separated from solvent liquefaction effluent 112 and exits solvent liquefaction reactor 108 as recycled stream 114. In some embodiments, recycled stream 114 can be a heavy liquid product having an initial boiling point of greater than or equal to 350°F, 5 wt. % at 500°F and an end boiling point of greater than 1350°F. In some embodiments, recycled stream 114 is recycled back to mixing unit 102 for making slurry feed 106 with solid biomass feedstock 104 as discussed above.

[0072] Stage 2 - Slurry Hydroconversion Process

[0073] System 100 further includes slurry hydroconversion reactor 118 for receiving solvent liquefaction effluent 112, a hydrogen stream 116 and a slurry hydroconversion catalyst 117 for carrying out a hydroconversion process. Slurry hydroconversion processes for preparing one or more upgraded hydrocarbonaceous products generally involve passing the liquid product containing the liquid product and unconverted solid biomass feedstock 104 and liquid carrier 101, as described above, through a slurry hydroconversion reaction zone in the presence of hydrogen and a slurry hydroconversion catalyst under slurry hydroconversion conditions to provide a slurry hydroconversion effluent comprising light liquid hydrocarbonaceous products.T-12604-W001 (538-356 PCT)

[0074] The hydroconversion process can be carried out in a variety of slurry hydroconversion reactors. Suitable slurry hydroconversion reactors include, for example, continuous stirred tank reactors, fluidized bed reactors, spouted bed reactors, spray reactors, bubble column reactors, liquid recirculation reactors, slurry recirculation reactors, and combinations thereof. Slurry hydroconversion reactor 118 may be a single-stage or multi-stage and may be comprised of a single reactor or multiple reactors. In some embodiments, one or more slurry hydroconversion reactor units may be utilized in parallel or in series. In one embodiment, slurry hydroconversion reactor 118 is an up-flow reactor. In another embodiment, slurry hydroconversion reactor 118 is a down-flow reactor. Generally, the vapor outlet from a slurry hydroconversion reactor is above the inlet. The slurry outlet may be above or below the inlet. In contrast to conventional integrated hydropyrolysis and hydroconversion (1H2) technology where catalyst is fluidized or suspended by means of a gas (e.g., hydrogen), the process of this disclosure uses a slurry hydroconversion reactor wherein solids and catalyst are dispersed in liquid.

[0075] In some embodiments, slurry hydroconversion reactor 118 is configured for sufficient backmixing of solvent liquefaction effluent 112, hydrogen stream 116 and slurry hydroconversion catalyst 117. In non-limiting illustrative embodiments, backmixing is provided by, for example, mechanical mixers such as top-mounted, side-mounted, or bottom-mounted agitators; rapid movement of solvent liquefaction effluent 112, hydrogen stream 116 and slurry hydroconversion catalyst 117 pumped into or through slurry hydroconversion reactor 118; and / or introducing or generating gases or vapors such as gas bubbles from one or more gas spargers in slurry hydroconversion reactor 118.

[0076] Hydrogen stream 116 includes hydrogen, which is contained in a hydrogen “treat gas,” for injecting into slurry hydroconversion reactor 118. The treat gas can be either pure hydrogen or a hydrogen-containing gas, which is a gas stream containing hydrogen in an amount that is sufficient for the intended reaction(s), optionally including one or more other gases (e.g., nitrogen and light hydrocarbons such as methane). The treat gas stream introduced into a reaction stage can contain at least about 50 vol. % or at least about 75 vol. % hydrogen. Optionally, the hydrogen treat gas can be substantially free (less than 1 vol. %) of impurities such as H2S and NH3 and / or such impurities can be substantially removed from a treat gas prior to use. Hydrogen can be supplied co-currently with the input feed to slurry hydroconversion reactor 118 or separatelyT-12604-W001 (538-356 PCT)via a separate gas conduit. The amount of hydrogen stream 116 used for the hydrotreating process can range from about 1 vol. % to about 8 vol. %.

[0077] In some embodiments, the hydroconversion process uses a dispersed catalyst which is continuously doped into the feed.

[0078] In some embodiments, slurry hydroconversion catalyst 117 can correspond to one or more catalytically active metals in particulate form and / or supported on particles. Catalytically active metals for use in the hydrotreating process can include those from Groups 4-12 of the IUPAC Periodic Table of Elements. Suitable metals include, for example, iron, nickel, molybdenum, zinc, vanadium, tungsten, cobalt, ruthenium, and any combination thereof. The catalytically active metal may be present as a solid particulate in elemental form or as an organic compound or an inorganic compound such as a sulfide or other ionic compound. Metal or metal compound nanoaggregates may also be used to form the solid particulates.

[0079] A catalyst in the form of a solid particulate is generally a compound of a catalytically active metal, or a metal in elemental form, either alone or supported on a refractory material such as an inorganic metal oxide (e.g., alumina, silica, titania, zirconia, and any combination thereof). Other suitable refractory materials can include carbon, coal, and clays. Zeolites and non-zeolitic molecular sieves are also useful as solid supports. Generally, supported catalyst can have from about 0.01 wt. % to about 30 wt. % of the catalytic active metal based on the total weight of the catalyst.

[0080] In some embodiments, it can be desirable to form slurry hydroconversion catalyst 117 for the hydrotreating process in situ, such as forming a catalyst from a metal sulfate (e.g., iron sulfate monohydrate) catalyst precursor or another type of catalyst precursor that decomposes or reacts in the hydroprocessing reaction zone environment, or in a pretreatment step, to form a desired, well-dispersed and catalytically active solid particulate (e.g., as iron sulfide). Precursors also include oil-soluble organometallic compounds containing the catalytically active metal of interest that thermally decompose to form the solid particulate (e.g., iron sulfide) having catalytic activity. Other suitable precursors include metal oxides that may be converted to catalytically active (or more catalytically active) compounds such as metal sulfides. In a particular embodiment, a metal oxide containing mineral may be used as a precursor of a solid particulateT-12604-W001 (538-356 PCT)comprising the catalytically active metal (e.g., iron sulfide) on an inorganic refractory metal oxide support (e.g., alumina).

[0081] In some embodiments, slurry hydroconversion catalyst 117 includes sulfided catalytically active metals. Examples of suitable catalytically active metals include, without limitation, sulfided nickel, sulfided cobalt, sulfided molybdenum, sulfided tungsten, sulfided CoMo, sulfided NiMo, sulfided MoW, sulfided NiW, and combinations thereof.

[0082] A catalyst bed / zone may have a mixture of two types of catalysts and / or successive beds / zones, including stacked beds, and may have the same or different catalysts and / or catalyst mixtures. In case of such sulfided hydrotreating catalyst, a sulfur source will typically be supplied to the catalyst to keep the catalyst in sulfided form during the hydroconversion process.

[0083] The amount of slurry hydroconversion catalyst 117 in the process may be less than about 5% by weight of the weight of solvent liquefaction effluent 112. In some embodiments, suitable slurry catalyst concentrations can range from about 0.005% to about 3% on a metal basis (e.g., about 0.02% to about 1% on a metal basis).

[0084] Slurry hydroconversion catalyst 117 used in conjunction with the processes described herein may have an average particle size of about 300 microns or less (e.g., about 100 microns or less, or 10 microns or less). The particle size is the length of the largest orthogonal axis through the particle. Average particle size is the average particle diameter of all the catalyst particles fed to the reactor which may be determined by a representative sampling.

[0085] The hydroconversion process can be operated under slurry hydroconversion conditions including, for example, a pressure in a range of from about 20 bar to about 200 bar, and a reactor temperature in a range from about 500°F to about 800°F. The liquid hourly space velocity (LHSV) is typically below about 4 h'1on a fresh feed basis, with a range of from about 0.1 h1to about 3 h or about 0.1 h1to about 1 h1.

[0086] The hydroconversion process generally involves passing solvent liquefaction effluent 112 through a slurry hydroconversion reaction zone in the presence of hydrogen stream 116 and slurry hydroconversion catalyst 117 under slurry hydroconversion conditions to provide a slurry hydroconversion effluent 120. Hydrogen stream 116 may be mixed with solvent liquefaction effluent 112 upstream of the feed inlet to slurry hydroconversion reactor 118. Alternatively, hydrogen stream 116 may be added to slurry hydroconversion reactor 118T-12604-W001 (538-356 PCT)independently, but concurrently, with solvent liquefaction effluent 112 and slurry hydroconversion catalyst 117 (not shown). Likewise, slurry hydroconversion catalyst 117 may be added to slurry hydroconversion reactor 118 independently, but concurrently, with solvent liquefaction effluent 112 and hydrogen stream 116. Alternatively, slurry hydroconversion catalyst 117 may be mixed with solvent liquefaction effluent 112 and hydrogen stream 116 upstream of the feed inlet to slurry hydroconversion reactor 118 (not shown).

[0087] In some embodiments, solvent liquefaction effluent 112 can be fed through a filtering zone to capture fouling and / or particulate matter before flowing to the slurry hydroconversion reaction zone.

[0088] In some embodiments, greater than or equal to about 90% of solid biomass feedstock 104 (on a dry weight basis) of solvent liquefaction effluent 112 is converted into liquid and / or gaseous products.

[0089] The reaction catalyzed in slurry hydroconversion reactor 118 includes, for example, hydrodeoxygenation, hydrogenation, hydrodemetallization, etc. The hydroconversion reaction in the slurry hydroconversion zone results in the formation of slurry hydroconversion effluent 120. In some embodiments, solvent liquefaction effluent 112 is partially deoxygenated to provide slurry hydroconversion effluent 120. In some embodiments, the reaction catalyzed in slurry hydroconversion reactor 118 results in the removal of oxygen such that slurry hydroconversion effluent 120 has an oxygen content less than the oxygen content of solvent liquefaction effluent 112. Slurry hydroconversion effluent 120 is in the form of a gas-liquid-solid mixture.

[0090] Slurry hydroconversion effluent 120 can be sent to a first separation unit 122 for separating into a hydrogen rich off gas stream and a bottoms liquid stream. First separation unit 122 can include one or more separators (e.g., a hot separator operated at between about 260°C and about 426°C and preferably at about the pressure of slurry hydroconversion reactor 118 and a cold separator operated at between about 60°C and about 300°C and a pressure of about the pressure of the hot separator).

[0091] The bottoms liquid stream can be separated into two or more streams. For example, there can be a naphtha and diesel stream, which can be sent as a hydrotreating feed stream 130 for further processing, such as by hydrotreating. Another stream could be a light vacuum gas oil (LVGO) stream. There could be a heavy vacuum gas oil (HVGO) stream. One or more of theseT-12604-W001 (538-356 PCT)streams can be recycled to the slurry hydrocracking reactor for use as the liquid carrier. For example, in some embodiments, a portion of the bottoms liquid stream in slurry hydroconversion effluent 120 can be separated from slurry hydroconversion effluent 120 to provide a recycled bottoms liquid effluent 124. In some embodiments, recycled bottoms liquid effluent 124 can be a heavy liquid product having an initial boiling point of greater than or equal to 350°F, 5 wt. % at 500°F and an end boiling point of greater than 135O°F. Recycled bottoms liquid effluent 124 exits first separation unit 122 and can be sent back to mixing unit 102 as recycled bottom liquid stream 128 for forming slurry feed 106 with solid biomass feedstock 104 as discussed above and another portion exits system 100 as bleed stream 126.

[0092] In some embodiments, slurry hydroconversion effluent 120 includes at least about 50 wt. % naphtha, kerosene and diesel range components, such as at least about 75 wt. % naphtha, kerosene and diesel range components, based on the total slurry hydrocracking effluent. In an exemplary embodiment, slurry hydroconversion effluent 120 includes from about 15 wt. % to about 30 wt. % naphtha range components and from about 40 wt. % to about 60 wt. % diesel range components, based on the total slurry hydrocracking effluent. Further, slurry hydroconversion effluent 120 can include about 30 wt. % or less (e.g., about 20 wt. % or less, or about 10 wt. % or less) heavier components, such as components having boiling points of greater than 343°C.

[0093] Stage 3- Hydrotreating Process

[0094] System 100 further includes hydrotreating reactor 134 for receiving hydrotreating feed stream 130, a hydrogen stream 132 and a hydrotreating catalyst 133 for carrying out one or more hydrotreating processes. In a hydrotreating reactor, hydrotreating feed stream 130 taken from slurry hydroconversion effluent 120 may be hydrotreated in the presence of hydrogen stream 132 over hydrotreating catalyst 133 to produce a liquid hydrocarbon product 136 comprising naphtha and diesel range hydrocarbons. Essentially, the hydrotreating reaction removes heteroatoms from hydrocarbonaceous materials and saturates olefins in the feed stream.

[0095] In some embodiments, the slurry hydrotreating processes can be carried out in a fixed-bed reactor such as a trickle bed reactor. Hydrotreating reactor 134 may be a single-stage or multi-stage and may be comprised of a single reactor or multiple reactors. In some embodiments, hydrotreating reactor 134 includes two or more hydrotreating reactors utilized in parallel or in series.T-12604-W001 (538-356 PCT)

[0096] The hydrotreating is carried out in the presence of hydrogen. Hydrogen stream 132 is, therefore, fed or injected into a vessel or reaction zone or hydroprocessing zone in which the hydroprocessing catalyst is located. Hydrogen stream 132 includes hydrogen, which is contained in a hydrogen “treat gas,” for injecting to the reaction zone in hydrotreating reactor 134. The treat gas can be either pure hydrogen or a hydrogen-containing gas, which is a gas stream containing hydrogen in an amount that is sufficient for the intended reaction(s), optionally including one or more other gases (e.g., nitrogen and light hydrocarbons such as methane). The treat gas stream introduced into a reaction stage can contain at least about 50 vol. % or at least about 75 vol. % hydrogen. Optionally, the hydrogen treat gas can be substantially free (less than 1 vol. %) of impurities such as H2S and NH3 and / or such impurities can be substantially removed from a treat gas prior to use. Hydrogen can be supplied co-currently with the input feed to hydrotreating reactor 134 and / or reaction zone or separately via a separate gas conduit to the hydrotreatment zone.

[0097] In some embodiments, the hydrotreating processes uses a dispersed catalyst which is continuously doped into the feed. In some embodiments, hydrotreating catalyst 133 can correspond to one or more catalytically active metals in particulate form and / or supported on particles. In some embodiments, hydrotreating catalyst 133 can be one or more of a transition metal catalyst or a noble metal catalyst that is used in typical hydrotreating processes. For example, catalytically active metals for use in the hydrotreating processes can include those from Groups 4 to 12 of the IUPAC Periodic Table of Elements. Suitable metals include, for example, iron, nickel, molybdenum, zinc, tungsten, cobalt and any combination thereof. The catalytically active metal may be present as a solid particulate in elemental form or as an organic compound or an inorganic compound such as a sulfide or other ionic compound. Metal or metal compound nanoaggregates may also be used to form the solid particulates.

[0098] In some embodiments, a transition metal catalyst can be one or more of Al, W, Ir, Re, Ni, Mo, Zr, Co, Ru, Rh, Pt or Pd based catalyst including, for example, Ni-Mo, Co-Mo, Ni-W or Ni-Co-Mo.

[0099] In some embodiments, a noble metal catalyst can include those from Groups 8-10 of the IUPAC Periodic Table of Elements including, for example, palladium and platinum.

[0100] A catalyst in the form of a solid particulate is generally a compound of a catalytically active metal, or a metal in elemental form, either alone or supported on a refractoryT-12604-W001 (538-356 PCT)material such as an inorganic metal oxide. In some embodiments, a catalyst support includes, for example, alumina, silica, zeolite, activated carbon, and any combination thereof. Other suitable refractory materials can include carbon, coal, and clays. Zeolites and non-zeolitic molecular sieves are also useful as solid supports. In some embodiments, a supported catalyst can have from about 0.01 to about 30 wt. % of the catalytic active metal based on the total weight of the catalyst.

[0101] In some embodiments, hydrotreating catalyst 133 includes sulfided catalytically active metals. Examples of suitable catalytically active metals include, without limitation, sulfided nickel, sulfided cobalt, sulfided molybdenum, sulfided tungsten, sulfided CoMo, sulfided NiMo, sulfided MoW, sulfided NiW, and combinations thereof.

[0102] In some embodiments, suitable catalyst concentrations can range from about 0.005% to about 3% on a metal basis (e.g., about 0.02% to about 1% on a metal basis).

[0103] A catalyst bed / zone in hydrotreating reactor 134 may have a mixture of two types of catalysts and / or successive beds / zones, including stacked beds, and may have the same or different catalysts and / or catalyst mixtures.

[0104] Hydrotreating catalyst 133 used in conjunction with the processes described herein may have an average particle size of about 300 microns or less (e.g., about 100 microns or less, or 10 microns or less). The particle size is the length of the largest orthogonal axis through the particle. Average particle size is the average particle diameter of all the catalyst particles fed to the reactor which may be determined by a representative sampling.

[0105] The hydrotreating process generally involves passing hydrotreating feed stream 130, through a one or more hydrotreating reaction zones in the presence of hydrogen stream 132 and hydrotreating catalyst 133 under hydrotreating conditions to provide a liquid hydrocarbon product 136. Hydrogen stream 132 may be mixed with hydrotreating feed stream 130 upstream of the feed inlet to hydrotreating reactor 134. Alternatively, hydrogen stream 132 may be added to hydrotreating reactor 134 independently, but concurrently, with hydrotreating feed stream 130. In some embodiment, hydrotreating reactor 134 is a fixed-bed reactor. In some embodiments, hydrotreating catalyst 133 may be loaded to hydrotreating reactor 134.

[0106] The reaction catalyzed in hydrotreating reactor 134 includes, for example, hydrodeoxygenation, hydrogenation, hydrodemetallization, etc. In a non-limiting illustrative embodiment, the hydrotreating process includes passing hydrotreating feed stream 130 into aT-12604-W001 (538-356 PCT)hydrodeoxygenation zone in hydrotreating reactor 134 in the presence of hydrogen stream 132 and hydrotreating catalyst 133 (also referred to as a hydrodeoxygenated catalyst) to remove most, if not all the remaining oxygen present in hydrotreating feed stream 130 to produce a hydrodeoxygenated liquid effluent, followed by sending hydrodeoxygenated liquid effluent to a hydrogenation zone in hydrotreating reactor 134 in the presence of hydrogen stream 132 and hydrotreating catalyst 133 to produce a liquid hydrocarbon product 136.

[0107] In some embodiments, the hydrodeoxygenation reaction is operated at conditions sufficient to cause a hydrodeoxygenation reaction to produce a hydrodeoxygenated liquid effluent having a reduced oxygen content relative to the oxygen content in hydrotreating feed stream 130. The hydrodeoxygenation reaction may be conducted under hydrodeoxygenation reaction conditions including a pressure of from about 500 psig to about 3000 psig, a reactor temperature of from about 230°C to 400°C, a weight hourly space velocity (WHSV) of from about 0.1 h'1to about 10 h'1, and a hydrogen flow of from about 350 to about 900 NL H2 / L feed. The ratio of hydrogen gas to hydrotreating feed stream 130 supplied to the hydrodeoxygenation zone can be in a range of from about 100 to about 1500 normal L (at standard conditions of 0°C and 1 atm (0.1 MPa)) per kg of hydrotreating feed stream 130.

[0108] Hydrodeoxygenated liquid effluent is thereafter sent to a hydrogenation zone in hydrotreating reactor 134 provided with hydrogen stream 132 and hydrotreating catalyst 133 (also referred to as a hydrogenation catalyst). The catalyst used as hydrotreating catalyst 133 for the hydrogenation process can be the same or different as the catalyst for the hydrodeoxygenation process. The hydrogenation zone is operated at conditions sufficient to cause a hydrogenation reaction of hydrodeoxygenated liquid effluent thereby producing liquid hydrocarbon product 136. For example, the hydrogenation process can involve saturating the aromatic compounds such as phenols present in hydrodeoxygenated liquid effluent.

[0109] The hydrogenation process can be operated under hydrogenation conditions including, for example, a pressure in a range of from about 100 psig to about 3000 psig, and a reactor temperature in a range from about 121 °C to about 300°C, a weight hourly space velocity (WHSV) of from about 0.1 h-1to about 10 h’1, and a hydrogen flow of from about 350 to about 900 NL H2 / L feed. The ratio of hydrogen gas to hydrotreating feed stream 130 supplied to theT-12604-W001 (538-356 PCT)hydrodeoxygenation zone can be in a range of from about 100 to about 1500 normal L (at standard conditions of 0°C and 1 atm (0.1 MPa)) per kg of hydrotreating feed stream 130.

[0110] In some embodiments, hydrotreating feed stream 130 can first be fed through a filtering zone to capture fouling and / or particulate matter before flowing to the hydrodeoxygenation zone and the hydrogenation zone. By reducing fouling and / or particulate matter before flowing to the catalyst beds, pressure drop across catalyst bed(s) in the fixed-bed reactor is reduced.

[0111] System 100 further includes a second separation unit 138 for separating liquid hydrocarbon product 136 into desired various products. In some embodiments, liquid hydrocarbon product 136 may first be fractioned to separate any by-products such as carbon monoxide, carbon dioxide, water, etc. which exits second separation unit 138 as by-product stream 140 for further use or processing. In some embodiments, liquid hydrocarbon product 136 may further be fractionated (e.g., by distillation) into different fuel grades, each of which is known to be within a certain boiling point range. For example, fractionation may be conducted at a determined fractionation temperature or boiling point cut-off (e.g., about 120°C to about 300°C, or about 300°C to about 400°C) to separate out various boiling point fractions appropriate to a desired fuel product and to collect olefinic light products for further processing. In some embodiments, liquid hydrocarbon product 136 is separated by fractionating such products as a heavy product having an initial boiling point of greater than or equal to 680°F to provide recycled upgraded stream 142. Recycled upgraded stream 142 exits second separation unit 138 and can be sent back to mixing unit 102 for solid biomass feedstock 104 as discussed above.

[0112] In some embodiments, liquid hydrocarbon product 136 is separated into such products as, for example, a first product 144 including, for example, renewable gasoline, a second product 146 including, for example, a sustainable aviation fuel, and a third product 148 including, for example, renewable diesel.

[0113] According to an aspect of the present disclosure, a process for upgrading a solid biomass feedstock comprises:

[0114] processing, in a solvent liquefaction reactor, a slurry feed comprising a solid biomass feedstock comprising a lignocellulosic material and a liquid carrier under solventT-12604-W001 (538-356 PCT)liquefaction conditions to produce a solvent liquefaction effluent comprising a liquefied biomass comprising the lignocellulosic material and unconverted solid biomass feedstock,

[0115] processing, in a slurry hydroconversion reactor, the solvent liquefaction effluent comprising the liquefied biomass comprising the lignocellulosic material and unconverted solid biomass feedstock in the presence of a slurry hydroconversion catalyst and hydrogen in a slurry hydroconversion zone and under slurry hydroconversion conditions to produce a slurry hydroconversion effluent, and

[0116] processing, in a hydrotreating reactor, the slurry hydroconversion effluent by subjecting the slurry hydroconversion effluent to a hydrodeoxygenation catalyst and under hydrodeoxygenation reaction conditions to produce a hydrodeoxygenated liquid effluent, and subjecting the hydrodeoxygenated liquid effluent to a hydrogenation catalyst and under hydrogenation reaction conditions to produce a liquid hydrocarbon product.

[0117] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the lignocellulosic material comprises a cellulosic material, a hemicellulosic material and lignin.

[0118] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the solid biomass feedstock is ground, pulverized, chipped or in a particulate, pellet, powder, shaving, chip, dust, or pulverized form, or a combination thereof.

[0119] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the liquid carrier is one of a hydrocarbon liquid carrier or an oxygenated liquid carrier.

[0120] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the slurry feed comprises from about 5 wt. % to about 35 wt. % of the solid biomass feedstock and from about 65 wt. % to about 95 wt. % of the liquid carrier.

[0121] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, about 50% to about 70% of the solid biomass feedstock comprising the lignocellulosic material is converted to a liquid phase and a gas phase in the solvent liquefaction reactor.

[0122] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, processing the slurry feed comprising the solid biomass feedstockT-12604-W001 (538-356 PCT)comprising the lignocellulosic material and the liquid carrier is carried out in the absence of hydrogen.

[0123] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the liquefied biomass is cooled to allow for oligomerization to occur to convert a portion of light liquid hydrocarbonaceous products into heavy hydrocarbons in the diesel range.

[0124] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the slurry hydroconversion conditions comprise a pressure in a range of about 20 bar to about 200 bar and a reactor temperature of about 500°F to about 800°F.

[0125] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, greater than about 90% of the solid biomass feedstock comprising the lignocellulosic material is converted to a liquid phase and a gas phase in the slurry hydroconversion reactor.

[0126] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the slurry feed comprising the solid biomass feedstock comprising the lignocellulosic material and the liquid carrier is formed by mixing the solid biomass feedstock comprising the lignocellulosic material and the liquid carrier upstream of the solvent liquefaction reactor.

[0127] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the process further comprises:

[0128] passing the slurry hydroconversion effluent to one or more separation units to separate at least a portion of a heavy liquid bottom product from the slurry hydroconversion effluent, and

[0129] combining the heavy liquid bottom product with the solid biomass feedstock comprising the lignocellulosic material as the liquid carrier upstream of the solvent liquefaction reactor as part of a continuous process.

[0130] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the process further comprises fractioning the liquid hydrocarbon product at a selected fractionation temperature to obtain individual fractions, wherein a given individual fraction is a sustainable aviation fuel.T-12604-W001 (538-356 PCT)

[0131] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, another given individual fraction is one or more of a renewable gasoline or a renewable diesel fuel.

[0132] According to another aspect of the present disclosure, a system comprises:

[0133] a solvent liquefaction reactor configured to process a slurry feed comprising a solid biomass feedstock comprising a lignocellulosic material and a liquid carrier to produce a solvent liquefaction effluent comprising a liquefied biomass comprising the lignocellulosic material and unconverted solid biomass,

[0134] a slurry hydroconversion reactor configured to process the solvent liquefaction effluent comprising the liquefied biomass comprising the lignocellulosic material and unconverted solid biomass in the presence of a slurry hydroconversion catalyst and hydrogen in a slurry hydroconversion zone and under slurry hydroconversion conditions to produce a slurry hydroconversion effluent, and

[0135] a hydrotreating reactor configured to process the slurry hydroconversion effluent by subjecting the slurry hydroconversion effluent to a hydrodeoxygenation catalyst and under hydrodeoxygenation reaction conditions to produce a hydrodeoxygenated liquid effluent, and subject the hydrodeoxygenated liquid effluent to a hydrogenation catalyst and under hydrogenation reaction conditions to produce a liquid hydrocarbon product.

[0136] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the solvent liquefaction reactor is further configured to convert about 50% to about 70% of the solid biomass feedstock comprising the lignocellulosic material to a liquid phase and a gas phase.

[0137] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the slurry hydroconversion conditions comprise a pressure in a range of from about 20 bar to about 200 bar and a reactor temperature of about 500°F to about 800°F.

[0138] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the slurry hydroconversion reactor is further configured to convert greater than about 90% of the solid biomass feedstock comprising the lignocellulosic material to a liquid phase and a gas phase in the slurry hydroconversion reactor.T-12604-W001 (538-356 PCT)

[0139] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the system further comprises one or more separation units configured to fractionate the liquid hydrocarbon product at a selected fractionation temperature to obtain individual fractions, wherein a given individual fraction is a sustainable aviation fuel.

[0140] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, another given individual fraction is one or more of a renewable gasoline or a renewable diesel fuel.

[0141] Various features disclosed herein are, for brevity, described in the context of a single embodiment, but may also be provided separately or in any suitable sub-combination. All combinations of the embodiments are specifically embraced by the illustrative embodiments disclosed herein just as if each and every combination was individually and explicitly disclosed. In addition, all sub-combinations listed in the embodiments describing such variables are also specifically embraced by the present disclosure and are disclosed herein just as if each and every such sub-combination was individually and explicitly disclosed herein.

[0142] While the above description contains many specifics, these specifics should not be construed as limitations of the invention, but merely as exemplifications of preferred embodiments thereof. Those skilled in the art will envision many other embodiments within the scope and spirit of the invention as defined by the claims appended hereto.

Claims

T-12604-W001 (538-356 PCT)WHAT IS CLAIMED IS:

1. A process for upgrading a solid biomass feedstock, comprising:processing, in a solvent liquefaction reactor, a slurry feed comprising a solid biomass feedstock comprising a lignocellulosic material and a liquid carrier under solvent liquefaction conditions to produce a solvent liquefaction effluent comprising a liquefied biomass comprising the lignocellulosic material and unconverted solid biomass feedstock;processing, in a slurry hydroconversion reactor, the solvent liquefaction effluent comprising the liquefied biomass comprising the lignocellulosic material and unconverted solid biomass feedstock in the presence of a slurry hydroconversion catalyst and hydrogen in a slurry hydroconversion zone and under slurry hydroconversion conditions to produce a slurry hydroconversion effluent; andprocessing, in a hydrotreating reactor, the slurry hydroconversion effluent by subjecting the slurry hydroconversion effluent to a hydrodeoxygenation catalyst and under hydrodeoxygenation reaction conditions to produce a hydrodeoxygenated liquid effluent, and subjecting the hydrodeoxygenated liquid effluent to a hydrogenation catalyst and under hydrogenation reaction conditions to produce a liquid hydrocarbon product.

2. The process according to claim 1, wherein the lignocellulosic material comprises a cellulosic material, a hemicellulosic material and lignin.

3. The process according to claim 2, wherein the solid biomass feedstock is ground, pulverized, chipped or in a particulate, pellet, powder, shaving, chip, dust, or pulverized form, or a combination thereof.

4. The process according to any one of claims 1-3, wherein the liquid carrier is one of a hydrocarbon liquid carrier or an oxygenated liquid carrier.

5. The process according to any one of claims 1-4, wherein the slurry feed comprises from about 5 wt. % to about 35 wt. % of the solid biomass feedstock and from about 65 wt. % to about 95 wt. % of the liquid carrier.T-12604-W001 (538-356 PCT)6. The process according to any one of claims 1-5, wherein about 50% to about 70% of the solid biomass feedstock comprising the lignocellulosic material is converted to a liquid phase and a gas phase in the solvent liquefaction reactor.

7. The process according to any one of claims 1-5, wherein greater than about 90% of the solid biomass feedstock comprising the lignocellulosic material is converted to a liquid phase and a gas phase in the slurry hydroconversion reactor.

8. The process according to any one of claims 1-7, wherein processing the slurry feed comprising the solid biomass feedstock comprising the lignocellulosic material and the liquid carrier is carried out in the absence of hydrogen.

9. The process according to any one of claims 1-8, wherein the liquefied biomass is cooled to allow for oligomerization to occur to convert a portion of light liquid hydrocarbonaceous products into heavy hydrocarbons in the diesel range.

10. The process according to any one of claims 1-9, wherein the slurry hydroconversion conditions comprise a pressure in a range of about 20 bar to about 200 bar and a reactor temperature of about 500°F to about 800°F.

11. The process according to any one of claims 1-10, wherein the slurry feed comprising the solid biomass feedstock comprising the lignocellulosic material and the liquid carrier is formed by mixing the solid biomass feedstock comprising the lignocellulosic material and the liquid carrier upstream of the solvent liquefaction reactor.

12. The process according to any one of claims 1-11, further comprising:passing the slurry hydroconversion effluent to one or more separation units to separate at least a portion of a heavy liquid bottom product from the slurry hydroconversion effluent; andT-12604-W001 (538-356 PCT)combining the heavy liquid bottom product with the solid biomass feedstock comprising the lignocellulosic material as the liquid carrier upstream of the solvent liquefaction reactor as part of a continuous process.

13. The process according to any one of claims 1-11, further comprising fractioning the liquid hydrocarbon product at a selected fractionation temperature to obtain individual fractions, wherein a given individual fraction is a sustainable aviation fuel.

14. The process according to claim 13, wherein another given individual fraction is one or more of a renewable gasoline or a renewable diesel fuel.

15. A system, comprising:a solvent liquefaction reactor configured to process a slurry feed comprising a solid biomass feedstock comprising a lignocellulosic material and a liquid carrier to produce a solvent liquefaction effluent comprising a liquefied biomass comprising the lignocellulosic material and unconverted solid biomass;a slurry hydroconversion reactor configured to process the solvent liquefaction effluent comprising the liquefied biomass comprising the lignocellulosic material and unconverted solid biomass in the presence of a slurry hydroconversion catalyst and hydrogen in a slurry hydroconversion zone and under slurry hydroconversion conditions to produce a slurry hydroconversion effluent; anda hydrotreating reactor configured to process the slurry hydroconversion effluent by subjecting the slurry hydroconversion effluent to a hydrodeoxygenation catalyst and under hydrodeoxygenation reaction conditions to produce a hydrodeoxygenated liquid effluent, and subject the hydrodeoxygenated liquid effluent to a hydrogenation catalyst and under hydrogenation reaction conditions to produce a liquid hydrocarbon product.

16. The system according to claim 15, wherein the solvent liquefaction reactor is further configured to convert about 50% to about 70% of the solid biomass feedstock comprising the lignocellulosic material to a liquid phase and a gas phase.T-12604-W001 (538-356 PCT)17. The system according to claim 15 or 16, wherein the slurry hydroconversion conditions comprise a pressure in a range of from about 20 bar to about 200 bar and a reactor temperature of from about 500°F to about 800°F.

18. The system according to any one of claims 15-17, wherein the slurry hydroconversion reactor is further configured to convert greater than about 90% of the solid biomass feedstock comprising the lignocellulosic material to a liquid phase and a gas phase in the slurry hydroconversion reactor.

19. The system according to any one of claims 15-18, further comprising one or more separation units configured to fractionate the liquid hydrocarbon product at a selected fractionation temperature to obtain individual fractions, wherein a given individual fraction is a sustainable aviation fuel.

20. The system according to claim 19, wherein another given individual fraction is one or more of a renewable gasoline or a renewable diesel fuel.

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