Processing of solid biomass in an ebullated bed residue hydrocracking unit

Abstract

A solid biomass ebullated bed hydroconversion process that is useful for producing renewable fuels. The process comprises feeding solid biomass feedstock and liquid feedstock to an ebullated bed hydrocracking reactor. The ebullated bed hydrocracking reactor comprises an ebullated bed hydrocracking catalyst. The solid biomass feedstock and the liquid feedstock is contacted with the ebullated bed hydrocracking catalyst under hydrocracking process conditions in the presence of hydrogen to convert the solid biomass feedstock and the liquid feedstock to one or more liquid and / or gas products. The one or more liquid and / or gas products may be withdrawn from the reactor or further reacted to produce other desirable product(s).

Description

PROCESSING OF SOLID BIOMASS IN AN EBULLATED BED RESIDUE HYDROCRACKING UNITCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 761,881, filed February 21, 2025, the disclosure of which is incorporated herein by reference in its entirety.FIELD OF THE DISCLOSURE

[0002] This application relates to processes and systems for processing biomass with hydrocarbons.BACKGROUND AND SUMMARY OF THE DISCLOSURE

[0003] Renewable fuels (biofuels) are seen as being important to reduce carbon and greenhouse emissions. Biofuels derived from food are fuels typically made from food sources produced on arable land, while biofuels derived from non-food sources are typically produced from lignocellulosic biomass like forestry residuals or agricultural residues / waste. Renewable fuels derived from non-food sources are often preferred over biofuels derived from competing biomass food sources. Typical non-food source feedstocks include wood, grasses, algae, crop byproduct, municipal solid waste, and the like.

[0004] While lignocellulosic materials, such as wood, algae, agriculture products and wastes, etc., are abundant renewable feedstocks it has been a challenge to convert them into fuels reliably and competitively. Traditionally the solid lignocellulosic materials (biomass) are converted in two steps: they are first liquified via pyrolysis or hydropyrolysis to generate unstable pyrolysis oils together with significant amount of coke or biochar formation; secondly, the pyrolysis oils, after some pretreatment or H2 saturation to remove easy-to-polymerize olefins, are further upgraded in a hydroconversion step (hydrotreating / hydrocracking) to remove oxygen and contaminates. These conventional processes are very capital and energy intensive.

[0005] What is needed are new cost-effective processes for processing biomass. It would further be beneficial if such processes provided for the direct use of solid biomass in a hydroconversion process for producing renewable fuels (or products useful to make renewable fuels). Further benefits would be achieved if the new processes reduced or eliminated pre-processing of the solid biomass and / or allowed for the use of conventional catalysts and catalyst support materials. It would further be beneficial if the process minimized fossil fuel use and / or if the renewable fuel products were similar in chemical composition and / or performance to conventional fossil fuel products produced without biomass. Advantageously, the processes described herein provide at least one of the aforementioned benefits.

[0006] In a representative embodiment the process described herein pertains to a solid biomass ebullated bed hydroconversion process that is useful for producing renewable fuels. The process comprises feeding solid biomass feedstock and liquid feedstock to an ebullated bed hydrocracking reactor. The ebullated bed hydrocracking reactor comprises an ebullated bed hydrocracking catalyst. Solid biomass feedstock and the liquid feedstock are contacted with the ebullated bed hydrocracking catalyst under hydrocracking process conditions in the presence of hydrogen to convert the solid biomass feedstock and the liquid feedstock to one or more liquid and / or gas products. The one or more of the liquid and / or gas products may be withdrawn from the reactor or further reacted to produce other desirable product(s). Multiple stages of ebullated beds may be employed with feeding of solid biomass in a non-slurry form and recycle of unconverted liquid feedstock to facilitate higher conversion and / or efficient processing of feedstock.BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Figure 1 shows one embodiment of an ebullated bed reactor system configuration to process residue and solid biomass in an EB residue hydrocracking unit, by injecting solid biomass to the last stage of an EB reactor system, i.e., using only one stage of an EB reactor for biomass conversion, and to obtain high biomass conversion.

[0008] Figure 2 shows an embodiment of an ebullated bed reactor system configuration to process residue and solid biomass in an EB residue hydrocracking unit, e.g., by directly injecting solid biomass to the third stage of an EB reactor, without any carrier oil, and to obtain high biomass conversion.

[0009] Figure 3 shows an embodiment of an ebullated bed reactor system configuration to add solid biomass to a reaction section including, e.g., by direct injection of solid biomass, without any solvent or carrier oil, via a pressure transfer vessel, extruder, rotatory valve, lock hoppers, or via pneumatic addition with carrier gas. Solid biomass can also be added to an EB reactor via an EB catalyst addition system or directly to, e.g., the third EB reactor in series, as shown in Figure 3 with recycle of unconverted oil.DETAILED DESCRIPTION

[0010] Although illustrative embodiments of one or more aspects are provided herein, the disclosed processes may be implemented using any number of techniques. The disclosure is not limited to the illustrative or specific embodiments, any drawings, and any techniques illustrated herein, including any exemplary designs and embodiments illustrated and described herein, and may be modified within the scope of the appended claims along with their full scope of equivalents.

[0011] The following description of embodiments provides non-limiting representative examples referencing numerals to particularly describe features and teachings of different aspects of the invention. The embodiments described should be recognized as capable of implementation separately, or in combination, with other embodiments from the description of the embodiments. A person of ordinary skill in the art reviewing the description of embodiments should be able to learn and understand the different described aspects of the invention. The description of embodiments should facilitate understanding of the invention to such an extent that other implementations, not specifically covered but within the knowledge of a person of skill in the art having read the description of embodiments, would be understood to be consistent with an application of the invention.Definitions

[0012] Unless otherwise indicated, the following terms, if used, have the meanings as defined hereinbelow.

[0013] The term “hydroconversion” refers to processes or steps performed in the presence of hydrogen for the hydrocracking, hydrogenation, hydroisomerization and / or dewaxing, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallation, hydrodechlorination, hydrodecarboxylation, hydrodecarbonylation and / or hydrodearomatization (e.g., impurities) of a hydrocarbon or biomass feedstock, and / or for the hydrogenation of unsaturated compounds in the feedstock. Depending on the type of hydrocracking and the reaction conditions, products of hydrocracking processes may have improved aromatic content, oxygen content, viscosities, viscosity indices, saturates content, low temperature properties, volatilities and depolarization, for example.

[0014] The term “conventional catalyst support” is used according to the normal usage in the art and includes typical catalyst support materials such as alumina, silica-alumina, activated carbon, zeolites and non-zeolite molecular sieves, and the like.

[0015] “Catalyst precursor” refers to a compound containing one or more catalytically active metals, from which compound the catalyst is eventually formed, and which compound may be catalytically active as a hydroprocessing catalyst. An example is a sulfided metal precursor. Suitable catalyst precursors may include, for example, organometallic compounds known in the art, such as Mo octoate.

[0016] “Biomass” is intended to refer to any suitable biomass feedstock, including biomass that has not been chemically processed or modified prior to being used in the process, as well as biomass that has been mechanically and / or chemically modified. Chemically processed or modified biomass materials include, e.g., lignocellulosic materials that have been treated toremove or reduce the content of certain components, or modify such components, such as the removal of cellulose or hemicellulose or the modification of lignin. Other modified biomass materials may include biomass materials that have been modified through torrefaction, or biomass treated using slow pyrolysis, fast or flash pyrolysis, hydrothermal liquefaction, hydropyrolysis, kraft processing, and the like. Biomass materials may include mechanically modified biomass materials or dried biomass materials. Thermally processed biomass materials may be “biomass” materials within the context of the invention, including when such biomass materials are chemically modified, e.g., pyrolysis products derived from biomass. Typical drying processes do not alter the biomass composition and only remove moisture and are therefore not chemical modifications.

[0017] The term “pore volume”, as used to describe the porosity of solid biomass, may be described in terms of the “wet pore volume” and the “pore volume” determined by mercury intrusion. The “incipient wet pore volume” or “wet pore volume” is measured by the incipient wetness impregnation method. In the method, an amount of dried biomass is impregnated with a liquid, typically water, by capillary action until all the biomass pores are saturated. The wet “pore volume” is calculated by dividing the total volume of water absorbed in the biomass pores by the total weight of the solid biomass. The mercury intrusion pore volume of the solid biomass is measured according to ASTM D4284 and is typically provided by a commercial mercury intrusion porosimeter.

[0018] The Periodic Table of the Elements referred to in this disclosure is the CAS version published by the Chemical Abstract Service in the Handbook of Chemistry and Physics, 72nd edition (1991-1992).

[0019] Unless otherwise specified, the recitation of a genus of elements, materials, or other components from which an individual component or mixture of components can be selected is intended to include all possible sub-generic combinations of the listed components and mixtures thereof. Also, "include" and its variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that may also be useful in the materials, compositions, and methods of this invention.

[0020] General Process

[0021] Generally, the inventive process is a solid biomass ebullated bed hydroconversion process to produce, for example, renewable fuels. Solid biomass feedstock and liquid feedstock are fed to an ebullated bed hydrocracking reactor comprising an ebullated bed hydrocracking catalyst.

[0022] The feeding may be done in a number of different ways depending upon the equipment and ingredients. In particularly preferred embodiments the solid biomass feedstock (with or without slurry mixed with it) is directly fed to the ebullated bed hydrocracking reactor (or to one or more of multiple ebullated bed reactors connected in series) separately from the liquid feedstock as opposed to fed co-currently or with a carrier oil. In some embodiments the solid biomass feedstock is mixed with liquid feedstock such that the solid biomass feedstock absorbs or becomes impregnated with the liquid before or during the feeding. However, the solid biomass feed does not comprise so much liquid that it is a slurry, dispersion, or the liquid is a continuous phase for the biomass feedstock during injection. Once the separately fed solid biomass feedstock and the liquid feedstock are in the one or more ebullated beds they are contacted with a hydrocracking catalyst under hydrocracking process conditions in the presence of hydrogen.

[0023] The biomass may undergo various hydroconversion reactions within the EB reactors, including, but not limited to, hydrocracking, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenization, hydrodemetallization, hydrodechlorination, hydrodecarboxylation, hydrodecarbonylation, hydrodearomatization, or a combination thereof. This converts the solid biomass feedstock and the liquid feedstock to one or more liquid and / or gas products which may be withdrawn from the reactor. Such products may vary depending upon the starting ingredients and the reaction conditions but typically may include, for example, one or more of naphtha, jet fuel, diesel, vacuum gas oil, or unconverted oil or any mixture thereof.

[0024] The amounts of solid biomass and liquid feedstock may vary depending upon the specific composition of each and the desired products. The feeds to the hydroconversion reactor may generally comprise 0-90 wt.% liquid feedstock, and 1-80 wt.% solid biomass feedstock. The ebullated bed reactor stage or stages are generally loaded with about 40 to about 60% catalyst in the reactor. One or more liquid products may also be recycled to the hydroconversion reactor. In some embodiments the feeds to the hydrocracking reactor comprise at least about 10 wt.% solid biomass and 0-20 wt.% liquid feedstock. If the solid biomass feed comprises a liquid feedstock then in some embodiments the solid biomass feed to the hydrocracking reactor comprises about 80-100 wt.% solid biomass and 0-20 wt.% liquid feedstock.Biomass

[0025] The solid biomass employed may generally include a wide variety of available materials. For example, the solid biomass may comprise a solid biomass component selected from wood or wood mill byproduct, tree leaves, grass, algae, crop byproduct, municipal solid waste, or acombination thereof, optionally, wherein the solid biomass component is ground, pulverized, chipped or in a particulate, pellet, powder, shaving, chip, dust, or pulverized form, or a combination thereof. Any biomass may be used, including, but not limited to, hard wood, soft wood, algae, crop byproduct, etc. Biomass materials can be crushed or otherwise treated to any desired size or size range, e.g., to 50 microns to 10 mm, or into wood chips up to 3 cm in length, and the like.

[0026] The biomass may be used in any form, e.g., it may be chemically processed or modified or may be unprocessed or unmodified. The solid biomass may comprise lignocellulosic materials that have not been chemically processed. In some embodiments, certain modified biomass materials such as lignin, e.g., from a papermaking process, may also be used as porous solid biomass within the context of the invention. In other embodiments, the solid biomass may include chemically modified components, e.g., to increase the absorption and impregnation of oil and / or water-based catalyst precursors.

[0027] In some embodiments the solid biomass feedstock comprises solid biomass selected from wood or wood mill byproduct, tree leaves, grass, algae, crop byproduct, lignin-containing solids, municipal solid waste, or a combination thereof. Such biomass may be ground, pulverized, chipped or in a particulate, pellet, powder, shaving, chip, dust, or pulverized form, or a combination thereof.

[0028] In some embodiments the solid biomass feedstock may be mixed with a recycle stream, a hydrocarbon oil diluent, or a combination thereof. Such components to be mixed with the solid biomass feedstock are not particularly limited and may include an aromatic diluent selected from fluid catalytic cracking (FCC) slurry oils, main column bottoms (MCB), heavy cycle oil (HCO), medium cycle oil (MCO), decant oil (DCO), petroleum-derived pyrolysis oil, steam cracker residue oil, or a combination thereof.

[0029] In general, any suitable hydroconversion process conditions may be used. For example, typical hydroconversion (hydrocracking) process conditions include operation within a temperature range of about 600-950°F, a reactor pressure of about 300-3000 psig, an average residence time of from 10 min to 10 hrs, and a space velocity of about 0.1, or 0.2 up to 5.0, or about 0.05 up to 5.0, or about 0.3 up to to 2.0 hr-1. Mixing within the reactor helps to improve solids dispersion and the reactor thermometry and may be accomplished using mechanical mixing, liquid recirculation, gas bubbling, and the like.

[0030] In some embodiments, the hydrocracking process conditions include operation within a temperature range of about 700-850°F, a reactor pressure of about 1500-3000 psig, an LHSV of about 0.1 to 1.0 hr-1, and a hydrogen to feed ratio of 2000 to 8000 SCF / bbl. Advantageously, insome embodiments the coke yield may be less than about 3 wt.%, or less than about 2 wt.%, or less than about 1 wt.% of the solid biomass fed to the process.

[0031] If desired, the process may comprise two or more stages of ebullated bed reactors, or two ebullated bed reactors, or three ebullated bed reactors. The ebullated bed reactors may be connected in any desired manner and in some embodiments the reactors are fluidly connected in series. If connected in series, then it may be useful to feed the liquid feedstock to a first ebullated bed reactor and then feed the products to a second ebullated bed reactor. Products from the second ebullated bed reactor may then be separated in a convenient manner. For example, an interstage separator may be employed to provide a heavy bottoms stream which may then, if desired, be fed to a third ebullated bed reactor. Products from any ebullated reactor, e.g., the second ebullated bed reactor or third ebullated bed reactor may be further separated and / or fractionated to provide hydroconversion process products comprising one or more of naphtha, jet fuel, diesel, vacuum gas oil, or unconverted oil.Catalyst

[0032] The solid catalyst is generally pre-loaded to the ebullated bed reactor before operation of the system. During operation, fresh catalyst may be added to the reactor via a catalyst addition pipe and spent catalyst may be removed through a withdrawal pipe. . Transfer of the catalyst to the reactor may be through a variety of single or combined means, including, e.g., the use of a pipe, pressure transfer vessel, extruders, a rotatory valve, or a lock hopper.

[0033] The catalysts in the EB reactors are typical extrudate hydrocracking catalysts for EB service. The catalyst in each reactor can be the same or different. The catalyst may be in sulfide form, comprising at least one Group VIB metal such as Mo or W, or a combination thereof, or at least one Group VIII metal such as Co, Ni or Fe, or at least one Group IIB metal such as Zn, or a combination thereof. The catalysts may be unsulfided or sulfided before being added to the reactor. Suitable catalysts may include, e.g., molybdenum sulfide, nickel sulfide, molybdenum nickel sulfide, molybdenum cobalt sulfide, tungsten nickel sulfide, iron sulfide, zinc sulfide, or iron zinc sulfide. The catalyst can also be the precursor of those catalysts which can be activated in the EB reactors.

[0034] In some embodiments the ebullated bed hydrocracking catalyst may be in the form of self-supported pellets, extrudate, or other form dispersed within the reactor. In some embodiments, the ebullated bed hydrocracking catalyst comprises a supported catalyst wherein the support is selected from alumina, silica, silica-alumina, activated carbon, clay, zeolite, or a combination thereof.Liquid Feedstock

[0035] The liquid feedstock may generally comprise a heavy boiling point component having a boiling point of at least about 800°F. For example, while not limited thereto, the liquid feedstock may typically be selected from vacuum gas oil, atmospheric residue, vacuum residue, FCC heavy cycle oil or decanted oil, FCC medium cycle oil, hydrocracker unconverted oil, or a combination thereof. The heavy boiling point component having a boiling point of at least about 800°F may be present in the liquid feedstock in an amount of up to about 50 wt.%, or 40 wt.%, or 30 wt.%, or 20 wt.%, or 10 wt.%, or in the range from about 10-50 wt.%, or 10-40 wt.%, or 10-30 wt.%, or 20-30 wt.%. The liquid feedstock may comprise one or more components having a high boiling point of at least about 650°F, or 675°F, or 700°F, or 725°F, or 750°F. The amount of the liquid feedstock component having a high boiling point present in the liquid feedstock may be at least about 10 wt.%, or 20 wt.%, or 30 wt.%, or 40 wt.%, or 50 wt.%, or 60 wt.%, or 70 wt.%, or 80 wt.%, or 90 wt.% of the liquid feedstock.

[0036] In some embodiments liquid feedstock comprises one or more components having a high boiling point of at least about 650°F, or 675°F, or 700°F, or 725°F, or 750°F. The amount of the liquid feedstock component having a high boiling point present in the liquid feedstock may vary and in some embodiments it is at least about 10 wt.%, or 20 wt.%, or 30 wt.%, or 40 wt.%, or 50 wt.%, or 60 wt.%, or 70 wt.%, or 80 wt.%, or 90 wt.% of the liquid feedstock.

[0037] In some embodiments the liquid feedstock comprises a heavy boiling point component having a boiling point of at least about 800°F, and / or the liquid feedstock is a hydrocarbon residue feedstock selected from atmospheric residue, vacuum residue, bitumen, asphalt, deasphalted oil, deasphalter pitch, tar, shale oil residue, coal-derived residue, tall oil pitch, waste plastics, or a combination thereof. The amount of the heavy boiling point component having a boiling point of at least about 800°F may vary and in some embodiments it is present in an amount of up to about 97 wt.%, or up to about 95 wt.%„ or up to about 90 wt.%„ or up to about 80 wt.%„ or up to about 70 wt.%„ or up to about 60 wt.%, or up to amounts of about 50 wt.%, or 40 wt.%, or 30 wt.%, or 20 wt.%, or 10 wt.%, or in the range from about 10-50 wt.%, or 10-40 wt.%, or 10-30 wt.%, or 20-30 wt.%, or 50-97%, or 50-90%, or 20-80%.

[0038] The liquid feedstock may further comprise a renewable feedstock, such as lipid (e.g., vegetable oil, including used cooking oil, seed oils, animal fats, waste oils, algae oils, and the like), renewable biocrude, intermediate and / or product streams from thermochemical processes (e.g., pyrolysis, gasification and subsequent upgrading, and / or liquefaction), or any product or byproduct of a process using a renewable feedstock like tall oil and / or tall oil pitch, hydrothermal liquefaction product, distillation bottoms, or a combination thereof. The liquidfeedstock may further comprise a feedstock derived from recycled or recovered materials (sometimes referred to as circular materials). While not limited thereto, suitable examples of recycled or recovered materials include polymers, plastics, rubbers, tire-derived pyrolysis oil, or a combination thereof.

[0039] While it is less preferred the liquid feedstock may be combined with a solid biomass feedstock before being directly fed to a hydroconversion reactor. All or part of any recycled liquid product may be included as part of the liquid feedstock.Figures 1-3 Process Description

[0040] Figures 1, 2, and 3 show representative configurations for an ebullated bed hydrocracking reactor system. While not shown, hydrogen is typically injected into each system as appropriate to convert the separately introduced solid biomass and liquid feedstocks to a desired liquid and / or gas products. Figure 1 shows an ebullated bed reactor system configuration to process residue 10 and solid biomass 20 in an EB residue hydrocracking unit comprising a first stage 30 and a second stage 40 with inter-stage separation / fractionation (ISF) 50 therebetween, by injecting solid biomass 20 to the last stage 40 of EB reactor, i.e., using only one stage of EB reactor for biomass conversion, and obtain high biomass conversion. Separation and fractionation system 60 produces other products 70 and unconverted oil, e.g., vacuum tower bottoms 80.

[0041] Figure 2 shows an ebullated bed reactor system configuration to process residue 10 and solid biomass 20 in an EB residue hydrocracking unit with stage one 30, stage two 40 and stage three 90 with ISF 50 therebetween, by directly injecting solid biomass 20 to the third stage of EB reactor 90, without any carrier oil, and obtain high biomass conversion. Unconverted oil 80 may be removed or recycled recycled to one or more of the reactor stages (e.g., via 100 as shown in Figure 4).

[0042] Figure 3 shows an ebullated bed reactor system configuration, according to the system of Figure 2, with solid biomass fed to a reaction section including, e.g., direct injection of solid biomass, without any solvent or carrier oil, via a pressure transfer vessel, extruder, rotatory valve, lock hoppers, or via pneumatic addition with carrier gas. If desired, additionally or alternatively, solid biomass can also be added to one of the EB reactors in Figures 1, 2, and 3 via an EB catalyst addition system. Unconverted oil 80 may be removed and / or recycled via 100 to one or more of the stages.

[0043] The systems in Figures 1-3 may be employed in an ebullated-bed (EB) hydrocracking process to process solid biomass with hydrocarbon residue which achieves high biomass conversion even with one single stage of EB reactor.

[0044] The process may include, if desired, at least two stages of EB reactors, preferably two to three stages, to convert residue feedstocks with hydrogen and optional with aromatic diluent to control product sedimentation. The hydrocarbon residue is first delivered to the first EB reactor with typical EB hydrocracking catalyst. The residue is partially converted, the first reactor effluent enters an optional inter-stage separator, and the heavy stream further hydrocracked in the next EB stage. Solid biomass is either directly injected to the first EB stage, without any premixing with carrier oils, or it is injected to the last stage of EB reactor, with or without carrier oil. The final products pass through separation and fractionation sections to obtain naphtha, jet fuel, diesel, vacuum gas oil and unconverted oil.

[0045] The hydrocarbon residue feed includes, but is not limited to, at least one selected from atmospheric residue, vacuum residue, bitumen, asphalt, deasphalted oil, deasphalter pitch, tar, shale oil residue, coal-derived oil residue, tall oil pitch, and waste plastics.

[0046] Aromatic diluent includes, but is not limited to, fluid catalytic cracking (FCC) slurry oils such as main column bottoms (MCB), heavy cycle oil (HCO), medium cycle oil (MCO) and decant oil (DCO), petroleum-derived pyrolysis oil and steam cracker residue oil, or a combination thereof.

[0047] The solid biomass feed includes, but is not limited to, at least one selected from wood, tree leaves, grass, algae, crop byproducts, lignin containing solids, municipal solid waste containing lignocellulosic fraction, etc. It can be fed into the first stage of EB reactor in solid state, without any solvent or carrier oils, via pressure transfer vessel, extruder, rotatory valve, lock hoppers, or via pneumatic addition with carrier gas. It may also be added to the first EB reactor via the EB catalyst addition system.

[0048] The solid biomass may also be injected into the last stage of EB reactor in solid form without any addition of carrier oil, in the similar way as it is injected into the first stage of EB reactor. It can be also injected into the last stage of EB reactor as a slurry stream after mixing with aromatic diluent or recycled heavy VGO generated in the unit. The solid biomass may be in powder form to be dispersed into liquid carrier or transported via solid feeding system.

[0049] The catalysts in the EB reactors are typical extrudate hydrocracking catalysts for EB service. The catalyst in each reactor can be the same or different. The catalyst is usually in sulfide form, comprising at least one Group VIB metal such as Mo or W, or at least one Group VIII metal such as Co, Ni or Fe, or at least one Group IIB metal such as Zn, or a combination thereof, e.g., molybdenum sulfide, nickel sulfide, molybdenum nickel sulfide, molybdenum cobalt sulfide, tungsten nickel sulfide, iron sulfide, zinc sulfide, or iron zinc sulfide. It can also be the precursor of those catalysts which can be activated in the EB reactors.

[0050] EB catalyst is periodically added and withdrawn from EB reactors to maintain a steady performance. The catalyst withdrawn from a latter EB stage can be added to an upstream EB stage. The biomass solids can also be added to the reactor via the catalyst addition system or added together with the EB catalyst.

[0051] When two or more stages of EB reactors are used, optionally an inter-separator can be used to remove light-ends, and thus only heavy unconverted fractions are fed to next EB stage, which will make the EB reactor more effective.

[0052] All feeds in reactors undergo various reactions in the presence of hydrogen and catalyst, such as hydrogenation, hydrocracking, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenization, hydrodemetallization, decarbonylation, decarboxylation, etc. The desired processing conditions are: liquid hourly space velocity at 0.1 to 1 hr-1, pressure at 1500-3000 psig, temperature at 700 to 850°F, and H2 to feed ratio at 2000-8000 SCF / bbl.

[0053] Unreacted hydrogen may be recycled back to the front-end reactor.EXAMPLESExample 1

[0054] A 1 -liter autoclave reactor is used to simulate performance in an EB reactor, which is charged with 400 grams of vacuum residue and cycle oil mixture, 100 g wood sawdust and 4.4 grams of MoNi EB catalyst. The reactor is pressurized with hydrogen to 2500 psig and heated up to 805°F. After reacting for two hours at 805°F in flowing hydrogen at 2000 SCF / bbl, the reactor is quenched down to 150°F. Subsequently, the main product in reactor and the light product and water in a downstream knockout pot are drained and analyzed. The solids in the product, including spend catalyst and coke, are separated from liquid with filtration and analyzed for composition.

[0055] The conversion of solid biomass is calculated as follows: Biomass Conversion = 1-(Weight of Coke from Biomass) / (Weight of Biomass Feed). At the end of experiment, 1.3 g of coke is generated from wood sawdust. Therefore, the solid biomass conversion is 98.7%.

[0056] The VR (1075°F+) conversion is calculated as follows: VR (1075°F+) Conversion = 1-(Weight of 1075°F+ in product) / (Weight of 1075°F+ in Residue Feed). The VR (1075°F+) conversion of hydrocarbon residue is 75%.Example 2

[0057] A case study of biomass processing in a commercial EB unit based on kinetics developed from various lab and commercial studies. There are two stages of EB reactors. The residue is VR which is injected to the first EB reactor. Solid biomass is directly injected to the second stage of EB reactor, without any carrier oil. High conversion of solid biomass is achieved.

[0058] Feed - Residue (VR) 170.53 MTPH; Biomass (wood) 42.63 MTPH; H2 (Net Consumption) 4.91 MTPH

[0059] Reactor Conditions - Pressure 2500 psig; EB Rx Temperature 790 °F; LHSV 0.15 hr-1

[0060] Products - H2S 7.31 MTPH; NH3 0.63 MTPH; Liquid Oils 137.61 MTPH; Unconverted VR 34.11 MTPH; Other Gases (C1-C4, CO, CO2) 25.03 MTPH; Water 12.79 MTPH; Coke from Biomass 0.55 MTPH; Coke from Residue 0.05 MTPHExample 3

[0061] Another case study of biomass processing in a commercial EB unit based on kinetics developed from studies. There are three stages of EB reactor. The residue is VR which is injected to the first EB reactor. Solid biomass is also injected directly to the last stage of EB reactor, without any carrier oil. High conversion of solid biomass is achieved.

[0062] Feed - Residue (VR) 272.85 MTPH; Biomass (wood) 68.21 MTPH; H2 (Net Consumption) 8.34 MTPH

[0063] Reactor Conditions - Pressure 2500 psig; EB Rx Temperature 795°F; LHSV 0.16 hr-1;

[0064] Products - H2S 11.99 MTPH; NH3 1.04 MTPH; Liquid Oils 232.58 MTPH; Unconverted VR 40.93 MTPH; Other Gases (C1-C4, CO, CO2) 41.61 MTPH; Water 20.46 MTPH; Coke from Biomass 0.68 MTPH; Coke from Residue 0.11 MTPHEmbodiments

[0065] The present disclosure is directed to at least the subject-matter described in the following numbered paragraphs:1. A solid biomass ebullated bed hydroconversion process, which is useful for producing renewable fuels, the process comprising:feeding solid biomass feedstock and liquid feedstock to an ebullated bed hydrocracking reactor comprising a first stage and a second stage, wherein the ebullated bed hydrocracking reactor comprises an ebullated bed hydrocracking catalyst;contacting the solid biomass feedstock and the liquid feedstock with the ebullated bed hydrocracking catalyst under hydrocracking process conditions in the presence of hydrogen to convert the solid biomass feedstock and the liquid feedstock to one or more liquid and / or gas products, andwithdrawing one or more of the liquid and / or gas products from the reactor; wherein the solid biomass feedstock is directly fed in a non-slurry form to the second stage of the ebullated bed hydrocracking reactor, andwherein at least a portion of unconverted liquid feedstock is recycled to the first stage, the second stage, or both.2. A solid biomass ebullated bed hydroconversion process, which is useful for producing renewable fuels, the process comprising:feeding solid biomass feedstock and liquid feedstock to an ebullated bed hydrocracking reactor, wherein the ebullated bed hydrocracking reactor comprises an ebullated bed hydrocracking catalyst;contacting the solid biomass feedstock and the liquid feedstock with the ebullated bed hydrocracking catalyst under hydrocracking process conditions in the presence of hydrogen to convert the solid biomass feedstock and the liquid feedstock to one or more liquid and / or gas products, andwithdrawing one or more of the liquid and / or gas products from the reactor; wherein, the solid biomass feedstock is directly fed in a non-slurry form to the ebullated bed hydrocracking reactor.3. The process of paragraph 2 wherein the ebullated bed hydrocracking reactor comprises a first stage and a second stage and the solid biomass feedstock is fed to the second stage.4. The process of paragraph 2 wherein at least a portion of any unconverted liquid hydrocarbon feedstock is recycled to the first stage, the second stage, or both.5. The process of paragraph 2, wherein the process provides a renewable fuel product or a product component useful to make a renewable fuel from the liquid and / or gas products, or wherein the hydroconversion process products comprise one or more of naphtha, jet fuel, diesel, vacuum gas oil, or unconverted oil.6. The process of paragraph 2, wherein the feeds to the hydrocracking reactor comprise at least about 3 wt.% solid biomass and 0-20 wt.% liquid feedstock based on the total feed.7. The process of paragraph 6 wherein the liquid feedstock comprises one or more components having a high boiling point of at least about 650°F, or 675°F, or 700°F, or 725°F, or 750°F.8. The process of paragraph 7, wherein the amount of the liquid feedstock component having a high boiling point present in the liquid feedstock is at least about 10 wt.%, or 20 wt.%, or 30 wt.%, or 40 wt.%, or 50 wt.%, or 60 wt.%, or 70 wt.%, or 80 wt.%, or 90 wt.% of the liquid feedstock.9. The process of any one of paragraphs 1-8, wherein the liquid feedstock comprises a heavy boiling point component having a boiling point of at least about 800°F, and / or wherein the liquid feedstock is a hydrocarbon residue feedstock selected from atmospheric residue, vacuum residue, bitumen, asphalt, deasphalted oil, deasphalter pitch, tar, shale oil residue, coal-derived residue, tall oil pitch, waste plastics, or a combination thereof.10. The process of paragraph 9, wherein the liquid feedstock comprises the heavy boiling point component having a boiling point of at least about 800°F in an amount of up to about 50 wt.%, or 40 wt.%, or 30 wt.%, or 20 wt.%, or 10 wt.%, or in the range from about 10-50 wt.%, or 10-40 wt.%, or 10-30 wt.%, or 20-30 wt.%.11. The process of any one of the preceding paragraphs wherein the liquid feedstock is sourced from a renewable source, a fossil source, or a mixture thereof, comprises a fossil fuel. 12. The process of any one of paragraphs 1-11, wherein the solid biomass feedstock comprises solid biomass selected from wood or wood mill byproduct, tree leaves, grass, algae, crop byproduct, lignin-containing solids, municipal solid waste, or a combination thereof, wherein the solid biomass component is ground, pulverized, chipped or in a particulate, pellet, powder, shaving, chip, dust, or pulverized form, or a combination thereof.13. The process of paragraph 12, wherein the solid biomass feedstock in a non-slurry form is mixed with a recycle stream, a hydrocarbon oil diluent, or a combination thereof.14. The process of any preceding paragraph wherein the solid biomass feedstock in a nonslurry form is directly fed to the ebullated reactor via a catalyst addition pipe, a catalyst withdrawal pipe, or a combination thereof.15. The process of paragraph 13, wherein the hydrocarbon oil diluent is an aromatic diluent selected from fluid catalytic cracking (FCC) slurry oils, main column bottoms (MCB), heavy cycle oil (HCO), medium cycle oil (MCO), decant oil (DCO), petroleum-derived pyrolysis oil, steam cracker residue oil, or a combination thereof.16. The process of any one of paragraphs 1-15, wherein the ebullated bed hydrocracking catalyst comprises a metal selected from Group VIB, Group VIII, or Group IIB of the Periodic Table, or a combination thereof and is unsulfided or sulfided before being added to the reactor.17. The process of paragraph 16, wherein the Group VIB metal is selected from Mo, W, or a combination thereof; or the Group VIII is selected from Co, Ni, Fe, or a combination thereof; or the Group IIB metal is Zn.18. The process of any one of paragraphs 1-17, wherein the ebullated bed hydrocracking catalyst comprises a supported catalyst wherein the support is selected from alumina, silica-alumina, zeolite, or a combination thereof.19. The process of paragraph 18, wherein the ebullated bed hydrocracking catalyst comprises molybdenum sulfide, nickel sulfide, molybdenum nickel sulfide, molybdenum cobalt sulfide, tungsten nickel sulfide, iron sulfide, zinc sulfide, iron zinc sulfide, or a combination thereof. 20. The process of any one of paragraphs 1-19, wherein the hydrocracking process conditions include operation within a temperature range of about 700-850°F, a reactor pressure of about1500-3000 psig, anLHSV of about 0.1 to 1.0 hr1, and a hydrogen to feed ratio of 2000 to 8000 SCF / bbl.21. The process of any one of paragraphs 1-20, wherein the coke yield is less than about 3 wt.%, or less than about 2 wt.%, or less than about 1 wt.% of the solid biomass fed to the process.22. The process of any one of paragraphs 1-21, wherein the process comprises two or more stages of ebullated bed reactors, or two ebullated bed reactors, or three ebullated bed reactors, wherein the ebullated bed reactors are fluidly connected in series.23. The process of paragraph 22, wherein the liquid feedstock is fed to a first ebullated bed reactor, the products from the ebullated bed reactor are separated in an interstage separator to provide a heavy bottoms stream, and the heavy bottoms stream is fed to a second ebullated bed reactor.24. The process of paragraph 23, wherein the liquid feedstock is fed to a first ebullated bed reactor, the products from the ebullated bed reactor are fed to a second ebullated bed reactor, the products from the second ebullated bed reactor are separated in an interstage separator to provide a heavy bottoms stream, and the heavy bottoms stream is fed to a third ebullated bed reactor. 25. The process of paragraph 23 or paragraph 24, wherein the solid biomass is directly fed to the first ebullated bed reactor or the solid biomass is fed to the second ebullated bed reactor or the solid biomass is fed to the third ebullated bed reactor.26. The process of paragraph 25, wherein products from the second ebullated bed reactor or the products from the third ebullated bed reactor are further separated and fractionated to provide hydroconversion process products comprising one or more of naphtha, jet fuel, diesel, vacuum gas oil, or unconverted oil.27. The process of paragraph 26 which further comprises recycling at least a portion of the vacuum gas oil, unconverted oil, or a mixture thereof to the first stage.

[0066] It will be understood that the invention is not limited to the embodiments described above and various modifications and improvements can be made without departing from the concepts described herein. Except where mutually exclusive, any of the features may be employed separately or in combination with any other features and the disclosure extends to and includes all combinations and sub-combinations of one or more features described herein.

Claims

WE CLAIM:

1. A solid biomass ebullated bed hydroconversion process, which is useful for producing renewable fuels, the process comprising:feeding solid biomass feedstock and liquid feedstock to an ebullated bed hydrocracking reactor comprising a first stage and a second stage, wherein the ebullated bed hydrocracking reactor comprises an ebullated bed hydrocracking catalyst;contacting the solid biomass feedstock and the liquid feedstock with the ebullated bed hydrocracking catalyst under hydrocracking process conditions in the presence of hydrogen to convert the solid biomass feedstock and the liquid feedstock to one or more liquid and / or gas products, andwithdrawing one or more of the liquid and / or gas products from the reactor; wherein the solid biomass feedstock is directly fed in a non-slurry form to the second stage of the ebullated bed hydrocracking reactor, andwherein at least a portion of unconverted liquid feedstock is recycled to the first stage, the second stage, or both.

2. A solid biomass ebullated bed hydroconversion process, which is useful for producing renewable fuels, the process comprising:feeding solid biomass feedstock and liquid feedstock to an ebullated bed hydrocracking reactor, wherein the ebullated bed hydrocracking reactor comprises an ebullated bed hydrocracking catalyst;contacting the solid biomass feedstock and the liquid feedstock with the ebullated bed hydrocracking catalyst under hydrocracking process conditions in the presence of hydrogen to convert the solid biomass feedstock and the liquid feedstock to one or more liquid and / or gas products, andwithdrawing one or more of the liquid and / or gas products from the reactor; wherein, the solid biomass feedstock is directly fed in a non-slurry form to the ebullated bed hydrocracking reactor.

3. The process of claim 2 wherein the ebullated bed hydrocracking reactor comprises a first stage and a second stage and the solid biomass feedstock is fed to the second stage.

4. The process of claim 2 wherein at least a portion of any unconverted liquid hydrocarbon feedstock is recycled to the first stage, the second stage, or both.

5. The process of claim 2, wherein the process provides a renewable fuel product or a product component useful to make a renewable fuel from the liquid and / or gas products, orwherein the hydroconversion process products comprise one or more of naphtha,jet fuel, diesel, vacuum gas oil, or unconverted oil.

6. The process of claim 2, wherein the feeds to the hydrocracking reactor comprise at least about 3 wt.% solid biomass and 0-20 wt.% liquid feedstock based on the total feed.

7. The process of claim 6 wherein the liquid feedstock comprises one or more components having a high boiling point of at least about 650°F, or 675°F, or 700°F, or 725°F, or 750°F.

8. The process of claim 7, wherein the amount of the liquid feedstock component having a high boiling point present in the liquid feedstock is at least about 10 wt.%, or 20 wt.%, or 30 wt.%, or 40 wt.%, or 50 wt.%, or 60 wt.%, or 70 wt.%, or 80 wt.%, or 90 wt.% of the liquid feedstock.

9. The process of any one of claims 1-8, wherein the liquid feedstock comprises a heavy boiling point component having a boiling point of at least about 800°F, and / or wherein the liquid feedstock is a hydrocarbon residue feedstock selected from atmospheric residue, vacuum residue, bitumen, asphalt, deasphalted oil, deasphalter pitch, tar, shale oil residue, coal-derived residue, tall oil pitch, waste plastics, or a combination thereof.

10. The process of claim 9, wherein the liquid feedstock comprises the heavy boiling point component having a boiling point of at least about 800°F in an amount of up to about 50 wt.%, or 40 wt.%, or 30 wt.%, or 20 wt.%, or 10 wt.%, or in the range from about 10-50 wt.%, or 10-40 wt.%, or 10-30 wt.%, or 20-30 wt.%.

11. The process of claim 2 wherein the liquid feedstock is sourced from a renewable source, a fossil source, or a mixture thereof comprises a fossil fuel.

12. The process of claim 2, wherein the solid biomass feedstock comprises solid biomass selected from wood or wood mill byproduct, tree leaves, grass, algae, crop byproduct, lignincontaining solids, municipal solid waste, or a combination thereof, wherein the solid biomass component is ground, pulverized, chipped or in a particulate, pellet, powder, shaving, chip, dust, or pulverized form, or a combination thereof.

13. The process of claim 12, wherein the solid biomass feedstock in a non-slurry form is mixed with a recycle stream, a hydrocarbon oil diluent, or a combination thereof.

14. The process of claim 2 wherein the solid biomass feedstock in a non-slurry form is directly fed to the ebullated reactor via a catalyst addition pipe, a catalyst withdrawal pipe, or a combination thereof.

15. The process of claim 13, wherein the hydrocarbon oil diluent is an aromatic diluent selected from fluid catalytic cracking (FCC) slurry oils, main column bottoms (MCB), heavycycle oil (HCO), medium cycle oil (MCO), decant oil (DCO), petroleum-derived pyrolysis oil, steam cracker residue oil, or a combination thereof.

16. The process of claim 2, wherein the ebullated bed hydrocracking catalyst comprises a metal selected from Group VIB, Group VIII, or Group IIB of the Periodic Table, or a combination thereof and is unsulfided or sulfided before being added to the reactor.

17. The process of claim 16, wherein the Group VIB metal is selected from Mo, W, or a combination thereof; or the Group VIII is selected from Co, Ni, Fe, or a combination thereof; or the Group IIB metal is Zn.

18. The process of claim 2, wherein the ebullated bed hydrocracking catalyst comprises a supported catalyst wherein the support is selected from alumina, silica-alumina, zeolite, or a combination thereof.

19. The process of claim 18, wherein the ebullated bed hydrocracking catalyst comprises molybdenum sulfide, nickel sulfide, molybdenum nickel sulfide, molybdenum cobalt sulfide, tungsten nickel sulfide, iron sulfide, zinc sulfide, iron zinc sulfide, or a combination thereof.

20. The process of claim 2, wherein the hydrocracking process conditions include operation within a temperature range of about 700-850°F, a reactor pressure of about 1500-3000 psig, an LHSV of about 0.1 to 1.0 hr1, and a hydrogen to feed ratio of 2000 to 8000 SCF / bbl.

21. The process of claim 2, wherein the coke yield is less than about 3 wt.%, or less than about 2 wt.%, or less than about 1 wt.% of the solid biomass fed to the process.

22. The process of claim 2, wherein the process comprises two or more stages of ebullated bed reactors, or two ebullated bed reactors, or three ebullated bed reactors, wherein the ebullated bed reactors are fluidly connected in series.

23. The process of claim 22, wherein the liquid feedstock is fed to a first ebullated bed reactor, the products from the ebullated bed reactor are separated in an interstage separator to provide a heavy bottoms stream, and the heavy bottoms stream is fed to a second ebullated bed reactor.

24. The process of claim 23, wherein the liquid feedstock is fed to a first ebullated bed reactor, the products from the ebullated bed reactor are fed to a second ebullated bed reactor, the products from the second ebullated bed reactor are separated in an interstage separator to provide a heavy bottoms stream, and the heavy bottoms stream is fed to a third ebullated bed reactor.

25. The process of claim 23, wherein the solid biomass is directly fed to the first ebullated bed reactor or the solid biomass is fed to the second ebullated bed reactor or the solid biomass is fed to the third ebullated bed reactor.

26. The process of claim 25, wherein products from the second ebullated bed reactor or the products from the third ebullated bed reactor are further separated and fractionated to provide hydroconversion process products comprising one or more of naphtha,jet fuel, diesel, vacuum gas oil, or unconverted oil.

27. The process of claim 26 which further comprises recycling at least a portion of the vacuum gas oil, unconverted oil, or a mixture thereof to the first stage.

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