Hydrotreating renewable biomass feed slurries

Abstract

For example, a renewable biomass feed slurry hydroprocessing is described, including a slurry hydroconversion process in which a feedstock containing renewable biomass components is subjected to slurry hydroconversion. The process generally involves contacting a solid biomass feedstock and a slurry hydroconversion catalyst under suitable hydroconversion conditions to convert a portion of the feedstock into liquid and / or gas products. The process can utilize raw biomass as a feedstock and does not require the use of chemically treated or modified biomass feeds. Low coke yields can be obtained.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 326,803, filed April 1, 2022, entitled “RENEWABLE BIOMASS FEED SLURRY HYDROPROCESSING,” the disclosure of which is incorporated herein in its entirety.

[0002] The present disclosure relates to renewable biomass feed slurry hydroprocessing, including, for example, slurry hydroconversion processes, in which a feedstock containing renewable biomass components is subjected to slurry hydroconversion. [Background technology]

[0003] The use of renewable resources has attracted significant attention and effort in the progress of developing alternatives to fossil fuels. The variety, availability, and versatility of various biomass materials, especially certain lignocellulosics and other carbohydrates, has generated much interest. However, despite the promise and much interest, the development and commercial use of bio-based fuel technologies has not been as successfully implemented as desired. Although several biofuel technologies have been commercialized, so-called second generation renewable feedstocks, especially second generation renewable biofuel feedstocks, have not been widely developed.

[0004] Renewable fuels (biofuels) are considered important in reducing carbon and greenhouse emissions. First generation biofuels are fuels made from food crops grown on arable land, while second generation biofuels are made from lignocellulosic biomass or agricultural residues / wastes. Unlike first generation biofuels that compete with biomass food sources, second generation renewable fuels are generally not derived from human food sources and are therefore preferred over first generation renewable fuels. Typical second generation feedstocks include wood, grass, algae, crop by-products, municipal solid waste, etc. However, second generation biomass processing usually requires more complex two-step or multi-step processes to convert the usable portion of the solid biomass into suitable feedstock. Specifically, the first step is typically to convert the solid biomass feedstock into a liquid biocrude form by pyrolysis, hydrolysis, hydrothermal liquefaction, or other process steps. Then, upgrading of the biocrude is usually further carried out using conventional refining units, such as hydrotreaters or FCC units, to produce transportation fuels.

[0005] Other difficulties associated with the prior art have resulted in fuels with low energy density, such as bioethanol, or fuels such as methanol, biodiesel, hydrogen, and methane that are not fully compatible with existing engine designs and transportation infrastructure, or dilute aqueous solutions produced that are not cost-effective for further processing. It would be a significant advantage if a simplified process for directly using solid biomass in a hydroconversion process to produce renewable fuels (or products useful for making renewable fuels), without the need for pretreatment of the solid biomass, was provided. The use of high biomass content feeds that minimize or eliminate the use of fossil fuel co-feeds is particularly desirable in light of the global attempt to utilize methods to reduce fossil fuel use. It would be highly desirable to provide a cost- and energy-efficient method of processing lignocellulosic biomass into renewable fuels with similar chemical compositions to fossil fuels, so as to alleviate the aforementioned concerns and challenges. Summary of the Invention

[0006] The present invention generally relates to the hydroprocessing of renewable biomass feed slurries. In one aspect, a slurry hydroconversion process is provided in which a feedstock containing renewable biomass components is subjected to slurry hydroconversion. The process generally includes contacting a solid biomass feedstock with a slurry hydroconversion catalyst under hydroprocessing conditions suitable for converting a portion of the feedstock into hydroconversion products (e.g., liquid and / or gas products). The process can utilize intact biomass as a feedstock and does not require the use of chemically treated or modified biomass feeds. One advantage associated with the process is that a low yield of coke may be obtained. One objective of the present invention, although not necessarily limited thereto, is to provide a simplified and effective process for making renewable fuels and / or other products from untreated biomass feedstocks.

[0007] Generally, a process according to the invention includes feeding a solid biomass feedstock, a liquid feedstock, and a slurry hydroconversion catalyst or a precursor thereof to a slurry hydroconversion reactor, contacting the solid biomass feedstock and the liquid feedstock with the slurry hydroconversion catalyst in the presence of hydrogen under hydroconversion process conditions for a time sufficient to convert a portion of the solid biomass feedstock and the liquid feedstock to one or more hydroconversion products, such as liquid and / or gas products, and removing the hydroconversion products from the reactor. The solid biomass feedstock is typically provided as an unprocessed biomass feedstock that is fed directly to the slurry hydroconversion reactor and contains biomass components that have not been chemically treated or modified prior to being fed directly to the slurry hydroconversion reactor. [Brief description of the drawings]

[0008] It is to be understood that the scope of the present invention is not limited by any of the representative drawings attached to this disclosure, but is defined by the claims of this application.

[0009] [Figure 1] 1 is a schematic diagram of an overall block diagram of an embodiment in accordance with the present invention in which solid biomass feedstock is fed directly to a reactor and separated to provide a solid biomass hydroconversion product. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0011] The following description of the embodiments provides non-limiting representative examples with reference to figures to specifically describe the features and teachings of different aspects of the present invention. It should be recognized that the described embodiments can be implemented separately or in combination with other embodiments from the description of the embodiments. Those skilled in the art who review the description of the embodiments should be able to learn and understand the different described aspects of the present invention. The description of the embodiments should facilitate the understanding of the present invention to the extent that other implementations are understood to be consistent with the application of the present invention within the knowledge of those skilled in the art who read the description of the embodiments, although not specifically covered.

[0012] Unless otherwise indicated, the following terms have the meanings defined herein below.

[0013] The term "hydroconversion" refers to a process or step carried out in the presence of hydrogen for the hydrocracking, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodechlorination, hydrodecarboxylation, hydrodecarbonylation, and / or hydrodearomatization of constituents (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 hydroconversion and reaction conditions, products of hydroconversion processes may exhibit, for example, improvements in specific gravity, acidity, aromatics content, viscosity, viscosity index, saturates content, low temperature properties, volatility, and depolarization.

[0014] The term "catalyst support" is used in its conventional sense in accordance with common usage in the art and includes typical catalyst support materials such as alumina, silica-alumina, metal oxides, zeolites and non-zeolitic materials, activated carbon, and the like.

[0015] "Catalyst precursor" refers to a compound containing one or more catalytically active metals from which a slurry catalyst is ultimately formed, which may be catalytically active as a hydrotreating catalyst. One example is an aqueous catalyst prior to the conversion step with a hydrocarbon diluent, and another example is a sulfide metal precursor. Catalyst precursors and the preparation of slurry catalysts are described in various patents, such as U.S. Pat. No. 8,802,586 and WO 2012 / 092006.

[0016] The term "intact biomass" is intended to mean a suitable biomass raw material that has not been subjected to chemical treatment and modification before being used in the process. Such chemically treated or modified biomass materials include, for example, lignocellulosic materials that have been treated to remove or reduce the content of certain components or to chemically modify such components (e.g., to remove cellulose or hemicellulose or to modify lignin). Other chemically modified biomass materials can include biomass materials modified by torrefaction or biomass processed using slow pyrolysis, fast or fast pyrolysis, hydrothermal liquefaction, hydrothermal decomposition, kraft processing, and the like. Intact biomass materials can include mechanically modified biomass materials or dried biomass materials. However, if such biomass materials are chemically modified, including, for example, pyrolysis products derived from the biomass, the heat-treated biomass materials cannot be "intact biomass" materials within the context of the present invention. Typical drying processes do not change the composition of the biomass, but merely remove moisture, and therefore are not chemically modified.

[0017] The term "pore volume" used to describe the porosity of solid biomass can be described in terms of "wet pore volume" and "pore volume" measured by mercury intrusion. "Incipient wet pore volume" or "wet pore volume" is measured by the incipient wetness impregnation method. In this method, a volume of dry biomass is impregnated with a liquid, usually water, until all the pores of the biomass are saturated by capillary action. The wet "pore volume" is calculated by dividing the total volume of water absorbed in the pores of the biomass by the total weight of the solid biomass. Mercury intrusion pore volume of solid biomass is measured according to ASTM D4284 and is usually provided by a commercially available mercury intrusion porosimeter.

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

[0019] Unless otherwise specified, the listing of a genus of elements, materials, or other components from which individual components or mixtures of components may be selected is intended to include all possible subcombinations of the listed components and mixtures thereof. Also, "include" and variations thereof are intended to be non-limiting, such that the recitation of an item in a list does not exclude other similar items that may also be useful in the materials, compositions, and methods of the invention.

[0020] In the process of the present invention, the solid biomass feedstock and the liquid feedstock are fed separately to a slurry hydroconversion reactor. The slurry catalyst can be fed separately or can be added to the reactor in combination with the liquid feedstock. Hydrogen is also typically fed to the reactor and can be combined with any of the feeds or fed separately to the reactor. The slurry hydroconversion catalyst, the liquid feedstock, and the hydrogen can be premixed in any combination or amount before being fed to the hydroconversion reactor. The slurry hydroconversion catalyst can be a precursor thereof.

[0021] The feed to the hydroconversion reactor typically comprises at least about 10% or 20% or 30% or 40% or 50% or 60% by weight of solid biomass, 0-40% by weight of liquid feedstock, and less than about 5% or less than about 2% or less than about 1% by weight of slurry hydroconversion catalyst or its precursor. One or more liquid hydrocarbon products and / or slurry catalyst may also be recycled to the hydroconversion reactor. In general, any suitable hydroconversion process conditions may be used. Typical hydroconversion process conditions include a temperature range of about 650-950° F., a reactor pressure of about 300-3500 psig, an average residence time of 10 minutes to 5 hours, and a reaction time of about 0.1-5.0, or 0.5-5.0, or 0.5-2.0 hours. -1 Mixing within the reactor aids in dispersion of solids and improves reactor temperature measurement and can be achieved by using mechanical mixing (e.g., agitators and impellers), liquid recirculation (e.g., pumps, thermosiphons), gas bubbling (e.g., bubble column reactors), etc.

[0022] Among other advantages, the present invention is the ability to use solid biomass feedstock as a direct feed to a hydrocracker, rather than chemically converting or modifying the biomass prior to use as a direct hydrocracker feed. For example, the present invention does not require the conversion of solid biomass to a liquid form, such as biocrude, prior to use. Other processes that modify the biomass prior to use in the process, such as hydrothermal decomposition, hydrothermal carbonization, torrefaction, or removal of certain carbohydrate components, such as cellulose, hemicellulose, or lignin, are also not necessarily required.

[0023] Direct injection of solid biomass according to the process, compared to simultaneous feeding of combined solid biomass and liquid feedstocks, including as a dispersion or suspension, also removes the challenges associated with the use of liquid co-feeds. Many biomass feedstocks, such as wood, grasses, and other agricultural products, are characterized by relatively low density and high pore volume, and when the biomass solids content reaches a certain range, e.g., 35-50% by weight, the liquid becomes trapped within the solids, leaving little or no free liquid. Essentially, the mixture of solid biomass and liquid results in a wet solid, rather than a slurry, suspension, or dispersion. For such processes, there is a limit to the maximum biomass content in the solid biomass and liquid co-feed. However, with direct solid biomass injection, such a limit is avoided, and the total content of solid biomass fed to the reactor (compared to any separate liquid feedstock fed to the reactor) can be much higher. Operation of the reactor under slurry hydroconversion conditions requires sufficient liquid to retain the solids in the slurry, so the solid biomass content fed directly to the reactor can be enriched by combining the liquid with any separate liquid feed produced from the hydroconversion of the solid biomass fed to the reactor.

[0024] Direct solid biomass injection allows for the realization of certain product benefits, including reduced coke yields, which are typically less than about 5% by weight, or less than about 2% by weight, or less than about 1% by weight of the solid biomass fed to the process. The oxygen content of the liquid product can also be less than about 3% by weight or less than about 1% by weight, and / or the total acid number (TAN) can be less than about 1.

[0025] Other operational advantages associated with direct feeding of solid biomass include significantly reduced energy consumption by using less liquid feedstock because direct solids injection allows for the handling of larger and more variable size biomass solids, and mitigation of biomass feedstock limitations imposed by slurry or liquid handling means (e.g., pumping).

[0026] Without being limited thereto, the process of the present invention can be used to provide renewable fuels or product components useful for making renewable fuels from liquid and / or gaseous products derived from the process.

[0027] The solid biomass feedstock can include solid biomass components selected from wood or wood mill by-products, leaves, grass, algae, crop by-products, municipal solid waste, or combinations thereof, and the solid biomass components can be ground, powdered, shingled, or in particulate, pellet, powder, shavings, chips, dust, or shingled form, or combinations thereof. The transfer of the solid biomass to the hydroconversion reactor can be by a variety of means, alone or in combination, including, for example, the use of a pressure transfer vessel, an extruder, a rotary valve, or a lock hopper. The intact biomass material can be ground or otherwise processed to any desired size or size range, such as, for example, wood chips from 50 micrometers to 10 mm, or up to 3 cm in length. The intact biomass can be dried or in a green state.

[0028] Generally, the solid biomass feedstock is provided as raw biomass feedstock, containing biomass components that have not been chemically treated or modified prior to being fed directly into the slurry hydroconversion reactor. For example, certain modified biomass materials, such as lignin from papermaking processes, are not intended to be included in the process described in, for example, U.S. Pat. No. 8,795,472 B2.

[0029] The solid biomass feedstock fed to the slurry hydroconversion reactor can undergo a variety of reactions including hydrocracking, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodechlorination, hydrodecarboxylation, hydrodecarbonylation, hydrodearomatization, or combinations thereof.

[0030] The liquid feedstock typically includes heavy boiling components having a boiling point of at least about 800°F. For example, but not limited to, the liquid feedstock can typically be selected from vacuum gas oil, atmospheric residue, vacuum residue, FCC heavy cycle oil or decant oil, FCC medium cycle oil, hydrocracker unconverted oil, or combinations thereof. The heavy boiling components having a boiling point of at least about 800°F can be present in the liquid feedstock in an amount of up to about 50%, or 40%, or 30%, or 20%, or 10% by weight, or in a range of about 10-50%, or 10-40%, or 10-30%, or 20-30% by weight. The liquid feedstock can include 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 liquid feedstock component having a high boiling point present in the liquid feedstock is at least about 10%, or 20%, or 30%, or 40%, or 50%, or 60%, or 70%, or 80%, or 90% by weight of the liquid feedstock. The liquid feedstock may further comprise renewable feedstocks selected from plastic and / or wood pyrolysis oils, lipids, vegetable oils, or combinations thereof.

[0031] Additionally, the liquid feedstock can be combined with recycled slurry hydroconversion reactor product before being fed directly to the slurry hydroconversion reactor. All or a portion of any liquid product can be recycled to the slurry hydroconversion reactor. Any recycled liquid product can be first treated to reduce or remove solids present during recycling, for example, by solid-liquid separation of the hydroconversion reactor liquid product. Typical means of separating solids from liquids can be utilized, including, but not limited to, settling, sieving, filtration, or centrifugation.

[0032] The slurry hydroconversion catalyst is typically provided in the form of fine particles dispersed within the reactor liquid reaction medium and can be a supported catalyst, an unsupported catalyst, or a combination thereof. The slurry catalyst typically comprises a metal selected from Group VIB, Group VIII, or Group IIB of the Periodic Table, or a combination thereof. The slurry hydroconversion catalyst may be unsulfided or may be presulfided prior to addition to the reactor. The slurry catalyst may also be dispersed within a hydrocarbon oil diluent. A sufficient amount of slurry catalyst is typically fed to the slurry reactor(s) for each reactor to have a slurry catalyst concentration of 100 wppm, or 300 wppm, or 500 wppm, up to about 3 wt.% (ratio of catalyst metal to feedstock). The slurry catalyst may comprise one or more different slurry catalysts, either as a single combined feed stream or as separate feeds to the reactor.

[0033] In some cases, the slurry hydroconversion catalyst comprises a non-supported catalyst selected from molybdenum sulfide, iron sulfide, nickel sulfide, zinc sulfide, zinc iron, or a combination thereof. The slurry hydroconversion catalyst can also be provided in the form of a catalyst precursor selected from an oil-soluble Group VIB metal (e.g., molybdenum) compound, an aqueous Group VIB metal (e.g., molybdenum) compound, an aqueous Group VIB metal (e.g., molybdenum) trisulfide suspension, or colloid, or a combination thereof. Still further, the slurry hydroconversion catalyst can comprise a supported catalyst, the support being selected from alumina, silica alumina, transition metal oxide, activated carbon, zeolite, or a combination thereof.

[0034] Suitable slurry catalysts, slurry catalyst precursors, and preparation of slurry catalysts are described in various patents, such as U.S. Pat. No. 8,802,586, WO 2012 / 092006, U.S. 2015 / 0329790 A1, etc. For example, suitable catalysts for use in slurry hydroprocessing systems can most often include at least one Group VIII metal (e.g., Ni and / or Co) combined with at least one Group VIB metal (e.g., Mo) on a refractory inorganic oxide support such as alumina or silica. These supported catalysts typically contain 0.5-10 wt. % of at least one Group VIII metal (calculated as metal oxide) and 1-30 wt. % of at least one Group VIB metal (calculated as metal oxide), and may contain at least one Group IIB metal (e.g., Zn). Such supported catalysts are typically produced as cylindrical pellets, spherical solids, or extrudates, which can be ground into fine powders for use as slurry catalysts. In some cases, the slurry catalyst can be a multimetallic catalyst comprising at least one non-noble Group VIII metal and at least two Group VIB metals, where the ratio of the at least two Group VIB metals to the non-noble Group VIII metals is from 10:1 to 1:10.

[0035] The slurry catalyst has the formula (M t ) a (Xu ) b (S v ) d (C w ) e (H x ) f (O y ) g (N z ) h where M represents at least one Group VIB metal, such as Mo, W, etc., or combinations thereof, and X serves as a promoter metal and represents at least one of Group VIII non-noble metals, such as Fe, Ni, Co, Group IVB metals, such as Ti, Group IIB metals, such as Zn, and combinations thereof (X is a "promoter metal"). The superscripts t, u, v, w, x, y, and z represent the total charge on each of M, X, S, C, H, O, and N, respectively, where (ta+ub+vd+we+xf+yg+zh)=0. The ratio of the subscripts b to a has a value between 0 and 5 (0≦b / a≦5). S is sulfur and the subscript d has a value between (a+0.5b) and (5a+2b). C is carbon and the subscript e has a value between 0 and 11(a+b). H is hydrogen and the subscript f has a value from 0 to 7(a+b). O is oxygen and the subscript g has a value from 0 to 5(a+b). N represents nitrogen and the subscript h has a value from 0 to 0.5(a+b). In some embodiments relating to a single metal component catalyst, for example a Mo-only catalyst and no promoter, the subscript b has a value of 0.

[0036] The slurry catalyst can be prepared from catalyst precursors, including organometallic complexes or compounds, such as oil-soluble compounds or complexes of transition metals and organic acids. Examples of such compounds include naphthenates, pentanedionates, octanoates, and acetates of Group VIB and Group VIII metals. In some cases, the slurry catalyst can be prepared from crushed or recovered supported hydrotreating catalyst powder in oil.

[0037] The slurry catalyst can have an average particle size of at least 0.1 micrometers in the diluent. In one embodiment, the slurry catalyst has an average particle size of 1-100 micrometers, e.g., 2-10 micrometers. In some cases, the slurry catalyst particles can include aggregates of catalyst molecules and / or very small particles of colloidal size (i.e., less than 100 nm, less than about 10 nm, less than about 5 nm, or less than about 1 nm). In one embodiment, the slurry catalyst includes aggregates of single-walled MoS clusters of nanometer size, e.g., 5-10 nm edges. The colloidal / nanometer sized particles can form aggregates in the hydrocarbon diluent forming a slurry catalyst having an average particle size of 1-20 micrometers.

[0038] A block process schematic according to an embodiment of the invention is shown in FIG. 1. A hydroconversion reactor 10 is fed separately with solid biomass feedstock 1 (12) and may be fed with liquid feedstock (14). Slurry catalyst is either fed directly to the reactor (16a) or pre-combined with the liquid feedstock before being fed to the reactor (16b). The hydroconversion process in the reactor produces gas and liquid products (18). A product recycle feed can also be fed directly to the hydroconversion reactor (22a) and / or pre-mixed with the liquid feedstock before being fed to the reactor (22b). The liquid product containing the slurry catalyst and other solids is removed in stream (24) from the reactor and fed to a solid-liquid separation stage 20. The solids are separated from the liquid product (26) and the liquid is recycled to the reactor (22a) and / or recycled to the liquid feedstock before being fed to the reactor (22b). EXAMPLES

[0039] Experimental studies and reactor case study simulations were conducted to evaluate the performance of direct biomass feed slurry hydrotreating. Ground wood flour was used as a representative solid biomass direct injection feedstock, and an autoclave reactor was used to evaluate the performance of the slurry hydrocracker. The case study was simulated based on the reaction kinetics developed from the hydroconversion studies and hydroconversion process simulations.

[0040] Example 1 - Pore characterization of solid biomass and slurry characterization Ground wood flour was used as a representative solid biomass raw material. The initial (wet) pore volume was measured by the incipient wetness impregnation method. Approximately 5 grams of wood flour was weighed into a 50 ml beaker. Deionized water was gradually peptized into the wood flour. Water was drawn into the pores of the wood flour by capillary action until all pores were saturated. When the absorption capacity was reached, all excess liquid could be visually observed. The wet pore volume was calculated by dividing the total volume of water absorbed into the pores by the total weight of the wood flour. Mercury intrusion pore volume was measured with a Micromeritics according to ASTM D4284. In this test, mercury intrusion porosimetry measures the intrusion pore volume distribution of solids. The applicable pore size range is controlled by the pressure of mercury intrusion. The range is typically about 0.003 micrometers (3 nm) to 100 micrometers apparent pore intrusion diameter.

[0041] Table 1 shows the pore characterization information measured using incipient wetness and mercury porosimetry. The wood flour had a wet pore volume measured by incipient wetness of 1.39 cc / g and a wet pore volume measured by mercury porosimetry of 1.68 cc / g. [Table 1]

[0042] As shown in Table 1, the incipient wet solids content for the combined solid biomass and liquid feedstock using the vacuum residue was 36.5 wt.% for mercury porosimetry and 41 wt.% for incipient wetness, indicating that only small amounts of solid biomass can be present in the slurry composition.

[0043] The suitability of wood flour and FCC medium cycle oil (MCO) mixtures in forming slurries was also evaluated. Various contents of wood flour in FCC MCO were prepared. Mixtures with less than 20 wt% wood flour resulted in slurries that showed good flow behavior. At 30 wt% wood flour, the resulting slurry showed good flow behavior and free liquid was observed immediately after preparing the mixture. Within 1 hour, the MCO had infiltrated into the pores of the wood flour or was trapped in external nooks and crannies. Free liquid was not evident to the naked eye and the flow behavior of the resulting slurry was similar to a sludge. As the solids content increased, for example above 40%, the mixtures became partially wet solids.

[0044] Example 2 - Hydroconversion of solid biomass and liquid feedstocks (vacuum residue and FCC slurry oil). 100 g of ground wood as described in Example 1 was added to an autoclave reactor containing liquids (vacuum residue and FCC slurry oil) and 200 ppm of dispersed sulfided molybdenum catalyst, presulfided slurry catalyst containing 5 wt% active molybdenum, as described in US Patents 8,802,586 and 9,040,446. It was processed in the autoclave reactor at 835°F. The reactor pressure was kept constant at 2500 psig and a low flow rate hydrogen feed was maintained during the reaction. Sufficient hydrogen and gas products were vented throughout the test. After 2 hours, the reactor was cooled. The top product was collected from a knockout pot downstream of the reactor, while the heavy liquid and solid product slurry was collected from the reactor. The top product had two layers, a lower layer produced mainly by hydrodeoxygenation of wood, and a liquid oil layer of lighter products from hydroconversion of biomass and hydrocarbon feedstocks. The reactor slurry contained high boiling products, catalyst, and coke. The slurry phase solids were separated by filtration and analyzed. The biomass conversion was calculated as follows: Biomass conversion rate = 1 - (weight of coke derived from biomass) / (weight of biomass feed)

[0045] At the end of the test, 1.4 g of wood flour-derived solids were collected, with a corresponding biomass conversion of 98.6%.

[0046] Example 3 - Simulation of hydroconversion of solid biomass and liquid feedstock (vacuum residue) Based on the reaction kinetics developed from hydroconversion studies and hydroconversion process simulations, a case study was simulated using a 100 cubic meter reactor. In the simulation, ground wood flour described in Example 1 was used as the solid biomass and vacuum residue (VR) was used as the liquid feedstock. Molybdenum octoate containing 15 wt% molybdenum was used as the simulated catalyst. The VR and catalyst were premixed and pumped into the reactor. The solid feedstock was added (e.g., using a screw feeder) from the top of the reactor. The reactor process conditions included a temperature of 805°F and a pressure of 1500 psig. The process feed rates included separate feeds of ground wood flour at 55.17 MTPH (metrics per hour), VR liquid feedstock at 8.83 MTPH, and hydrogen at 4.10 MTPH (net consumption). A molybdenum sulfide catalyst of 300 wpm Mo / feed was used. The feed composition and product yields are shown in Table 2. [Table 2]

[0047] Example 4 - Simulation of hydroconversion of solid biomass and liquid feedstock (pyrolysis oil) A further case study was simulated using the 100 cubic meter reactor of Example 2 with wood pyrolysis oil (PY oil) as the liquid feedstock so that the renewable content in the feed was essentially 100%. The slurry catalyst of Example 2, i.e., a pre-sulfided catalyst containing 5 wt.% active molybdenum, was used as described in US Patents 8,802,586 and 9,040,446. A catalyst dosage of 500 wppm total feed in terms of active molybdenum was used in the simulation. Wood pyrolysis oil and catalyst were pumped separately into the reactor since they are immiscible. Solid feedstock was added (e.g., using a screw feeder) from the top of the reactor. The reactor process conditions included a temperature of 750°F and a pressure of 2500 psig. Process feed rates included ground wood flour at 52.41 MTPH (metrics per hour), wood PY oil liquid carrier (feedstock) at 26.21 MTPH, and hydrogen (net consumption) at 4.34 MTPH. Molybdenum sulfide catalyst was used at 300 wpm Mo / feed. [Table 3]

[0048] Example 5 - Simulation of solid biomass hydroconversion without liquid feedstock Another case study was simulated using the 100 cubic meter reactor of Example 2 to show the advantage of direct solid biomass injection without the need for liquid feed. Unlike slurry feed, i.e., feed containing liquid raw materials, direct solid injection does not require any liquid raw materials as a carrier for the solid raw materials. Applicants have discovered that products formed from solid raw materials include liquids that can be used to disperse catalyst and coke in a slurry reactor, thereby eliminating the need for the use of liquid raw materials.

[0049] In this example, no liquid feedstock was added. The feed contained only solid feedstock and catalyst. To keep more product in the liquid phase, the reactor was operated at a relatively low temperature of 750°F and a pressure of 2500 psig. The slurry catalyst of Example 2 was used, i.e., a pre-sulfided catalyst containing 5 wt.% active molybdenum, as described in U.S. Pat. Nos. 8,802,586 and 9,040,446. A catalyst dosage of 500 wppm of total feed in terms of active molybdenum was used in the simulation. The reactor slurry phase contained liquid product, catalyst, and coke, and the solids content was 24.8 wt.% based on the process simulation. The feed composition and product yields are shown in Table 4. [Table 4]

[0050] The above results show that useful products, including renewable fuel-grade products, can be produced by directly feeding solid biomass to a slurry hydroconversion process. Solid biomass feeds can be enriched, including up to 100% renewable feed content (e.g., with recycled or liquid renewable feedstocks). Prior art processes that require the use of a liquefaction process step to reprocess the biomass are not necessary. Thus, any concerns related to instability of intermediate liquefaction products should be reduced, as should any concerns related to high TAN (total acid number) content. In addition, the use of heavy oil feedstocks, such as vacuum residue (VR), as liquid carriers (feedstocks) is possible without significant aromaticity limitations.

[0051] For the avoidance of doubt, this disclosure relates to subject matter set forth in the following numbered clauses:

[0052] Clause 1. A direct biomass hydroconversion process useful for producing renewable fuels, said process comprising: separately feeding a solid biomass feedstock and a liquid feedstock to a slurry hydroconversion reactor, the slurry hydroconversion reactor comprising a slurry hydroconversion catalyst; contacting the solid biomass feedstock and the liquid feedstock with the slurry hydroconversion catalyst in the presence of hydrogen under hydroconversion process conditions for a time sufficient to convert the solid biomass feedstock and the liquid feedstock to hydroconversion products; and removing a hydroconversion product from said reactor. The direct biomass hydroconversion process, wherein the solid biomass feedstock is fed directly to the slurry hydroconversion reactor and is provided as an unprocessed biomass feedstock containing biomass components that have not been chemically treated or modified prior to being fed directly to the slurry hydroconversion reactor.

[0053] Clause 2. The process of clause 1, wherein the process provides a renewable fuel or a hydroconversion product useful for making a renewable fuel.

[0054] Clause 3. The process of clause 1 or clause 2, wherein the slurry hydroconversion catalyst or a precursor thereof is fed separately to the hydroconversion reactor or is combined with the liquid feedstock and the combination is fed to the hydroconversion reactor.

[0055] Clause 4. The process of any one of clauses 1-3, wherein the solid biomass feedstock is at least about 10%, or 20%, or 30%, or 40%, or 50%, or 60%, or 70%, or 75%, or 80% by weight of the combined biomass and liquid feedstocks separately fed to the hydroconversion reactor.

[0056] Clause 5. The process of any one of clauses 1-4, wherein the liquid feedstock comprises heavy boiling point components having a boiling point of at least about 800°F, and / or the liquid feedstock is selected from vacuum gas oil, atmospheric residue, vacuum residue, FCC heavy cycle oil or decant oil, FCC medium cycle oil, hydrocracker unconverted oil, or combinations thereof, and the liquid feedstock may further comprise renewable feedstocks selected from plastic and / or wood pyrolysis oil, lipids, vegetable oils, or combinations thereof.

[0057] Clause 6. The process of any one of clauses 1-5, wherein the liquid feedstock comprises the heavy boiling component having a boiling point of at least about 800°F in an amount of up to about 50%, or 40%, or 30%, or 20%, or 10% by weight, or in the range of about 10-50%, or 10-40%, or 10-30%, or 20-30% by weight.

[0058] Clause 7. The process of any one of clauses 1 to 6, wherein the liquid product is recycled to said hydroconversion reactor.

[0059] Clause 8. The process of any one of clauses 1-7, wherein the solid biomass feedstock comprises a solid biomass component selected from wood or wood mill by-products, tree leaves, grass, algae, crop by-products, municipal solid waste, or a combination thereof, and the solid biomass component may be ground, powdered, shingled, or in particulate, pellet, powder, shavings, chips, dust, or powdered form, or a combination thereof.

[0060] Clause 9. The process of any one of clauses 1-8, wherein the slurry hydroconversion catalyst is in the form of fine particles dispersed within the reactor liquid reaction medium and is a supported catalyst, an unsupported catalyst, or a combination thereof.

[0061] Clause 10. The process of any one of clauses 1-9, wherein the slurry hydroconversion catalyst is unsulfided or may be presulfided and dispersed in a hydrocarbon oil diluent prior to addition to the reactor, the slurry catalyst comprising a metal selected from Group VIB, Group VIII, or Group IIB of the Periodic Table, or a combination thereof.

[0062] Clause 11. The process of any one of clauses 1-10, wherein the slurry hydroconversion catalyst comprises an unsupported catalyst selected from molybdenum sulfide, iron sulfide, nickel sulfide, zinc sulfide, zinc iron, or combinations thereof.

[0063] Clause 12. The process of any one of clauses 1 to 11, wherein said slurry hydroconversion catalyst is provided in the form of a catalyst precursor selected from an oil soluble Group VIB metal compound, an aqueous Group VIB metal compound, an aqueous Group VIB metal trisulfide suspension, or a colloid, or a combination thereof.

[0064] Clause 13. The process of any one of clauses 1-12, wherein the slurry hydroconversion catalyst comprises a supported catalyst, the support being selected from alumina, silica alumina, zeolite, or combinations thereof.

[0065] Clause 14. The process of any one of clauses 1-13, wherein the slurry hydroconversion catalyst, the solid biomass feedstock, and hydrogen are fed to the hydroconversion reactor as separate feed streams to the reactor or are premixed in any combination prior to being fed to the reactor.

[0066] Clause 15. The process of any one of clauses 1-14, wherein the solid biomass feedstock fed to the slurry hydroconversion reactor undergoes hydrocracking, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodechlorination, hydrodecarboxylation, hydrodecarbonylation, hydrodearomatization, or a combination thereof.

[0067] Clause 16. The hydroconversion process conditions include a temperature range of about 650 to 950° F., a reactor pressure of about 300 to 3500 psig, an average residence time of 10 minutes to 5 hours, and a reaction time of about 0.1 to 5.0, or 0.5 to 5.0, or 0.5 to 2.0 hours. -1 and liquid product and / or slurry catalyst may be recycled to the slurry hydroconversion reactor.

[0068] Clause 17. The process of any one of clauses 1-16, wherein a coke yield is less than about 5% by weight, or less than about 2% by weight, or less than about 1% by weight of the solid biomass fed to the process.

[0069] Clause 18. The process of any one of clauses 1-17, wherein the hydroconversion products include a liquid hydrocarbon product having an oxygen content of less than about 3 wt.% or less than about 1 wt.% and / or a total acid number (TAN) of less than about 1.

[0070] The disclosure of the present application is not limited with respect to the specific embodiments described in the present application, which are intended to illustrate different aspects. Obviously, many modifications and variations can be made without departing from the spirit and scope thereof. In addition to those recited herein, functionally equivalent methods and systems within the scope of the present disclosure will be apparent from the above exemplary description. Such modifications and variations are intended to be included within the scope of the appended exemplary claims. The present disclosure should be limited only by the language of the appended exemplary claims, along with the full scope of equivalents to which such exemplary claims are entitled. It should also be understood that the terms used in the present specification are for the purpose of describing particular embodiments only, and are not intended to be limiting.

[0071] The foregoing description, together with its associated embodiments, is presented for illustrative purposes only. The description is not exhaustive and does not limit the invention to the precise form disclosed. Those skilled in the art will recognize from the above description that modifications and variations are possible in light of the above teachings or by practicing the disclosed embodiments. For example, in some cases, each step described need not be performed in the same order or to the same extent as described. Similarly, different steps can be omitted, repeated, or combined, as necessary, to achieve the same or similar purpose. Thus, the present invention is not limited to the above-described embodiments, but is instead defined by the appended claims in light of their full scope of equivalents.

[0072] In the above specification, different preferred embodiments have been described with reference to the accompanying drawings. However, it is apparent that various modifications and changes may be made to the invention and that further embodiments may be implemented without departing from the broader scope of the invention as set forth in the following claims. The specification and drawings are therefore to be regarded as illustrative rather than restrictive.

[0073] Where permitted, all publications, patents, and patent applications cited in this application are incorporated herein by reference in their entirety to the extent such disclosures are not inconsistent with the present invention.

Claims

1. 1. A direct biomass hydroconversion process useful for the production of renewable fuels, said process comprising: separately feeding a solid biomass feedstock and a liquid feedstock to a slurry hydroconversion reactor, the slurry hydroconversion reactor comprising a slurry hydroconversion catalyst; contacting the solid biomass feedstock and the liquid feedstock with the slurry hydroconversion catalyst in the presence of hydrogen under hydroconversion process conditions for a time sufficient to convert the solid biomass feedstock and the liquid feedstock to hydroconversion products; and removing a hydroconversion product from said reactor. The direct biomass hydroconversion process, wherein the solid biomass feedstock is fed directly to the slurry hydroconversion reactor and is provided as an unprocessed biomass feedstock containing biomass components that have not been chemically treated or modified prior to being fed directly to the slurry hydroconversion reactor.

2. 10. The process of claim 1, wherein the process provides a renewable fuel or a hydroconversion product useful for making renewable fuels.

3. 3. The process of claim 1 or claim 2, wherein the slurry hydroconversion catalyst or a precursor thereof is fed separately to the hydroconversion reactor or is combined with the liquid feedstock and the combination is fed to the hydroconversion reactor.

4. 4. The process of any one of claims 1 to 3, wherein the solid biomass feedstock is at least about 10%, or 20%, or 30%, or 40%, or 50%, or 60%, or 70%, or 75%, or 80% by weight of the combined biomass and liquid feedstocks fed separately to the hydroconversion reactor.

5. 5. The process of any one of claims 1 to 4, wherein the liquid feedstock comprises heavy boiling point components having a boiling point of at least about 800°F, and / or the liquid feedstock is selected from vacuum gas oil, atmospheric residue, vacuum residue, FCC heavy cycle oil or decant oil, FCC medium cycle oil, hydrocracker unconverted oil, or combinations thereof, and the liquid feedstock may further comprise renewable feedstocks selected from plastic and / or wood pyrolysis oil, lipids, vegetable oils, or combinations thereof.

6. 6. The process of any one of claims 1 to 5, wherein the liquid feedstock comprises heavy boiling components having a boiling point of at least about 800°F in an amount of up to about 50%, or 40%, or 30%, or 20%, or 10% by weight, or in the range of about 10-50%, or 10-40%, or 10-30%, or 20-30% by weight.

7. The process of any one of claims 1 to 6, wherein the liquid product is recycled to the hydroconversion reactor.

8. 8. The process of any one of claims 1 to 7, wherein the solid biomass feedstock comprises solid biomass components selected from wood or wood mill by-products, tree leaves, grass, algae, crop by-products, municipal solid waste, or combinations thereof, and the solid biomass components may be ground, powdered, shingled, or in particulate, pellet, powder, shavings, chips, dust, or powdered form, or combinations thereof.

9. 9. The process of any one of claims 1 to 8, wherein the slurry hydroconversion catalyst is in the form of fine particles dispersed within the reactor liquid reaction medium and is a supported catalyst, an unsupported catalyst, or a combination thereof.

10. 10. The process of any one of claims 1 to 9, wherein the slurry hydroconversion catalyst is unsulfided or may be presulfided and dispersed in a hydrocarbon oil diluent prior to addition to the reactor, the slurry catalyst comprising a metal selected from Group VIB, Group VIII, or Group IIB of the Periodic Table, or a combination thereof.

11. 11. The process of any one of claims 1 to 10, wherein the slurry hydroconversion catalyst comprises an unsupported catalyst selected from molybdenum sulfide, iron sulfide, nickel sulfide, zinc sulfide, zinc iron, or combinations thereof.

12. 12. The process of any one of claims 1 to 11, wherein the slurry hydroconversion catalyst is provided in the form of a catalyst precursor selected from an oil soluble Group VIB metal compound, an aqueous Group VIB metal compound, an aqueous Group VIB metal trisulfide suspension, or colloid, or combinations thereof.

13. The process of any one of claims 1 to 12, wherein the slurry hydroconversion catalyst comprises a supported catalyst, the support being selected from alumina, silica alumina, zeolite, or combinations thereof.

14. 14. The process of any one of claims 1 to 13, wherein the slurry hydroconversion catalyst, the solid biomass feedstock, and hydrogen are fed to the hydroconversion reactor as separate feed streams to the reactor or are premixed in any combination prior to being fed to the reactor.

15. 15. The process of any one of claims 1 to 14, wherein the solid biomass feedstock fed to the slurry hydroconversion reactor undergoes hydrocracking, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodechlorination, hydrodecarboxylation, hydrodecarbonylation, hydrodearomatization, or a combination thereof.

16. The hydroconversion process conditions include a temperature range of about 650-950° F., a reactor pressure of about 300-3500 psig, an average residence time of 10 minutes to 5 hours, and a reaction time of about 0.1-5.0, or 0.5-5.0, or 0.5-2.0 hr. －１ and liquid product and / or slurry catalyst may be recycled to the slurry hydroconversion reactor.

17. 17. The process of any one of claims 1 to 16, wherein the coke yield is less than about 5%, or less than about 2%, or less than about 1% by weight of the solid biomass fed to the process.

18. 18. The process of any one of claims 1 to 17, wherein the hydroconversion products comprise a liquid hydrocarbon product having an oxygen content of less than about 3 wt.%, or less than about 1 wt.%, and / or a total acid number (TAN) of less than about 1.

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