Renewable biomass feed slurry hydroprocessing

Abstract

Renewable biomass feed slurry hydrotreatment, including, for example, a slurry hydroconversion process, is described in which a feedstock comprising renewable biomass components is subjected to slurry hydroconversion. The processes generally include contacting a solid biomass feedstock and a slurry hydroconversion catalyst under suitable hydroconversion conditions to convert a portion of the feedstock to liquid and / or gaseous products. The process can utilize raw biomass as a feedstock and does not require the use of chemically treated or modified biomass feedstocks. A low coke yield can be obtained.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is related to and claims the benefit of priority of U.S. Provisional Patent Application Serial No. 63 / 326,803, filed on April 1, 2022, entitled “RENEWABLE BIO MASS FEED SLURRYHYDROPROCESSING,” the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] The present disclosure relates to renewable biomass feed slurry hydroprocessing, including, for example, a slurry hydroconversion process in which a feedstock comprising a renewable biomass component is subjected to slurry hydroconversion. Background Art

[0004] In the process of developing alternatives to fossil fuels, the use of renewable resources has attracted great attention and efforts. The diversity, availability and versatility of various biomass materials, especially certain lignocelluloses and other carbohydrates, have received great attention. However, despite the great promise and attention paid to bio-based fuel technologies, their development and commercial application have not been successfully implemented as hoped. Although some biofuel technologies have been commercialized, the so-called second-generation renewable feedstocks have not been widely developed, especially transportation fuels from second-generation renewable biofuel feedstocks.

[0005] Renewable fuel (biofuel) is regarded as an important means to reduce carbon and greenhouse gas emissions. The first generation of biofuel is a fuel made from food crops grown on arable land, while the second generation of biofuel is produced from lignocellulosic biomass or agricultural residues / waste. Unlike the first generation of biofuels from competitive biomass food sources, the second generation of renewable fuels is usually not from human food sources, and is therefore superior to the first generation of renewable fuels. Typical second generation feedstocks include wood, grass, algae, crop byproducts, municipal solid waste, etc. However, the processing of second generation biomass usually requires more complicated two-step or multi-step processes to convert the available portion of solid biomass into suitable raw materials. Specifically, the first step is usually to convert solid biomass feedstock into a liquid bio-crude oil form by pyrolysis, hydrolysis, hydrothermal liquefaction or other process steps. Conventional oil refining units (such as hydroprocessors or FCC units) are then usually used to further upgrade bio-crude oil to produce transportation fuels.

[0006] Other difficulties of the prior art produce fuels with low energy density, such as bioethanol, or fuels that are not fully compatible with existing engine designs and transportation infrastructure, such as methanol, biodiesel, hydrogen and methane, or produce dilute aqueous solutions that are not cost-effective for further processing. It would be a significant advantage if a simplified method could be provided to directly use solid biomass in a hydroconversion process for producing renewable fuels (or products for preparing renewable fuels) without pre-treating the solid biomass. In view of the global efforts to adopt methods to reduce the use of fossil fuels, it is particularly desirable to use feeds with high biomass content to minimize or eliminate the use of fossil fuel co-feeds. It is highly desirable to provide a low-cost, energy-efficient method for processing lignocellulosic biomass into renewable fuels with a chemical composition similar to that of fossil fuels to alleviate the above concerns and problems. Summary of the invention

[0007] The present invention generally relates to renewable biomass feed slurry hydroprocessing. In one aspect, a slurry hydroconversion method is provided, wherein a raw material comprising a renewable biomass component is subjected to slurry hydroconversion. The method generally includes contacting a solid biomass feedstock and a slurry hydroconversion catalyst under suitable hydroprocessing conditions to convert a portion of the feedstock into a hydroconversion product (e.g., a liquid and / or gaseous product). The method can utilize raw biomass as a raw material, and does not require the use of chemically treated or modified biomass feeds. Low coke yields can be obtained, which is one of the benefits associated with the method. Although not necessarily limited thereto, one of the objects of the present invention is to provide a simplified and effective method for preparing renewable fuels and / or other products with unprocessed biomass feedstocks.

[0008] Generally, the method according to the present 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 for a sufficient time under hydroconversion process conditions in the presence of hydrogen to convert a portion of the solid biomass feedstock and the liquid feedstock into one or more hydroconversion products, such as liquid and / or gaseous products, and removing the hydroconversion products from the reactor. The solid biomass feedstock is generally fed directly to the slurry hydroconversion reactor and is provided as a raw biomass feedstock containing biomass components that are not chemically treated or modified before being directly fed to the slurry hydroconversion reactor. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The scope of the present invention is not limited by any of the representative drawings attached to this disclosure, and should be understood to be defined by the claims of this application.

[0010] Figure 1is a general block diagram schematic representation of an embodiment according to the present invention wherein a solid biomass feedstock is fed directly to a reactor and separated to provide a solid biomass hydroconversion product. DETAILED DESCRIPTION

[0011] Although illustrative embodiments of one or more aspects are provided herein, the disclosed processes may be implemented using any number of techniques. The present disclosure is not limited to the exemplary or specific embodiments, any drawings, and any techniques (including any exemplary designs and embodiments illustrated and described herein) illustrated herein, and may be modified within the scope of the appended claims and the full scope of their equivalents.

[0012] The following description of the embodiments provides non-limiting representative examples, which reference numbers to specifically describe the features and teachings of different aspects of the present invention. The described embodiments should be considered to be able to be implemented alone or in combination with other embodiments from the description of the embodiments. A person of ordinary skill in the art should be able to learn and understand the different described aspects of the present invention when reading the description of the embodiments. The description of the embodiments should help to understand the present invention to such an extent that, after reading the description of the embodiments, other embodiments that are not specifically involved but within the scope of their knowledge will be understood as consistent with the application of the present invention.

[0013] Unless otherwise indicated, the following terms have the meanings as defined below.

[0014] The term "hydroconversion" refers to a process or step of hydrocracking, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodechlorination, hydrodecarboxylation, hydrodecarbonylation and / or hydrodearomatization of components (e.g., impurities) of hydrocarbon or biomass feedstocks in the presence of hydrogen, and / or hydrogenating unsaturated compounds in the feedstock. Depending on the type of hydroconversion and reaction conditions, the product of the hydroconversion process may have, for example, improved specific gravity, acidity, aromatic content, viscosity index, saturate content, low temperature characteristics, volatility, and depolarization.

[0015] The term "catalyst support" is used in a conventional sense according to normal usage in the art, and includes typical catalyst support materials such as alumina, silica-alumina, metal oxides, zeolite and non-zeolite materials, activated carbon, and the like.

[0016] "Catalyst precursor" refers to a compound containing one or more catalytically active metals from which a slurry catalyst is ultimately formed and which is catalytically active as a hydroprocessing catalyst. One example is a water-based catalyst with a hydrocarbon diluent prior to the conversion step, and another example is a sulfided metal precursor. The preparation of catalyst precursors and slurry catalysts is described in various patents, such as US 8,802,586, WO 2012 / 092006, etc.

[0017] The term "raw biomass" refers to suitable biomass raw materials that have not been chemically treated or modified before being used in the method. Such chemically treated or modified biomass materials include, for example, lignocellulosic materials, which have been treated to remove or reduce the content of certain components, or such components have been chemically modified, such as removing cellulose or hemicellulose, or lignin has been modified. Other chemically modified biomass materials may include biomass materials modified by roasting, or biomass processed using slow pyrolysis, fast or flash pyrolysis, hydrothermal liquefaction, hydrogenation pyrolysis, kraft pulping methods, etc. The raw biomass materials may include mechanically modified biomass materials or dried biomass materials. In the context of the present invention, the heat-treated biomass material may not be a "raw biomass" material, but, when such biomass material is chemically modified, includes, for example, a pyrolysis product derived from biomass. Typical drying processes do not change the biomass composition, only remove moisture, and are therefore not chemically modified.

[0018] The term "pore volume" used to describe the porosity of solid biomass can be described in terms of "wet pore volume" and "pore volume" determined by mercury intrusion. "Incipient wet pore volume" or "wet pore volume" is measured by the incipient wetness impregnation method. In this method, a certain amount of dry biomass is impregnated with a liquid (usually water) by capillary action until all 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 solid biomass is measured according to ASTM D4284 and is typically provided by a commercial mercury intrusion porosimeter.

[0019] The Periodic Table of the Elements referred to in this disclosure is the CAS version as published by the Chemical Abstract Service in the Handbook of Chemistry and Physics, 72nd Edition (1991-1992).

[0020] Unless otherwise indicated, the recitation of a class of elements, materials, or other components from which a single component or a mixture of components may be selected is intended to include all possible subclass combinations of the listed components and mixtures thereof. In addition, "comprising" and its variations are intended to be non-limiting, such that the recitation of items in a list does not exclude other similar items that may also be used in the materials, compositions, and methods of the present invention.

[0021] In the method of the present invention, solid biomass feedstock and liquid feedstock are fed to the slurry hydroconversion reactor separately. Slurry catalyst can be fed alone or added to the reactor as a combination with liquid feedstock. Hydrogen is usually also fed to the reactor, and can be combined with any feed or fed to the reactor alone. Slurry hydroconversion catalyst, liquid feedstock and hydrogen can be premixed in any combination or amount before being fed to the hydroconversion reactor. Slurry hydroconversion catalyst can be its precursor.

[0022] The feed to the hydroconversion reactor typically comprises at least about 10 wt%, or 20 wt%, or 30 wt%, or 40 wt%, or 50 wt%, or 60 wt% solid biomass, 0 wt% to 40 wt% liquid feedstock and less than about 5 wt%, or less than about 2 wt%, or less than about 1 wt% 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 an operating temperature range of about 650 to 950°F, a reactor pressure of about 300 psig to 3500 psig, an average residence time of 10 minutes to 5 hours, and a space velocity of about 0.1 to 5.0, or 0.5 to 5.0, or 0.5 to 2.0 hr -1 Mixing within the reactor helps improve solids dispersion and reactor temperature measurement and can be achieved using mechanical mixing (e.g., agitators and impellers), liquid recirculation (e.g., pumps, thermosyphons), gas bubbling (e.g., bubble column reactors), etc.

[0023] One of the advantages of the present invention is that solid biomass raw materials can be used as direct feeds to hydrocrackers, rather than chemically converting or modifying biomass before using it as direct hydrocracker feeds. For example, the present invention does not require solid biomass to be converted into liquid forms, such as bio-crude oil, before use. Other processes that modify biomass before being used in the method are also not necessary, such as hydropyrolysis, hydrothermal carbonization, roasting or removing certain carbohydrate components such as cellulose, hemicellulose or lignin.

[0024] Compared with the co-feed (including as dispersion or suspension) of the solid biomass and liquid raw materials of combination, the direct injection of solid biomass according to the method also eliminates the problems associated with the use of liquid co-feed. Many biomass raw materials such as wood, grass and other agricultural products are characterized by relatively low density and high pore volume, so that when the biomass solid content reaches a certain range, for example, 35% by weight to 50% by weight, the liquid is trapped in the solid, leaving little or no free liquid. Basically, the mixture of solid biomass and liquid forms a wet solid, rather than a slurry, suspension or dispersion. For this method, there is a restriction on the maximum biomass content in the solid biomass and liquid co-feed. However, by direct solid biomass injection, such restrictions are avoided, and the total solid biomass content (relative to any single liquid raw material provided to the reactor) fed to the reactor can be much higher. Since the operation of the reactor under the slurry hydroconversion conditions requires enough liquid to keep the solid in the slurry, the combination of any single liquid raw material fed to the reactor and the liquid produced by the hydroconversion of the solid biomass allows the solid biomass of higher content to be directly fed to the reactor.

[0025] Direct solid biomass injection allows certain product benefits to be achieved, including reduced coke yields, which are typically less than about 5 wt %, or less than about 2 wt %, or less than about 1 wt % of the solid biomass feed to the process. Liquid product oxygen content may also be less than about 3 wt %, or less than about 1 wt %, and / or the total acid number (TAN) may be less than about 1.

[0026] Other operational benefits associated with direct feeding of solid biomass may include: significantly reduced energy consumption due to the use of less liquid feedstock; and reduced limitations on slurry or liquid handling means (e.g., pumping) of the biomass feedstock due to the fact that direct solids injection allows processing of larger and more varied sized biomass solids.

[0027] Although not limited thereto, the process of the present invention may be used to provide a renewable fuel, or to provide product components that may be used to prepare a renewable fuel from liquid and / or gaseous products produced by the process.

[0028] The solid biomass feedstock can include a solid biomass component selected from wood or lumber mill byproducts, leaves, grass, algae, crop byproducts, municipal solid waste or a combination thereof, optionally wherein the solid biomass component is ground, crushed, sliced ​​or in a particle, pellet, powder, wood shavings, fragments, dust or pulverized form or a combination thereof. Solid biomass can be transferred to a hydroconversion reactor by various single or combined methods, including, for example, using a pressure transfer container, an extruder, a rotary valve or a lock hopper. The original biomass material can be crushed or otherwise processed into any desired size or size range, for example, in the range of 50 microns to 10 mm, or processed into wood chips of a maximum length of 3 cm, etc. The original biomass can be dry or under undried conditions.

[0029] Typically, the solid biomass feedstock is provided as a raw biomass feedstock containing a biomass component that is not chemically treated or modified before being fed directly to a slurry hydroconversion reactor. For example, certain modified biomass materials, such as lignin, e.g., lignin from a papermaking process, are not intended to be included in the method, e.g., according to U.S. Patent No. US 8795472B2.

[0030] The solid biomass feedstock fed to the slurry hydroconversion reactor may undergo various reactions including hydrocracking, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodechlorination, hydrodecarboxylation, hydrodecarbonylation, hydrodearomatization, or combinations thereof.

[0031] The liquid feedstock typically includes a heavy boiling point component having a boiling point of at least about 800°F. For example, but not limited to, the liquid feedstock typically can 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 a combination thereof. The heavy boiling point component 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% by weight, or 40% by weight, or 30% by weight, or 20% by weight, or 10% by weight, or in the range of about 10% by weight to 50% by weight, or 10% by weight to 40% by weight, or 10% by weight to 30% by weight, or 20% by weight to 30% by weight. The liquid feedstock may include one or more high boiling point components having a 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 raw material component with a high boiling point present in the liquid raw material 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 raw material. The liquid raw material may also include a renewable raw material selected from plastic and / or wood pyrolysis oil, lipids, vegetable oils, or a combination thereof.

[0032] In addition, the liquid feedstock can be combined with the recycled slurry hydroconversion reactor product before being directly fed to the slurry hydroconversion reactor. All or part of any liquid product can also be recycled to the slurry hydroconversion reactor. Any recycled liquid product can be first treated, for example, by solid-liquid separation of the hydroconversion reactor liquid product, to reduce or eliminate the solids present in the recycle. Typical means of separating solids from liquids can be used, for example, including but not limited to sedimentation, screening, filtration or centrifugation.

[0033] Slurry hydroconversion catalyst is usually provided in the form of fine particles dispersed in the reactor liquid reaction medium, and can be a supported catalyst, a non-supported catalyst or a combination thereof. Slurry catalyst usually comprises a metal selected from the periodic table VIB group, VIII group or IIB group or a combination thereof. Slurry hydroconversion catalyst can be non-sulfided or pre-sulfided before being added to the reactor. Slurry catalyst can also be dispersed in a hydrocarbon oil diluent. Usually a sufficient amount of slurry catalyst is fed to the slurry reactor so that the slurry catalyst concentration of each reactor is 100wppm, or 300wppm, or 500wppm up to about 3 weight % (ratio of catalyst metal to raw material). Slurry catalyst can include one or more different slurry catalysts as a single combined feed stream or as a separate feed to the reactor.

[0034] In some cases, the slurry hydroconversion catalyst comprises a non-supported catalyst selected from molybdenum sulfide, iron sulfide, nickel sulfide, zinc sulfide, iron zinc 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. In addition, the slurry hydroconversion catalyst may comprise a supported catalyst, wherein the carrier is selected from alumina, silica-alumina, a transition metal oxide, activated carbon, a zeolite or a combination thereof.

[0035] Suitable slurry catalyst, slurry catalyst precursor and the preparation of slurry catalyst are described in various patents, such as US 8,802,586, WO 2012 / 092006, US2015 / 0329790A1, etc. For example, suitable catalysts for slurry hydroprocessing systems may include at least one Group VIII metal (such as Ni and / or Co), which is most commonly combined with at least one Group VIB metal (such as Mo) on a refractory inorganic oxide carrier such as alumina or silica. These supported catalysts generally contain 0.5% to 10% by weight of at least one Group VIII metal (calculated as metal oxide) and 1% to 30% by weight of at least one Group VIB metal (calculated as metal oxide), and optionally contain at least one Group IIB metal (such as Zn). Such supported catalysts are generally made into the form of cylindrical pellets, spherical solids or extrudates, and can be ground into fine powders for use as slurry catalysts. In some cases, the slurry catalyst may be a multimetallic catalyst comprising at least one Group VIII non-noble metal and at least two Group VIB metals, and wherein the ratio of the at least two Group VIB metals to the Group VIII non-noble metal is from 10:1 to 1:10.

[0036] The slurry catalyst may have the formula (M t ) a (X u ) b (S v ) d (C w ) e (H x ) f (O y ) g (N z ) h, wherein M represents at least one Group VIB metal, such as Mo, W, etc., or a combination thereof, and X, as a promoter metal, represents at least one of a non-noble Group VIII metal such as Fe, Ni, Co; a Group IVB metal such as Ti; a Group IIB metal such as Zn; and a combination thereof (X is a "promoter metal"). Superscripts t, u, v, w, x, y, and z represent the total charge of each of M, X, S, C, H, O, and N, respectively; and wherein (ta+ub+vd+we+xf+yg+zh)=0. The subscript ratio of b to a has a value of 0 to 5 (0≤b / a≤5). S represents sulfur, and the value of subscript d is (a+0.5b) to (5a+2b). C represents carbon, and the value of subscript e is 0 to 11 (a+b). H is hydrogen, and the value of subscript f is 0 to 7 (a+b). O represents oxygen, and the value of subscript g is 0 to 5 (a+b). N represents nitrogen, and the value of subscript h is 0 to 0.5(a+b). In some embodiments, the value of subscript b is 0, for example, for a single metal component catalyst, such as a catalyst containing only Mo, and no promoter.

[0037] The slurry catalyst can be prepared from a catalyst precursor composition comprising an organometallic complex or compound, such as an oil-soluble compound or complex of a transition metal and an organic acid. Examples of such compounds include naphthenates, pentanedione salts, octoates and acetates of Group VIB and Group VIII metals. In some cases, the slurry catalyst can be prepared from a ground or recovered supported hydroprocessing catalyst powder in oil.

[0038] The slurry catalyst may have an average particle size of at least 0.1 microns in the diluent. In one embodiment, the slurry catalyst has an average particle size of 1 micron to 100 microns, such as 2 microns to 10 microns. In some cases, the slurry catalyst particles may include aggregates of catalyst molecules and / or colloidal particles of very small size (i.e., less than 100nm, less than about 10nm, less than about 5nm, or less than about 1nm). In one embodiment, the slurry catalyst includes aggregates of nano-sized monolayer MoS clusters, such as 5nm to 10nm on the edge. The colloid / nano-sized particles may form aggregates in the hydrocarbon diluent to form a slurry catalyst having an average particle size of 1 micron to 20 microns. `

[0039] Figure 1A block diagram of a process according to an embodiment of the present invention is shown. The hydroconversion reactor 10 is fed with a solid biomass feedstock 12 and an optional liquid feedstock 14, respectively. The slurry catalyst is fed directly to the reactor 16a, or pre-combined with the liquid feedstock 16b before being fed to the reactor. The hydroconversion process in the reactor produces gas and liquid products 18. The product recycle feed can also be fed directly to the hydroconversion reactor 22a, and / or pre-combined with the liquid feedstock 22b before being fed to the reactor. The liquid product containing the slurry catalyst and other solids is removed from the reactor through stream 24 and fed to the solid-liquid separation stage 20. The solids 26 are separated from the liquid product, wherein the liquid is recycled to the reactor 22a, and / or the liquid feedstock 22b is fed to the reactor before being fed.

[0040] Example

[0041] Experimental studies and reactor case study simulations were performed to evaluate the performance of direct biomass feed slurry hydroprocessing. Pulverized wood flour was used as a representative solid biomass direct injection feedstock and an autoclave reactor was used to evaluate the slurry hydrocracker performance. The case study simulations were performed based on the kinetics derived from the hydroconversion studies and hydroconversion process simulations.

[0042] Example 1 - Solid Biomass Pore Characterization and Slurry Characterization

[0043] Crushed wood powder is used as a representative solid biomass raw material. The initial (wet) pore volume is measured by the initial wet impregnation method. About 5 grams of wood powder are weighed in a 50-ml beaker. Deionized water is gradually peptized into the wood powder. Capillary action draws water into the pores of the wood powder until all pores are saturated. When the absorption capacity is reached, any excess liquid can be observed with the naked eye. The wet pore volume is calculated by dividing the total volume of water absorbed in the pores by the total weight of the wood powder. The mercury intrusion pore volume is measured in a mercury intrusion porosimeter (Micromeritics) according to ASTM D4284. The test determines the intrusion pore volume distribution of the solid by the mercury intrusion porosimetry method. The range of applicable pore sizes is controlled by the mercury intrusion pressure. This range is usually between the apparent pore entrance diameter of about 0.003 microns (3nm) to 100 microns.

[0044] Table 1 provides pore characterization information measured using incipient wetness and mercury intrusion techniques. The wood flour had a wet pore volume of 1.39 cc / g as measured by incipient wetness and 1.68 cc / g as measured by mercury intrusion.

[0045] Table 1 - Characterization of pore volume of wood flour biomass

[0046]

[0047] As shown in Table 1, the incipient wetness solids content of the combined solid biomass and liquid feedstock using vacuum resid was 36.5 wt% by mercury porosimetry and 41 wt% by incipient wetness, indicating that only low levels of solid biomass may be present in the slurry composition.

[0048] The suitability of a mixture of wood flour and FCC medium cycle oil (MCO) in forming a slurry was also evaluated. FCC MCO with different wood flour contents was prepared. Mixtures with wood flour content <20 wt% provided slurries showing good flow behavior. In the case of 30 wt% wood flour, the resulting slurry showed good flow behavior and free liquid could be observed immediately after preparation of the mixture. Within 1 hour, the MCO penetrated into the wood flour pores or was trapped in the outer nooks and cracks. No free liquid was visible and the resulting slurry flow behavior was similar to that of sludge. As the solid content increased, for example >40%, the mixture became a partially wetted solid.

[0049] Example 2 - Hydroconversion of solid biomass and liquid feedstocks (vacuum residue and FCC slurry oil)

[0050] As described in U.S. Pat. Nos. 8,802,586 and 9,040,446, 100 g of pulverized wood as described in Example 1 was added to an autoclave reactor with liquid (vacuum residue and FCC oil slurry) and 2000 ppm dispersed sulfided molybdenum catalyst (presulfided slurry catalyst containing 5 wt.% active molybdenum). It was treated in an autoclave reactor at 835°F. A low flow rate of hydrogen feed was maintained during the reaction, and the reactor pressure was kept constant at 2500 psig. A large amount of hydrogen and gas products were discharged throughout the test. After two hours, the reactor cooled down. The overhead product was collected from a separation tank downstream of the reactor, and heavy liquid and solid product slurry were collected from the reactor. The overhead product has two layers, the bottom water layer is mainly produced by the hydrodeoxygenation of wood, and the liquid oil layer is a light product produced by the hydroconversion of biomass and hydrocarbon feedstock. The reactor slurry contains high boiling products, catalysts and coke. The solids from the slurry phase are separated by filtration and analyzed. The conversion rate of biomass is calculated as follows:

[0051] Biomass conversion rate = 1-(weight of coke in biomass) / (weight of biomass feed)

[0052] At the end of the experiment, 1.4 g of solids originating from wood flour were collected. The corresponding biomass conversion rate was 98.6%.

[0053] Example 3 - Simulation of Hydroconversion of Solid Biomass and Liquid Feedstock (Vacuum Residue)

[0054] Based on the kinetics derived from hydroconversion studies and hydroconversion process simulations, a case study using a 100 cubic meter reactor was simulated. In the simulation, pulverized wood meal as described in Example 1 was used as solid biomass, and vacuum residue (VR) was used as liquid feedstock. Molybdenum octoate containing 15% by weight of molybdenum was used as a simulated catalyst. VR and catalyst were premixed and pumped into the reactor. Solid feedstock was added through the top of the reactor (e.g., using a screw feeder). Reactor process conditions included a temperature of 805°F and a pressure of 1500 psig. The process feed rate included 55.17 MTPH (metric tons / hour) of pulverized wood meal, 8.83 MTPH of VR liquid feedstock, and 4.10 MTPH of hydrogen (net consumption) as separate feeds. A 300 wppm Mo / feed molybdenum sulfide catalyst was used. The feed composition and product yields are shown in Table 2.

[0055] Table 2

[0056]

[0057] Example 4 - Simulation of Hydroconversion of Solid Biomass and Liquid Feedstock (Pyrolysis Oil)

[0058] Another case study of the 100 cubic meter reactor of Example 2 was simulated using wood pyrolysis oil (PY oil) as a liquid feedstock, so that the renewable content in the feed was essentially 100%. The slurry catalyst of Example 2, i.e., a presulfided catalyst containing 5 wt% active molybdenum, was used, as described in U.S. Patent Nos. 8802586 and 9040446. The catalyst dosage used in the simulation was 500wppm in the total feed in terms of active molybdenum. Due to the immiscibility of wood pyrolysis oil and catalyst, they were pumped into the reactor separately. Solid feedstock was added from the top of the reactor (e.g., using a screw feeder). Reactor process conditions included a temperature of 750°F and a pressure of 2500psig. The process feed rate included 52.41MTPH (metric tons / hour) of crushed wood powder, 26.21MTPH of wood PY oil liquid carrier (raw material) and 4.34MTPH of hydrogen (net consumption). A 300wppm Mo / feed sulfided molybdenum catalyst was used. The feed composition and product yields are shown in Table 3.

[0059] Table 3

[0060]

[0061] Example 5 - Simulation of solid biomass hydroconversion without liquid feedstock

[0062] Another case study of the 100 cubic meter reactor of Example 3 was simulated to illustrate the benefits of direct solid biomass injection without liquid feed. Unlike using a slurry feed (i.e., a feed containing a liquid feed), direct solid injection does not require any liquid feed as a carrier for the solid feed. Applicants have discovered that the product formed from the solid feed includes a liquid that can be used to disperse the catalyst and coke in the slurry reactor, thereby eliminating the need for the use of a liquid feed.

[0063] In this embodiment, no liquid feedstock is added. The feed contains only solid feedstock and catalyst. In order to keep more products in liquid phase, the reactor is operated at a relatively low temperature of 750°F and a pressure of 2500 psig. The slurry catalyst of Example 2, i.e., a presulfided catalyst containing 5% by weight of active molybdenum, is used, as described in U.S. Patent Nos. 8802586 and 9040446. The catalyst dosage used in the simulation is 500wppm in the total feed in terms of active molybdenum. Based on process simulation, the reactor slurry phase contains liquid products, catalyst and coke, and the solid content is 24.8% by weight. The feed composition and product yield are shown in Table 4.

[0064] Table 4

[0065]

[0066] The above results prove that solid biomass can be directly fed to the slurry hydroconversion process to produce available products, including renewable fuel grade products. High solid biomass feed content is possible, including up to 100% renewable feed content (for example, using recycling or using liquid renewable raw materials). It is not necessary to use the liquefaction process step required for the prior art method to pre-treat biomass. Therefore, any concerns related to the instability of the intermediate liquefied product should be reduced, and any concerns related to high TAN (total acid number) content should also be reduced. In addition, heavy oil feedstocks such as vacuum residue (VR) can be used, for example, as liquid carriers (raw materials), without obvious aromaticity restrictions.

[0067] For the avoidance of doubt, the present disclosure relates to the subject matter described in the following numbered paragraphs:

[0068] 1. A direct biomass hydroconversion process for producing renewable fuels, comprising:

[0069] Feeding a solid biomass feedstock and a liquid feedstock into a slurry hydroconversion reactor respectively; wherein the slurry hydroconversion reactor contains a slurry hydroconversion catalyst;

[0070] 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 sufficient time to convert the solid biomass feedstock and the liquid feedstock into a hydroconversion product; and

[0071] removing a hydroconversion product from the reactor;

[0072] Wherein, the solid biomass feedstock is directly fed into the slurry hydroconversion reactor and is provided as a raw biomass feedstock containing biomass components, and the biomass components are not chemically treated or modified before being directly fed into the slurry hydroconversion reactor.

[0073] 2. The method of paragraph 1, wherein the method provides a renewable fuel or a hydroconversion product that can be used to prepare a renewable fuel.

[0074] 3. The method of paragraph 1 or paragraph 2, wherein the slurry hydroconversion catalyst or a precursor thereof is fed to the hydroconversion reactor alone, or is combined with the liquid feedstock and the combination is fed to the hydroconversion reactor.

[0075] 4. A method as described in any of paragraphs 1 to 3, wherein the solid biomass feedstock is at least about 10 weight %, or 20 weight %, or 30 weight %, or 40 weight %, or 50 weight %, or 60 weight %, or 70 weight %, or 75 weight %, or 80 weight % of the total amount of the biomass and the liquid feedstock fed to the hydroconversion reactor, respectively.

[0076] 5. The process of any of paragraphs 1 to 4, wherein the liquid feedstock comprises heavy boiling components having a boiling point of at least about 800°F, and / or wherein 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 a combination thereof, optionally wherein the liquid feedstock further comprises a renewable feedstock selected from plastic and / or wood pyrolysis oil, lipids, vegetable oil, or a combination thereof.

[0077] 6. The process of any of paragraphs 1 to 5, wherein the liquid feedstock comprises the heavy boiling point component having a boiling point of at least about 800° F. in an amount up to about 50 wt.%, or 40 wt.%, or 30 wt.%, or 20 wt.%, or 10 wt.%, or in a range of about 10 wt.% to 50 wt.%, or 10 wt.% to 40 wt.%, or 10 wt.% to 30 wt.%, or 20 wt.% to 30 wt.%.

[0078] 7. The process of any of paragraphs 1 to 6, wherein liquid product is recycled to the hydroconversion reactor.

[0079] 8. A method as described in any of paragraphs 1 to 7, wherein the solid biomass feedstock comprises a solid biomass component selected from wood or lumber mill by-products, leaves, grasses, algae, crop by-products, municipal solid waste, or a combination thereof, optionally wherein the solid biomass component is ground, pulverized, sliced, or in the form of particles, pellets, powder, shavings, chips, dust, or crushed, or a combination thereof.

[0080] 9. The method of any one of paragraphs 1 to 8, wherein the slurry hydroconversion catalyst is in the form of fine particles dispersed in the reactor liquid reaction medium and is a supported catalyst, an unsupported catalyst, or a combination thereof.

[0081] 10. A process as described in any of paragraphs 1 to 9, wherein the slurry hydroconversion catalyst is unsulfided or presulfided prior to addition to the reactor, optionally dispersed in a hydrocarbon oil diluent, and wherein the slurry catalyst comprises a metal selected from Group VIB, Group VIII or Group IIB of the Periodic Table or a combination thereof.

[0082] 11. The process of any of paragraphs 1 to 10, wherein the slurry hydroconversion catalyst comprises an unsupported catalyst selected from molybdenum sulfide, iron sulfide, nickel sulfide, zinc sulfide, iron zinc, or a combination thereof.

[0083] 12. The method of any one of paragraphs 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 a combination thereof.

[0084] 13. The process of any of paragraphs 1 to 12, wherein the slurry hydroconversion catalyst comprises a supported catalyst, wherein the support is selected from alumina, silica-alumina, zeolite, or a combination thereof.

[0085] 14. The method of any of paragraphs 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.

[0086] 15. A method as described in any of paragraphs 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.

[0087] 16. The process of any of paragraphs 1 to 15, wherein the hydroconversion process conditions include an operating temperature in the range of about 650 to 950°F, a reactor pressure of about 300 psig to 3500 psig, an average residence time of 10 minutes to 5 hours, and a space velocity of about 0.1 to 5.0, or 0.5 to 5.0, or 0.5 to 2.0 hr -1 , and, optionally, wherein liquid product and / or slurry catalyst is recycled to the slurry hydroconversion reactor.

[0088] 17. The method of any of paragraphs 1 to 16, wherein the char yield is less than about 5 weight percent, or less than about 2 weight percent, or less than about 1 weight percent of the solid biomass fed to the method.

[0089] 18. The method of any of paragraphs 1 to 17, wherein the hydroconversion product comprises a liquid hydrocarbon product having an oxygen content of less than about 3 wt% or less than about 1 wt%, and / or wherein the total acid number (TAN) is less than about 1.

[0090] The present disclosure is not limited to the specific embodiments described in this application, which are intended to illustrate various aspects. Obviously, many modifications and changes can be made without departing from its spirit and scope. In addition to those methods and systems listed here, functionally equivalent methods and systems within the scope of the present disclosure can be apparent from the above representative descriptions. These modifications and changes are intended to fall within the scope of the attached representative claims. The present disclosure is only subject to the terms of the attached representative claims and the full range of equivalents authorized by these representative claims. It will also be understood that the terms used herein are only used for the purpose of describing specific embodiments and are not intended to be limited.

[0091] The foregoing description and its associated embodiments are given for illustrative purposes only. It is not exhaustive and does not limit the invention to the exact form disclosed. Those skilled in the art will appreciate from the foregoing description that modifications and changes may be made according to the above teachings, or modifications and changes may be obtained by practicing the disclosed embodiments. For example, in some cases, the steps described do not need to be performed in the same order discussed or with the same degree of separation. Similarly, various steps may be omitted, repeated or combined as needed to achieve the same or similar purposes. Therefore, the present invention is not limited to the above embodiments, but is defined by the appended claims according to the full scope of their equivalents.

[0092] In the foregoing description, various preferred embodiments have been described with reference to the accompanying drawings. However, it will be apparent that various modifications and variations may be made thereto, and that additional embodiments may be implemented, without departing from the broader scope of the invention as set forth in the appended claims. Therefore, the description and drawings should be regarded as illustrative rather than restrictive.

[0093] Where permitted, all publications, patents, and patent applications cited in this application are incorporated herein by reference in their entirety to the extent such disclosure is not inconsistent with the present invention.

Claims

1. A direct biomass hydroconversion process for producing renewable fuels, comprising: Feeding a solid biomass feedstock and a liquid feedstock into a slurry hydroconversion reactor respectively; wherein the slurry hydroconversion reactor comprises 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 sufficient time to convert the solid biomass feedstock and the liquid feedstock into a hydroconversion product; as well as removing a hydroconversion product from the reactor; Wherein, the solid biomass feedstock is directly fed into the slurry hydroconversion reactor and is provided as a raw biomass feedstock containing biomass components, and the biomass components are not chemically treated or modified before being directly fed into the slurry hydroconversion reactor.

2. The method of claim 1, wherein the method provides a renewable fuel or a hydroconversion product that can be used to prepare a renewable fuel.

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

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

5. The process of any one of claims 1 to 4, wherein the liquid feedstock comprises heavy boiling components having a boiling point of at least about 800°F, and / or wherein 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, optionally wherein the liquid feedstock further comprises a renewable feedstock selected from plastic and / or wood pyrolysis oil, lipids, vegetable oils, or combinations thereof.

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

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

8. The method of any one of claims 1 to 7, wherein the solid biomass feedstock comprises a solid biomass component selected from wood or lumber mill byproducts, leaves, grasses, algae, crop byproducts, municipal solid waste, or a combination thereof, optionally wherein the solid biomass component is ground, pulverized, sliced, or in the form of particles, pellets, powder, shavings, chips, dust, or pulverized, or a combination thereof.

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

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

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, iron zinc, or a combination thereof.

12. The method 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 a combination thereof.

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

14. The method 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 before being fed to the reactor.

15. The method 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 process of any one of claims 1 to 15, wherein the hydroconversion process conditions include an operating temperature in the range of about 650 to 950°F, a reactor pressure of about 300 psig to 3500 psig, an average residence time of 10 minutes to 5 hours, and a space velocity of about 0.1 to 5.0, or 0.5 to 5.0, or 0.5 to 2.0 hr -1 , and, optionally, wherein liquid product and / or slurry catalyst is recycled to the slurry hydroconversion reactor.

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

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

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