Renewable solid biomass slurry hydroconversion catalyst, production method, and slurry hydroconversion process

Abstract

A slurry hydroconversion catalyst formed from solid biomass having a porous structure encapsulating a slurry catalyst precursor in pores is described. The slurry hydroconversion catalyst is made by impregnating the porous structure with the slurry catalyst precursor. The catalyst is useful in a hydroconversion process that converts feedstocks including hydrocarbon-based feedstocks and biomass feedstocks into liquid and gaseous products including renewable fuels and other renewable products. The hydroconversion process can utilize solid biomass for preparing the slurry catalyst and as a feedstock, and does not require the use of chemically treated or modified biomass. Low coke formation rates and other advantages can be obtained.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application is related to and claims the benefit of priority under 35 U.S.C.§ 119(e) to U.S. Provisional Patent Application No. 63 / 355,560, filed on June 24, 2022, entitled "RENEWABLE SOLID BIOMASS SLURRY HYDROCONVERSION CATALYST, METHOD OF MAKING, AND SLURRY HYDROCONVERSION PROCESS", the entire disclosure of which is incorporated herein by reference.

[0002] This disclosure relates to renewable biomass slurry hydroconversion catalysts, methods of making the catalysts, and slurry hydroconversion processes using the catalysts.

Background Art

[0003] The use of renewable resources has received significant attention and effort in the push to develop alternatives to fossil fuels. A variety of biomass materials, particularly certain solid lignocellulosic materials and other carbohydrates, have been of great interest due to their diversity, availability, and versatility, which has led to the development and commercialization of multiple bio - based fuel technologies. The ongoing economic benefits and the desire to reduce the use of fossil fuels have motivated improvements in existing technologies and the development of new processes for producing renewable fuels and other renewable products using solid biomass.

[0004] Renewable fuels (biofuels) are considered important in reducing carbon dioxide and greenhouse gas emissions. Biofuels derived from food are typically fuels made from food supply sources produced on arable land, while biofuels derived from non-food sources are typically manufactured from lignocellulosic biomass such as forestry residues or agricultural residues / wastes. Renewable fuels derived from non-food sources are preferred over biofuels derived from competing biomass food sources. Typical feedstocks for non-food sources include wood, grass, algae, crop by-products, municipal solid waste, and the like.

[0005] Slurry catalysts have been used to process renewable feedstocks and other hydrocarbon feedstocks into various products. In some cases, using slurry hydrotreating requires limiting the feedstock to the slurry process or pretreating it so as to be suitable for slurry hydrotreating or to reduce contamination of conventional slurry catalysts. Conventional supported slurry catalysts include a support material such as a refractory base carrier containing alumina, silica, magnesia, titania, zeolite, silica-aluminate, carbon, phosphorus, and the like and combinations thereof. See, for example, U.S. Pat. Nos. 8,795,472; 8,802,586; 8,022,259; and 9,593,242. Coke formation and contaminant deposition on conventional supported catalysts can lead to a decrease in catalyst activity and catalyst life, and as a result, a significant increase in operating costs.

[0006] It would be highly beneficial to provide a simplified process for directly using solid biomass in a hydroconversion process for producing renewable fuels (or products useful in making renewable fuels). Reducing the pretreatment of solid biomass or using conventional catalyst support materials would be advantageous. In view of the global efforts to utilize methods for reducing fossil fuel use, the use of high-biomass-content feeds that minimize or eliminate the use of co-fed fossil fuels would be particularly desirable. It would be highly desirable to provide a cost-effective and energy-efficient method for processing solid biomass into renewable fuels having a chemical composition similar to fossil fuels in a manner that reduces the concerns and problems associated with the use of conventional slurry catalysts for biomass hydrogenation.

Summary of the Invention

[0007] The present invention generally relates to the slurry hydrogenation treatment of renewable biomass feeds. In one aspect, there is provided a solid biomass slurry hydroconversion catalyst, wherein the solid biomass has a porous structure and pore volume, and the slurry catalyst precursor is encapsulated within the pores of the solid biomass. The catalyst precursor typically comprises a Group VIB metal or a Group VIII metal or a Group IIB metal, or a combination thereof.

[0008] In another aspect, there is provided a method for producing a solid biomass slurry hydroconversion catalyst, comprising contacting a solid biomass feedstock having a porous structure and pore volume with a slurry catalyst precursor under conditions sufficient to impregnate the slurry catalyst precursor into the pores of the solid biomass; and recovering the impregnated solid biomass feedstock having pores impregnated with the slurry catalyst precursor. The slurry catalyst precursor typically comprises a Group VIB metal or a Group VIII metal or a Group IIB metal, or a combination thereof.

[0009] In a further aspect, there is provided a slurry hydroconversion process comprising contacting a solid biomass slurry hydroconversion catalyst with a feedstock in the presence of hydrogen under slurry hydroconversion conditions to convert a portion of the feedstock into liquid and / or gaseous products. The solid biomass slurry hydroconversion catalyst typically comprises a solid biomass having a porous structure and pore volume, with pores encapsulating a slurry catalyst precursor. The slurry catalyst precursor typically comprises a Group VIB metal or a Group VIII metal or a Group IIB metal, or a combination thereof.

[0010] The catalysts and hydroconversion processes of the present invention provide several advantages and benefits. For example, since the catalytically active sites are directly supported on the solid biomass, which is also the hydroconversion feedstock, high catalytic activity can be achieved due to the proximity of the active sites to the feedstock. The preparation of the solid biomass hydroconversion catalyst also provides a cost-effective approach of making a biomass slurry catalyst and using the biomass slurry catalyst in the hydroconversion process. Furthermore, better dispersion of the catalytically active sites (i.e., lower concentration of the active sites on the biomass support) and conversion of the biomass support as the feedstock during the hydroconversion process result in improved performance.

DETAILED DESCRIPTION OF THE INVENTION

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

[0012] The following description of embodiments provides non-limiting representative examples while referring to numerical values for detailing the features and teachings of various aspects of the present invention. The described embodiments should be recognized as being capable of being practiced separately from, or in combination with, other embodiments from the description of the embodiments. A person skilled in the art should be able to acquire and understand another described aspect of the present invention by reviewing the description of the embodiments. The description of the embodiments should facilitate the understanding of the present invention to the extent that other practical forms, although not specifically covered, that are within the scope of the knowledge of a person skilled in the art upon reading the description of the embodiments will be understood to be consistent with the application of the present invention.

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

[0014] The term "hydroconversion" refers to a process or step carried out in the presence of hydrogen for hydrocracking, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodechlorination, hydrodecarbonation, hydrodecarbonylation and / or hydrodearomatization (e.g., impurities) of hydrocarbon or biomass feedstocks and / or for hydrogenation of unsaturated compounds in the feedstock. Depending on the type of hydrocracking and reaction conditions, the products of the hydrocracking process can have, for example, improved aromatic content, oxygen content, viscosity, viscosity index, saturated fats content, low temperature properties, volatility, and depolarization degree.

[0015] The term "conventional catalyst support" is used in its ordinary sense in the art and includes typical catalyst support materials such as alumina, silica-alumina, activated carbon, zeolite and non-zeolite molecular sieves. The biomass materials used in the present invention are not conventional catalyst supports and can be referred to as "non-conventional" or "non-conventional supported materials", etc.

[0016] "Catalyst precursor" refers to a compound containing one or more catalytically active metals, which serves as the basis for ultimately forming a slurry catalyst and has catalytic activity as a hydrotreating catalyst. One example is an aqueous catalyst prior to the conversion step with a hydrocarbon diluent, and another example is a metal sulfide precursor. The preparation of catalyst precursors and slurry catalysts is described in various patents, such as US8,802,586, WO2012 / 092006, etc.

[0017] The term "biomass" is intended to refer to any suitable biomass feedstock, including biomass that has not been chemically treated or reformed prior to use in the process, as well as biomass that has been mechanically and / or chemically reformed. Chemically treated or reformed biomass materials include, for example, lignocellulosic materials that have been treated to remove or reduce the content of certain components or to reform such components, such as removing cellulose or hemicellulose or reforming lignin. Other reformed biomass materials may include biomass materials reformed by roasting, or biomass treated using slow pyrolysis, fast or flash pyrolysis, hydrothermal liquefaction, hydrocracking, kraft treatment, etc. Biomass materials may include mechanically reformed biomass materials or dried biomass materials. Heat-treated biomass materials are "biomass" materials that are included within the scope of the context of the present invention, including cases where such biomass materials have been chemically reformed, for example, in the case of pyrolysis products derived from biomass. A typical drying process does not change the biomass composition but only removes moisture and thus is not a chemical reforming.

[0018] The term "pore volume", when used to represent the porosity of solid biomass, may be described in terms of the "wet pore volume" and the "pore volume" determined by mercury intrusion porosimetry. The "initial wet pore volume" or "wet pore volume" is measured by the initial wet impregnation method. In this method, a certain amount of dry biomass is impregnated with a liquid, typically water, by capillary action until all the biomass pores are saturated. The wet "pore volume" is calculated by dividing the total volume of water absorbed in the biomass pores by the total weight of the solid biomass. The mercury intrusion pore volume of solid biomass is measured in accordance with ASTM D4284 and is typically provided by a commercially available mercury intrusion porosimeter.

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

[0020] The listing of classes of components, such as elements, materials, etc., from which individual components, or mixtures of components, may be selected is intended to include any and all possible sub - combinations of the listed components and their mixtures, unless otherwise specified. Also, "including" and its variations are intended to be non - limiting in such a way that a listing of items as a list is not made to exclude other similar items that may be equally useful in the materials, compositions, and methods of the present invention.

[0021] Certain advantages of using a porous solid biomass as a support for a catalytic metal have been described above in this specification, but it should be noted that other benefits may also be provided. For example, since a separate catalyst support material is not required, the biomass support itself can be used for hydroconversion and can typically be consumed during the process. Therefore, the need to handle spent catalyst support material can be reduced or eliminated if (or to the extent that) the biomass support is consumed in the reaction. The use of the biomass support also results in a higher degree of dispersion of the catalyst in the reaction system and the ability to use the catalyst with a more diverse feedstock morphology. Certain benefits regarding the product can also be realized, including a reduced coke formation rate that can be less than about 8 wt% or less than about 5 wt% of the biomass fed to the process. The oxygen content of the liquid product can also be less than about 3 wt% or less than about 1 wt%, and / or the total acid number (TAN) can be less than about 1.

[0022] Without limitation, the process of the present invention can be used to provide renewable fuels or product components useful in making renewable fuels from liquid and / or gaseous products derived from the process.

[0023] The solid biomass slurry hydroconversion catalyst comprises a solid biomass and a slurry catalyst precursor encapsulated within the porous structure of the biomass. The slurry catalyst precursor encapsulated within the porous structure of the solid biomass comprises a Group VIB metal or a Group VIII metal or a Group IIB metal, or a combination thereof.

[0024] Solid biomass may include solid biomass components selected from wood or lumber mill by-products, leaves, grass, algae, crop by-products, municipal solid waste, or combinations thereof. Optionally, the solid biomass may be ground, crushed, shredded, or in the form of particles, pellets, powder, shavings, chips, dust, or pulverized, or combinations thereof. For example, the slurry hydroconversion catalyst may be in the form of fine particles comprising a biomass-supported catalyst formed from a catalyst precursor, and may include an unsupported catalyst formed from the catalyst precursor. The fine particles may typically be the same particle size and shape as the solid biomass feedstock. Any porous biomass may be used, including but not limited to hardwood, softwood, algae, crop by-products, etc. The biomass material may be crushed or processed to any desired particle size or particle size range, e.g., 50 microns to 10 mm, or to wood chips up to 3 cm in length, etc.

[0025] Generally, solid biomass is porous and may be provided as biomass containing porous biomass components. Such biomass may be used in any form as long as it is porous, e.g., it may be chemically treated or modified before being used to make a slurry hydroconversion catalyst, or it may be untreated or unmodified. Solid biomass may include lignocellulosic materials that have not been chemically treated. In some embodiments, certain modified biomass materials, such as lignin, e.g., from a paper-making process, may also be used as the porous solid biomass within the scope of the present invention. In other embodiments, the solid biomass may include components that have been chemically modified, e.g., to enhance the absorption and impregnation of oily and / or aqueous workplace precursors.

[0026] Solid biomass typically has a pore volume of less than about 3 ml / g, or less than 2.5 ml / g, or less than 2 ml / g, or less than 1.5 ml / g, or less than 1 ml / g, as measured by mercury intrusion porosimetry, or is in the range of about 0.1 - 3 ml / g, or 0.3 - 3 ml / g, or 0.5 - 3 ml / g, or 0.5 - 2.5 ml / g, or 0.5 - 2 ml / g.

[0027] The slurry hydroconversion catalyst is generally dispersed in the liquid reaction medium of the reactor and encapsulates a catalyst precursor containing a Group VIB, Group VIII, or Group IIB metal, or a combination thereof, within the biomass pore structure of the solid biomass. The biomass slurry catalyst may or may not be sulfided or pre-sulfided before being added to the reactor. The biomass slurry catalyst may also be dispersed in a hydrocarbon oil diluent. It is typical to supply a sufficient amount of the slurry catalyst to the slurry reactor(s) such that the slurry catalyst concentration is 300 wppm or more, or 500 wppm or more, or up to about 3 wt% (ratio of catalyst metal to feedstock). The slurry catalyst may include one or more different slurry catalysts, either as a single mixed feed stream or as separate feeds to the reactor.

[0028] In some cases, the slurry hydroconversion catalyst includes a catalyst selected from molybdenum sulfide, iron sulfide, nickel sulfide, zinc sulfide, iron zinc, or combinations thereof. The slurry catalyst may be provided in the form of a catalyst precursor selected from oil-soluble Group VIB metal (e.g., molybdenum) compounds, water-soluble Group VIB metal (e.g., molybdenum) compounds, aqueous Group VIB metal (e.g., molybdenum) trisulfide suspensions or colloids, or combinations thereof.

[0029] Suitable slurry catalyst precursors, slurry catalysts formed from such catalyst precursors, and the preparation of slurry catalysts are described in various patents, such as US8,802,586, WO2012 / 092006, US2015 / 0329790A1, etc. Catalysts and precursors used in typical slurry hydrotreating systems can contain at least one Group VIB metal (e.g., Mo), and optionally, at least one Group VIII metal (e.g., Ni and / or Co), and optionally at least one Group IIB metal (e.g., Zn). Such precursors can also be used to form active catalysts in biomass materials according to the present invention. In some cases, the slurry catalyst can be formed from a multi-metal catalyst precursor containing at least two Group VIB metals and optionally at least one Group VIII metal, where the ratio of at least two Group VIB metals to the Group VIII metal is from 10:1 to 1:10.

[0030] In some cases, the slurry catalyst according to the present invention can contain (on a dry basis) about 1 to 60 wt%, or 10 to 60 wt%, or 10 to 50 wt% of at least one Group VIB metal (calculated as metal oxide), and optionally, 0.5 to 30 wt%, or 2 to 20 wt% of at least one Group VIII metal (calculated as metal oxide), and optionally at least one Group IIB metal. In other examples, the Group VIB metal content can be greater than 30 wt%. The weight ratio of Group VIII and / or Group IIB metals to the Group VIB metal can be in the range of 1 to 90%, or 2 to 50%, or 5 to 30%, or 10 to 20%.

[0031] The slurry catalyst formed according to the present invention has the formula: (M t ) a (X u ) b (S v ) d (C w ) e (H x ) f (O y )g (N z ) h may have, wherein M represents at least one Group VIB metal, such as Mo, W, etc., or a combination thereof, X functions as a promoter metal and represents at least one of non-noble Group VIII 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 each represent the total charge of each of M, X, S, C, H, O, and N, and (ta + ub + vd + we + xf + yg + zh) = 0. The ratio of b to a of the subscript has a value of 0 to 5 (0 ≦ b / a ≦ 5). S represents sulfur, and the subscript d has a value of (a + 0.5b) to (5a + 2b). C represents carbon, and the subscript e has a value of 0 to 11(a + b). H is hydrogen, and the subscript f has a value of 0 to 7(a + b). O represents oxygen, and the subscript g has a value of 0 to 5(a + b). N represents nitrogen, and the subscript h has a value of 0 to 0.5(a + b). The subscript b has a value of 0 in some embodiments, such as a single metal component catalyst without a promoter, such as a Mo-alone catalyst.

[0032] The slurry catalyst can be prepared from a catalyst precursor composition containing 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, pentanedionates, octanoates, and acetates of Group VIB and Group VIII metals.

[0033] The slurry catalyst can be in the form of fine particles having the same nominal particle size and shape as the biomass feedstock. The slurry catalyst can typically have any desired shape and particle size or particle size range, for example, an average particle size within the range of 50 microns to 10 mm. Also, large particle sizes may be used, including, for example, wood chips up to about 3 cm in length. The slurry hydroconversion catalyst may or may not be sulfided, or may be presulfided, before being added to the reactor. The methods and conditions for presulfiding the catalyst or sulfiding in the system are not particularly limited and can be carried out according to the conditions in the art of cultivation.

[0034] Generally, a method for making a solid biomass slurry hydroconversion catalyst involves contacting a solid biomass feedstock having a porous structure and pore volume with a slurry catalyst precursor under conditions sufficient to impregnate the slurry catalyst precursor into the pores of the solid biomass; and recovering the impregnated solid biomass feedstock having pores impregnated with the slurry catalyst precursor. The slurry catalyst precursor includes a Group VIB metal or a Group VIII metal or a Group IIB metal, or a combination thereof.

[0035] The solid biomass can be used as a support for the active catalyst and can be prepared by any suitable method, for example, by utilization of the dry incipient wetness impregnation technique. For example, in the incipient wetness technique, the biomass is mixed with an aqueous solution of the catalyst precursor metal to impregnate the biomass with the precursor. Optionally, the impregnated biomass may then be dried by any suitable method, for example, by using a sequential drying oven or by drying on a heated conveyor belt. The impregnation results in a concentration of the impregnated catalyst metal of about 0.01 to 10.0 wt%, or more notably 0.01 to 2 wt%, of the total biomass.

[0036] The impregnated biomass may be present at a concentration of 0.01 to 100.0 wt%, or 0.1 to 40.0 wt%, or less than 25 wt% relative to the feedstock. Multiple impregnation and drying steps may be used. In some cases, higher concentrations of biomass slurry catalyst can be obtained by impregnating the biomass material by spray coating an aqueous Group VIB metal compound onto the biomass material. Further details regarding impregnation techniques are disclosed in the patent literature. See, for example, U.S. Patent Nos. 4,559,130 and 5,190,641.

[0037] In the hydroconversion process of the present invention, the solid biomass slurry hydroconversion catalyst and any additional feedstock, such as a liquid hydrocarbon or a biomass feedstock, can be separately fed to the hydroconversion reactor. Combinations of one or more of the feedstocks and one or more solid biomass slurry hydroconversion catalysts can be used. The slurry biomass hydroconversion catalyst, any solid biomass feedstock, any liquid feedstock, and hydrogen can be premixed in any combination or amount before being fed to the hydroconversion reactor.

[0038] The feed to the hydroconversion reactor can typically contain at least about 10 wt% of the solid biomass slurry hydroconversion catalyst, 0 to 90 wt% of the liquid feedstock, and 0 to 80 wt% of the solid biomass feedstock. One or more liquid products and / or the slurry catalyst may be recycled to the hydroconversion reactor. Generally, any suitable hydroconversion process conditions may be used. For example, typical hydroconversion (hydrocracking) process conditions include operation within a temperature range of about 650 to 950°F, a reactor pressure of about 300 to 3000 psig, an average residence time of 10 minutes to 10 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 -1. Mixing within the reactor can help improve solid dispersion and reactor temperature dynamics and can be accomplished using mechanical mixing, liquid recirculation, gas bubbling, etc.

[0039] The solid biomass slurry hydroconversion catalyst can be used in its solid form or as a slurry in a liquid feedstock. The transport of the solid biomass slurry hydroconversion catalyst to the reactor can be carried out by various single or combined means, including, for example, the use of a pressure transport vessel, an extruder, a rotary valve or a lock hopper. The solid biomass feed to the hydroconversion reactor can contain about 80 - 100 wt% of solid biomass and 0 - 20 wt% of a liquid, such as a suitable feedstock.

[0040] The biomass used in the solid biomass slurry hydroconversion process can undergo various reactions, such as hydrocracking, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodechlorination, hydrodecarbonation, hydrodecarbonylation, hydrodearomatization, or combinations thereof, including the porous solid biomass used in the catalyst.

[0041] The liquid feedstock can usually contain heavy boiling point 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 centrifuged oil, FCC middle distillate, hydrocracking unconverted oil, or combinations thereof. The heavy boiling point 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 wt% or 40 wt% or 30 wt% or 20 wt% or 10 wt%, or in the range of about 10 - 50 wt%, or 10 - 40 wt%, or 10 - 30 wt%, or 20 - 30 wt%. The liquid feedstock can contain one or more components having a high boiling point of at least about 650°F, or 675°F, or 700°F, or 725°F, or 750°F. The amount of the high boiling point liquid feedstock components present in the liquid feedstock can be at least about 10 wt% or 20 wt% or 30 wt% or 40 wt% or 50 wt% or 60 wt% or 70 wt% or 80 wt% or 90 wt% of the liquid feedstock.

[0042] The liquid feedstock may further include renewable feedstocks such as liquids (e.g., vegetable oils including used cooking oil, seed oils, animal fats, waste oils, algal oils, etc.), renewable bio-crude oil, intermediates and / or product streams from thermochemical processes (e.g., pyrolysis, gasification and subsequent quality improvement, and / or liquefaction), or any product or by-product of a process using bottoms and / or tail oil pitch similar to renewable feedstocks, hydrothermal liquefaction products, distillation bottoms residues, or combinations thereof. The liquid feedstock may further include feedstocks derived from recycled or recovered materials (sometimes referred to as recycle materials). Suitable examples of recycled or recovered materials include, but are not limited to, polymers, plastics, rubbers, or combinations thereof.

[0043] In addition, the liquid feedstock can be combined with a solid biomass feedstock before being directly fed into the hydroconversion reactor. All or part of any recycled liquid product may be included as part of the liquid feedstock.

Examples

[0044] Experimental tests were conducted to prepare a solid biomass slurry hydroconversion catalyst and evaluate its hydroconversion performance. Wood powder was used as a representative material for the solid biomass feedstock, and an autoclave reactor was used to evaluate the hydroconversion performance of the biomass slurry hydroconversion catalyst.

[0045] Example 1 - Evaluation of the Characteristics of Solid Biomass Pores The crushed wood powder was used as a representative solid biomass feedstock. The initial (wet) pore volume was measured by the initial wet impregnation method. Approximately 5 grams of wood powder was weighed into a 50 ml beaker. The wood powder was gradually peptized with deionized water. Water was drawn into the pores of the wood powder by capillary action, and finally all the pores were saturated over a certain period of time, for example, 1 hour. When the absorption capacity was reached, all the excess liquid was visible. The wet pore volume was calculated by dividing the total volume of water absorbed by the pores by the total weight of the wood powder. The mercury intrusion pore volume was measured using a mercury intrusion porosimeter (Micrometritics) according to ASTM D4284. This test determines the intrusion pore volume distribution of a solid by the method of mercury intrusion porosimetry. The range of applicable pore diameters is controlled by the mercury intrusion pressure. The range is typically an apparent pore inlet diameter of about 0.003 microns (3 nm) to 100 microns.

[0046] The wood powder sample was used as a solid biomass feedstock and catalyst support for this test. The sample was mainly obtained from Japanese larch and was crushed to 80 mesh. The biomass pore volume of the wood powder determined using mercury intrusion porosimetry was 1.68 cc / g.

[0047] The results are shown in Table 1.

Table 1

[0048] The pore volume can also be estimated by the initial wet method. Using this method, the wood powder absorbed 1.39 cc of water per gram of the tested wood powder feedstock / catalyst support.

[0049] Example 2 - Preparation of Solid Biomass Catalyst Using the wood powder biomass feedstock of Example 1, the catalyst precursor was supported. Ammonium dimolybdate aqueous solution was used as the catalyst precursor. The precursor can be supported by well-established impregnation methods, such as dry impregnation, wet impregnation or the incipient wetness method. In this example, the catalyst precursor was supported on the biomass feedstock by the incipient wetness method. The ratio of molybdenum to the feedstock / carrier was 1:100. This allows for a high degree of dispersion of the catalyst precursor and the active sites in the subsequent carrier. The supported catalyst can be used either dried or without drying.

[0050] Example 3 - Hydroconversion of Solid Biomass A 1000 ml autoclave reactor was charged with 400 g of heavy oil (a mixture of vacuum residue (VR) and fluid catalytic cracking unit (FCC) centrifuge oil) and 100 g of ammonium dimolybdate aqueous solution-impregnated wood powder containing 1 g of Mo (equivalent to 2000 ppm of Mo in the total feed) from Example 2. 5 g of elemental sulfur was added as a sulfiding agent. The reactor was pressurized to 2500 psig, heated to a target temperature of 805°F, and maintained at 805°F for 2 hours. A low flow rate of hydrogen feed was maintained during the reaction while keeping the reactor pressure constant. A large amount of hydrogen and gaseous products were vented throughout the test. After 2 hours, the reactor was cooled. The overhead product was recovered from the gas-liquid separator on the downstream side of the reactor, while the heavy liquid and solid product slurry were recovered from the reactor. The overhead product was in two layers. The lower aqueous layer was mainly produced by the hydrodeoxygenation of wood, and the liquid oil layer of the light products was due to the hydrocracking of the biomass and hydrocarbon feedstock. The reactor slurry consisted of high-boiling products, catalyst, and coke. The solids from the slurry phase were separated by filtration and analyzed. The biomass conversion rate was calculated as follows: Biomass conversion rate = 1 - (weight of coke derived from biomass) / (weight of biomass feed)

[0051] At the end of the trial, 5.3 g of solid derived from the wood powder was recovered. The corresponding biomass conversion rate was 94.7%.

[0052] The above results demonstrate that useful products, including renewable fuel grade products, can be produced by the preparation of a solid biomass slurry hydroconversion catalyst and its use in a slurry hydroconversion process. The solid biomass and hydrocarbon feedstock contained in the catalyst can be highly converted. There is no need for prior art processes that require a liquefaction process step for biomass pretreatment. Therefore, any concerns regarding high TAN (total acid number) inclusions should be alleviated, as should any concerns regarding the instability of intermediate liquefaction products. In addition, heavy oil feedstocks such as vacuum residue (VR) can be used, for example, as a liquid carrier (feedstock) without significantly limiting the aromaticity.

[0053] For the avoidance of doubt, the present disclosure relates to the subject matter recited in the numbered clauses below: 1. A solid biomass supported slurry hydroconversion catalyst useful in the production of renewable fuels, wherein the solid biomass has a porous structure and pore volume, and the pores of the solid biomass are adapted to encapsulate a slurry catalyst precursor therein, and a slurry catalyst precursor encapsulated within the porous structure of the solid biomass, the catalyst precursor comprising a Group VIB metal or a Group VIII metal or a Group IIB metal, or a combination thereof. The catalyst comprising the above. 2. The catalyst according to clause 1, wherein the solid biomass comprises solid biomass components that have not been chemically treated or reformed. 3. The catalyst according to clause 1 or clause 2, wherein the solid biomass is selected from wood or sawmill by-products, leaves, grass, algae, crop by-products, municipal solid waste, or combinations thereof, and optionally, the solid biomass is in a ground, pulverized, shredded, or particulate, pellet, powder, shaving, chip, dust, or pulverized form, or combinations thereof. 4. The dry basis pore volume of the solid biomass, when measured by mercury intrusion porosimetry, is less than about 3 ml / g, or less than 2.5 ml / g, or less than 2 ml / g, or less than 1.5 ml / g, or less than 1 ml / g, or is in the range of about 0.1 to 3 ml / g, or 0.3 to 3 ml / g, or 0.5 to 3 ml / g, or 0.5 to 2.5 ml / g, or 0.5 to 2 ml / g, the catalyst according to any one of clauses 1 to 3. 5. The slurry hydroconversion catalyst has the same particle size and shape as the solid biomass, the catalyst according to any one of clauses 1 to 4. 6. The slurry hydroconversion catalyst is not sulfided or is pre-sulfided before use as a catalyst, and optionally is dispersed in a hydrocarbon oil diluent, or is in solid or slurry form, the catalyst according to any one of clauses 1 to 5. 7. The catalyst precursor is selected from an oil-soluble Group VIB metal compound, a water-soluble Group VIB metal compound, an aqueous Group VIB metal trisulfide suspension or colloid, or a combination thereof, the catalyst according to any one of clauses 1 to 6. 8. A method for producing a solid biomass-supported slurry hydroconversion catalyst useful in producing renewable fuels, contacting a solid biomass feedstock having a porous structure and pore volume with the slurry catalyst precursor under conditions sufficient to impregnate the slurry catalyst precursor into the pores of the solid biomass; and recovering the impregnated solid biomass feedstock having the pores impregnated with the slurry catalyst precursor comprising, the slurry catalyst precursor comprising a Group VIB metal or a Group VIII metal or a Group IIB metal, or a combination thereof, the method. 9. The solid biomass comprises solid biomass components that have not been chemically treated or reformed, the method according to clause 8. 10. The solid biomass is selected from wood or sawmill by-products, leaves, grass, algae, crop by-products, municipal solid waste, or combinations thereof, and optionally, the solid biomass is ground, pulverized, shredded, or in the form of microparticles, pellets, powders, shavings, chips, dust, or pulverized, or a combination thereof, according to the method of clause 8 or clause 9. 11. The dry basis pore volume of the solid biomass is less than about 3 ml / g, or less than 2.5 ml / g, or less than 2 ml / g, or less than 1.5 ml / g, or less than 1 ml / g, or is in the range of about 0.1 - 3 ml / g, or 0.3 - 3 ml / g, or 0.5 - 3 ml / g, or 0.5 - 2.5 ml / g, or 0.5 - 2 ml / g, according to the method of any one of clauses 8 - 10. 12. The slurry hydroconversion catalyst has the same particle size and shape as the solid biomass, according to the method of any one of clauses 8 - 11. 13. The slurry hydroconversion catalyst is not sulfided or pre-sulfided before use as a catalyst, and optionally, is dispersed in a hydrocarbon oil diluent or is in solid or slurry form, according to the method of any one of clauses 8 - 12. 14. The catalyst precursor is selected from an oil-soluble molybdenum compound, a water-soluble molybdenum compound, an aqueous molybdenum trisulfide suspension or colloid, or combinations thereof, according to the method of any one of clauses 8 - 13. 15. A slurry hydroconversion process useful for producing renewable fuels, contacting a solid biomass-supported slurry hydroconversion catalyst with hydrogen under slurry hydroconversion conditions to convert the solid biomass into a hydroconversion product comprising a solid biomass slurry hydroconversion catalyst containing a solid biomass having a porous structure and pore volume, wherein the pores of the solid biomass are adapted to encapsulate a slurry catalyst precursor therein, having the slurry catalyst precursor encapsulated within the solid biomass porous structure, and the slurry catalyst precursor comprises a Group VIB metal or a Group VIII metal or a Group IIB metal, or a combination thereof, said process. 16. The process according to clause 15, wherein the solid biomass comprises biomass components that have not been chemically treated or reformed. 17. The process according to clause 15 or clause 16, wherein the process results in a renewable fuel or a product component useful in making a renewable fuel from the hydroconversion product. 18. The process according to any one of clauses 15 to 17, further comprising contacting a feedstock with the slurry hydroconversion catalyst, wherein the feedstock is selected from a renewable feedstock, a recycle feedstock, a liquid hydrocarbon feedstock, or a combination thereof. 19. The process according to any one of clauses 15 to 18, further carried out in the presence of an added sulfurizing agent. 20. The process according to clause 18, wherein the renewable feedstock is selected from wood pyrolysis oil, lipids, vegetable oils, or a combination thereof, or the renewable feedstock comprises solid biomass. 21. The process according to any one of clauses 18 to 20, wherein the recycle feedstock is derived from a recycled or recovered material. 22. The process according to any one of clauses 18 to 21, wherein the liquid hydrocarbon feedstock comprises a heavy boiling point component having a boiling point of at least about 800°F, and the liquid hydrocarbon feedstock is selected from vacuum gas oil, atmospheric residue, vacuum residue, FCC heavy cycle oil or decanted oil, FCC middle distillate, hydrocracked unconverted oil, or a combination thereof. 23. The hydroconversion process includes a slurry hydrocracking reactor for performing the hydroconversion, and the feedstock and the slurry hydroconversion catalyst are supplied to the slurry hydroconversion reactor separately or as a combination of the feedstock and the slurry hydroconversion catalyst, according to the process of clause 18 or clause 19. 24. The feedstock is at least about 10 wt% or 20 wt% or 30 wt% or 40 wt% or 50 wt% or 60 wt% or 70 wt% or 75 wt% or 80 wt% of the total of the feedstock and the slurry hydroconversion catalyst supplied to the hydroconversion reactor, according to the process of any one of clauses 18 to 23. 25. The liquid hydrocarbon feedstock is combined with the solid biomass feedstock before being directly supplied to the slurry hydroconversion reactor, according to the process of any one of clauses 18 to 24. 26. The liquid hydrocarbon feedstock contains the heavy boiling point components in an amount of up to about 50 wt% or 40 wt% or 30 wt% or 20 wt% or 10 wt%, or in the range of about 10 - 50 wt%, or 10 - 40 wt%, or 10 - 30 wt%, or 20 - 30 wt%, according to the process of clause 22. 27. The process according to any one of clauses 15 to 26, wherein the liquid product is recycled. 28. The solid biomass is selected from wood or sawmill by-products, leaves, grass, algae, crop by-products, municipal solid waste, or combinations thereof, and optionally, the solid biomass is in a ground, pulverized, shredded, or particulate, pellet, powder, shaving, chip, dust, or pulverized form, or a combination thereof, according to the process of any one of clauses 15 to 27. 29. The slurry hydroconversion catalyst is not sulfided or pre-sulfided before use, and optionally, is dispersed in a hydrocarbon oil diluent or is in a solid or slurry form, according to the process of any one of clauses 15 to 28. 30. The process according to any one of clauses 15 to 29, wherein the slurry catalyst precursor is selected from an oil-soluble molybdenum compound, a water-soluble molybdenum compound, an aqueous molybdenum trisulfide suspension or colloid, or a combination thereof. 31. The process according to any one of clauses 15 to 30, wherein the solid biomass undergoes hydrocracking, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodechlorination, hydrodecarbonation, hydrodecarbonylation, hydrodearomatization, or a combination thereof. 32. The hydroconversion process conditions include operation within a temperature range of about 650 - 950°F, a reactor pressure of about 300 - 3000 psig, and an average residence time of 10 minutes - 10 hours, or 30 minutes - 5 hours, or 30 minutes - 2 hours, and a space velocity of about 0.1 - 5.0, or 0.5 - 5.0, or 0.5 - 2.0 hr -1 The process according to any one of clauses 15 to 31, wherein optionally, the liquid product and / or the slurry catalyst is recycled to the slurry hydroconversion reactor. 33. The process according to any one of clauses 15 to 32, wherein the coke formation rate 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. 34. The process according to any one of clauses 15 to 33, wherein the oxygen content of the liquid product is less than about 3 wt%, or less than about 1 wt%, and / or the total acid number (TAN) is less than about 1.

[0054] This disclosure is not to be limited by the specific embodiments described herein, which are intended to be examples of various aspects. Although it may be apparent, many modifications and changes can be made without departing from the spirit and scope thereof. Functional equivalent methods and systems within the scope of this disclosure may be apparent from the above representative description, in addition to the methods and systems recited herein. Such modifications and changes are intended to be included within the scope of the appended representative claims. This disclosure should be limited only by the appended representative claims and the full scope of equivalents allowed for such representative claims. It should also be understood that the terms used herein are for the purpose of describing particular embodiments only and are not intended to be limiting.

[0055] The above description, and the related embodiments presented, are for illustrative purposes only. It is not exhaustive and does not limit the invention to the precise forms disclosed. Modifications and changes are possible in light of the above teachings or may be brought about by the practice of the disclosed embodiments, and would be fully understood by those skilled in the art in view of the above description. For example, in some cases, the steps described need not be performed in the same order or with the same degree of separation as described. Similarly, various steps may be omitted, repeated, or combined as necessary to obtain the same or similar results. Accordingly, the invention is defined not by the embodiments described above, but by the appended claims, from the perspective of their full scope and equivalents.

[0056] In the foregoing specification, various preferred embodiments have been described with reference to the accompanying drawings. However, it may be apparent that various modifications and changes can be made to them, and further embodiments can be implemented, without departing from the broader scope of the invention shown in the claims that follow. Accordingly, the specification and drawings are to be regarded as illustrative rather than limiting.

[0057] Although it is permitted, all publications, patents, and patent applications cited in this specification are hereby incorporated by reference in their entirety to the extent that such disclosure is not inconsistent with the present invention.

Claims

**Claim 1** A solid biomass-supported slurry hydroconversion catalyst useful in the production of renewable fuels, comprising a solid biomass having a porous structure and pore volume, wherein the pores of the solid biomass are adapted to encapsulate a slurry catalyst precursor therein, said solid biomass, and a slurry catalyst precursor encapsulated within the porous structure of the solid biomass, said catalyst precursor comprising a Group VIB metal, a Group VIII metal, a Group IIB metal, or a combination thereof comprising said catalyst. **Claim 2** The catalyst according to claim 1, wherein the solid biomass comprises solid biomass components that have not been chemically treated or reformed. **Claim 3** The catalyst according to claim 1 or claim 2, wherein the solid biomass is selected from wood or lumber mill by-products, leaves, grass, algae, crop by-products, municipal solid waste, or combinations thereof, and optionally, the solid biomass is ground, pulverized, shredded, or in the form of particles, pellets, powders, shavings, chips, dusts, or combinations thereof. **Claim 4** The catalyst according to any one of claims 1 to 3, wherein the dry basis pore volume of the solid biomass as measured by mercury intrusion is less than about 3 ml / g, or less than 2.5 ml / g, or less than 2 ml / g, or less than 1.5 ml / g, or less than 1 ml / g, or is in the range of about 0.1 to 3 ml / g, or 0.3 to 3 ml / g, or 0.5 to 3 ml / g, or 0.5 to 2.5 ml / g, or 0.5 to 2 ml / g. **Claim 5** The catalyst according to any one of claims 1 to 4, wherein the slurry hydroconversion catalyst has the same particle size and shape as the solid biomass. **Claim 6** The catalyst according to any one of claims 1 to 5, wherein the slurry hydroconversion catalyst is not sulfided or pre-sulfided prior to use as a catalyst, and optionally, is dispersed in a hydrocarbon oil diluent or is in solid or slurry form. **Claim 7** The catalyst according to any one of claims 1 to 6, wherein the catalyst precursor is selected from oil-soluble Group VIB metal compounds, water-soluble Group VIB metal compounds, aqueous Group VIB metal trisulfide suspensions or colloids, or combinations thereof. **Claim 8** A method for producing a solid biomass-supported slurry hydroconversion catalyst useful in producing renewable fuels, comprising: contacting a solid biomass feedstock having a porous structure and pore volume with the slurry catalyst precursor under conditions sufficient to impregnate the slurry catalyst precursor into the pores of the solid biomass; and recovering the impregnated solid biomass feedstock having the pores impregnated with the slurry catalyst precursor. The method, wherein the slurry catalyst precursor comprises a Group VIB metal, a Group VIII metal, a Group IIB metal, or a combination thereof. **Claim 9** The method according to claim 8, wherein the solid biomass comprises solid biomass components that have not been chemically treated or reformed. **Claim 10** The method according to claim 8 or 9, wherein the solid biomass is selected from wood or lumber mill by-products, leaves, grass, algae, crop by-products, municipal solid waste, or combinations thereof, and optionally, the solid biomass is ground, crushed, shredded, or in the form of particles, pellets, powders, shavings, chips, dusts, or combinations thereof. **Claim 11** The method according to any one of claims 8 to 10, wherein the dry basis pore volume of the solid biomass is less than about 3 ml / g, or less than 2.5 ml / g, or less than 2 ml / g, or less than 1.5 ml / g, or less than 1 ml / g, or is in the range of about 0.1 to 3 ml / g, or 0.3 to 3 ml / g, or 0.5 to 3 ml / g, or 0.5 to 2.5 ml / g, or 0.5 to 2 ml / g. **Claim 12** The method according to any one of claims 8 to 11, wherein the slurry hydroconversion catalyst has the same particle size and shape as the solid biomass. **Claim 13** The method according to any one of claims 8 to 12, wherein the slurry hydroconversion catalyst is not sulfided or is pre-sulfided before use as a catalyst, and optionally, is dispersed in a hydrocarbon oil diluent or is in solid or slurry form. **Claim 14** The method according to any one of claims 8 to 13, wherein the catalyst precursor is selected from an oil-soluble molybdenum compound, a water-soluble molybdenum compound, an aqueous molybdenum trisulfide suspension or colloid, or combinations thereof. **Claim 15** A slurry hydroconversion process useful in producing renewable fuels, contacting a solid biomass-supported slurry hydroconversion catalyst with hydrogen under slurry hydroconversion conditions to convert the solid biomass into a hydroconversion product comprising, wherein the solid biomass slurry hydroconversion catalyst comprises a solid biomass having a porous structure and pore volume, and the pores of the solid biomass are adapted to encapsulate a slurry catalyst precursor therein, having the slurry catalyst precursor encapsulated within the solid biomass porous structure, the slurry catalyst precursor comprising a Group VIB metal or a Group VIII metal or a Group IIB metal, or a combination thereof, said process.

16. The process according to claim 15, wherein the solid biomass comprises biomass components that have not been chemically treated or reformed.

17. The process, results in a renewable fuel, or a product component useful in making a renewable fuel from the hydroconversion product The process according to claim 15 or claim 16.

18. The process according to any one of claims 15 to 17, further comprising contacting a feedstock with the slurry hydroconversion catalyst, wherein the feedstock is selected from a renewable feedstock, a recycle feedstock, a liquid hydrocarbon feedstock, or a combination thereof.

19. The process according to any one of claims 15 to 18, further being carried out in the presence of an added sulfurizing agent.

20. The renewable feedstock is selected from wood pyrolysis oil, lipids, vegetable oils, or a combination thereof, or the renewable feedstock comprises solid biomass, The process according to claim 18.

21. The process according to any one of claims 18 to 20, wherein the recycle feedstock is derived from a recycled or recovered material.

22. The liquid hydrocarbon feedstock comprises a heavy boiling point component having a boiling point of at least about 800°F, and the liquid hydrocarbon feedstock is selected from vacuum gas oil, atmospheric residue, vacuum residue, FCC heavy recycle oil or decant oil, FCC middle recycle oil, hydrocracked unconverted oil, or a combination thereof, the process according to any one of claims 18 to 21.

23. The hydrogenation conversion process includes a slurry hydrocracking reactor for performing the hydrogenation conversion, and the feedstock and the slurry hydrogenation conversion catalyst are supplied to the slurry hydrogenation conversion reactor separately or as a combination of the feedstock and the slurry hydrogenation conversion catalyst. The process according to claim 18 or claim 19.

24. The feedstock is at least about 10 wt% or 20 wt% or 30 wt% or 40 wt% or 50 wt% or 60 wt% or 70 wt% or 75 wt% or 80 wt% of the total of the feedstock and the slurry hydrogenation conversion catalyst supplied to the hydrogenation conversion reactor. The process according to any one of claims 18 to 23.

25. The liquid hydrocarbon feedstock is combined with the solid biomass feedstock before being directly supplied to the slurry hydrogenation conversion reactor. The process according to any one of claims 18 to 24.

26. The liquid hydrocarbon feedstock contains the heavy boiling point components in an amount of up to about 50 wt% or 40 wt% or 30 wt% or 20 wt% or 10 wt%, or in the range of about 10 - 50 wt%, or 10 - 40 wt%, or 10 - 30 wt%, or 20 - 30 wt%. The process according to claim 22.

27. The liquid product is recycled. The process according to any one of claims 15 to 26.

28. The solid biomass is selected from wood or sawmill by - products, leaves, grass, algae, crop by - products, municipal solid waste, or combinations thereof, and optionally, the solid biomass is ground, pulverized, shredded, or in the form of particles, pellets, powders, shavings, chips, dusts, or pulverized forms, or combinations thereof. The process according to any one of claims 15 to 27.

29. The slurry hydrogenation conversion catalyst is not sulfided or pre - sulfided before use, and optionally, is dispersed in a hydrocarbon oil diluent or is in solid or slurry form. The process according to any one of claims 15 to 28.

30. The process according to any one of claims 15 to 29, wherein the slurry catalyst precursor is selected from an oil-soluble molybdenum compound, a water-soluble molybdenum compound, an aqueous molybdenum trisulfide suspension or colloid, or a combination thereof.

31. The process according to any of claims 15 to 30, wherein the solid biomass undergoes hydrocracking, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodechlorination, hydrodecarbonation, hydrodecarbonylation, hydrodearomatization, or a combination thereof.

32. The hydrogenation conversion process conditions include operation within a temperature range of about 650 to 950 °F, a reactor pressure of about 300 to 3000 psig, and an average residence time of 10 minutes to 10 hours, or 30 minutes to 5 hours, or 30 minutes to 2 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 The process according to any one of claims 15 to 31, wherein optionally, a liquid product and / or a slurry catalyst are recycled to the slurry hydrogenation conversion reactor.

33. The process according to any one of claims 15 to 32, wherein the coke formation rate 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.

34. The process according to any one of claims 15 to 33, wherein the oxygen content of the liquid product is less than about 3 wt%, or less than about 1 wt%, and / or the total acid number (TAN) is less than about 1.

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