Renewable biomass hydroconversion of solid seed feedstock

Abstract

Renewable biomass feed hydroprocessing is described, including, for example, a slurry or ebullated bed hydroconversion process in which a feedstock comprising a renewable biomass component is subjected to hydroconversion. The process generally comprises contacting a solid biomass feedstock, such as whole solid seeds, and a hydroconversion catalyst under suitable hydroconversion conditions to convert a portion of the feedstock to liquid and / or gas products.

Description

RENEWABLE BIOMASS HYDROCONVERSION OF SOLID SEED FEEDSTOCKCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is related to and claims priority benefit to U.S. Provisional Appl. Ser. No. 63 / 553,134, filed on Feb. 13, 2024, herein incorporated in its entirety.FIELD OF THE DISCLOSURE

[0002] The present disclosure relates to renewable biomass feed hydroprocessing, including, for example, a slurry or ebullated bed hydroconversion process in which a solid seed feedstock is subjected to hydroconversion.BACKGROUND OF THE DISCLOSURE

[0003] The use of renewable resources has garnered significant attention and effort in the drive to develop fossil fuel alternatives. The use of biomass feeds is particularly desirable in light of global efforts to utilize methods that reduce fossil fuel use and increase the use of sustainable fuel sources.

[0004] Renewable fuels (biofuels) produced from bio-derived oil sources are seen as being important to reduce carbon and greenhouse emissions. For example, seed oils produced from a variety of seed sources, including food crops, have been used to produce renewable fuels. Several energy-intensive and costly processes have typically been needed to obtain useful feedstocks for use in available processes, however. The pre-processing and energy costs needed to produce plant oils from biomass for use as a renewable feedstock can be significant. In the case of seed oils, crushing, extraction and other processes have been necessary to produce seed oils in a useful form.

[0005] It would be very desirable to provide a cost and energy efficient way of processing solid seed biomass into renewable fuels having chemical compositions similar to fossil fuels in a manner that reduces or eliminates unnecessary processing and associated equipment. For example, a process that allows for the production of renewable products without the need to remove useful oil seed components from the seeds would be favorable.SUMMARY OF THE DISCLOSURE

[0006] The present disclosure is generally directed to renewable biomass feed hydroprocessing in which solid seeds are used as the biomass feedstock. In one aspect, a hydroconversion process is provided in which a feedstock comprising a renewable biomass solid seed component is subjected to hydroconversion, such as in slurry or ebullated bed hydroconversion processes. The process generally comprises contacting a solid seed feedstock and a hydroconversion catalyst under suitable hydroprocessing conditions to convert a portion of the feedstock to hydroconversion products (e.g., liquid and / or gas products). The process may provide a high conversion of solid seed feedstock to products with low ash yield. While not necessarily limited thereto, one of the goals of the invention is to provide asimplified and effective process for making renewable fuels and / or other products from solid seed feedstocks.

[0007] More particularly, the process according to the disclosure comprises feeding a solid seed feedstock, a liquid feedstock, hydrogen, and a hydroconversion catalyst or a precursor thereof, to a hydroconversion reactor; contacting the solid seed feedstock and the liquid feedstock with the hydroconversion catalyst for a sufficient time under hydroconversion process conditions in the presence of hydrogen to convert a portion of the solid seed feedstock and the liquid feedstock to one or more hydroconversion products, such as liquid and / or gas products, and withdrawing hydroconversion product(s) from the reactor. The solid seed feedstock may be directly fed to the hydroconversion reactor or combined with a liquid feedstock or liquid carrier. The solid seed feedstock may contain solid seed that has not been chemically processed or modified, or solid seed that has been modified or pre-treated, e.g., to remove a hull or skin, prior to being fed to the hydroconversion reactor. The process provides a distinct advantage in that it does not require the extraction of seed oil from the seed feedstock.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] The scope of the invention is not limited by any representative figures accompanying this disclosure and is to be understood to be defined by the claims of the application.

[0009] FIG. 1 is a general block diagram schematic illustration of an embodiment according to the disclosure in which solid seed feedstock is fed to a reactor and hydroconverted to provide solid seed hydroconversion products.DETAILED DESCRIPTION

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

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

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

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

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

[0015] “Catalyst precursor” refers to a compound containing one or more catalytically active metals, from which compound the slurry catalyst is eventually formed, and which compound may be catalytically active as a hydroprocessing catalyst. An example is a water-based catalyst prior to a transformation step with a hydrocarbon diluent (a sulfided metal precursor). Catalyst precursors may be oil soluble metal compounds, e.g., unsulfided precursors. Catalyst precursors and the preparation of slurry catalysts are described in various patents, e.g., US 8,802,586, WO 2012 / 092006, and the like.

[0016] The terms “solid seed” and “solid seeds” are intended to refer to suitable solid seed that may be used as feedstocks according to the disclosure to produce hydroconversion products. Suitable solid seed may be in any useful form, e.g., seed that has not been subjected to chemical and / or mechanical processing, or seed that has been modified or pre-treated to remove one or more components of a seed feedstock. The solid seed need not be chemically processed or modified prior to being used in the process. The extraction of seed oils from the solid seeds is not necessary. In general, the solid seeds will comprise one or more seed oil components of the seeds. Various mechanical modifications or pre-treatments, such as the removal of shells, seed skins, or other seed components from the solid seed, may be used. The solid seed may also be used in a dried and / or partially dried form.

[0017] 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, 72ndedition (1991-1992).

[0018] Unless otherwise specified, the recitation of a genus of elements, materials, or other components from which an individual component or mixture of components can be selected is intended to include all possible sub-generic combinations of the listed components and mixtures thereof. Also, “include” and its variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that may also be useful in the materials, compositions, and methods of this invention. In the process of the disclosure, solid seed feedstock and liquid feedstock are fed to the hydroconversion reactor, either separately or in partial or complete combination. The liquid feedstock may be or comprise, e.g., a bio-derived feedstock (also referred to herein as biofeedstock), i.e., the liquid feedstock may be aneat biofeedstock or a coprocessing feedstock comprising a biofeedstock and a fossil or other feedstock. The catalyst may be separately fed or added to the reactor as a combination with the feedstock(s). Hydrogen is also typically fed to the reactor and may be combined with any of the feeds or separately fed to the reactor. The hydroconversion catalyst, the liquid feedstock, and hydrogen may be provided or premixed in any combination or amount before being fed to the hydroconversion reactor. The hydroconversion catalyst may be a precursor thereof. The hydroconversion reactor may comprise, e.g., one or more slurry or ebullated bed reactor hydroconversion reactors.

[0019] The feeds to the hydroconversion reactor generally comprise at least about 2 wt.%, or 5 wt. %, or 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.%, or about 100 wt.% solid seed, and liquid feedstock, preferably biofeedstock. In the case of a slurry reactor process, the slurry catalyst may typically be fed in an amount of less than about 5 wt.%, or less than about 2 wt.% or less than about 1 wt.%, slurry hydroconversion catalyst or a precursor thereof. One or more liquid products and / or catalyst may also be recycled to the hydroconversion reactor, including products derived from renewable, circular, and / or combined fossil / renewable / circular feedstocks. In general, any suitable hydroconversion process conditions may be used. Typical hydroconversion process conditions include operation within a temperature range of about 600-850°F, a reactor pressure of about 300-3500 psig, an average residence time of 10 min. to 5 hrs., and a space velocity of about 0.1 to 1.5, or 0.5 to 1.5 hr1, and a hydrogen flowrate of about 3-30 wt.% of the combined solid and liquid feedstock (excluding any recycle).

[0020] Among the advantages of the invention, is the ability to use solid seed feedstock as a feed to a hydrocracker rather than chemically converting or modifying the solid seeds before use as a feed. For example, the invention does not require the conversion of solid seed to a liquid form before use and does not require the extraction of seed oils, e.g., by seed pressing, prior to use as a feedstock. Processes of modifying solid seeds, e.g., the removal of certain seed components such as seed shells, hulls, or skins, or to obtain only certain seed components through chemical means, are also not necessary before use of the solid seed feedstock in the process.

[0021] The use of solid seed feedstock allows for certain benefits to be realized, including high solid seed conversion (“MAF”, moisture ash free basis), which is typically greater than about 95 wt.%, or more than about 98 wt.%, or more than about 99 wt.% of the solid seed fed to the process.

[0022] Other benefits associated with feeding solid seeds may include, in the case of direct feeding of whole seed feedstock, significantly reduced energy consumption due to the use of less liquid feedstock and the mitigation of biomass feedstock limitations imposed by slurry or liquid handling means (e.g., pumping) since direct solid seed feeding may allow for the handling of larger and more variably-sized biomass solids.

[0023] While not limited thereto, the process of the disclosure may be used to provide a renewable fuel or a product component useful to make a renewable fuel from the liquid and / or gas products derived from the process. Other products, such as ammonia, may also be provided by the process.

[0024] The solid seed feedstock may comprise a solid seed component selected from pennycress (Thlaspi arvense L.), soybean, camelina, rapeseed, canola, carinata, grape, weedseed, coconut, sunflower, palm kernel, peanut, linseed (flax), colza, com, rice bran, castor, jatropha (curcas), jojoba, olive, hempseed, cottonseed, safflower, mustard, cuphea, crambe, babassu, or a combination thereof. More broadly, the solid seed biomass feedstock may be obtained from a plant family selected from Brassicaceae, Cruciferaceae, Limnanthaceae, Simmondsiaceae, Tropaeolaceae, Olocaceae, or a combination thereof. The solid seed feedstock may be also provided in a form comprising stems, roots, leaves, shells, skins, stalks, pods, or a combination thereof.

[0025] Transfer of the solid seed feedstock to the hydroconversion reactor may be through a variety of single or combined means, including, e.g., the use of a pressure transfer vessel, extruders, a rotatory valve, or a lock hopper. While not required, solid seeds may be crushed or used in any desired size or size range. The solid seeds may be dried, partially dried, or in an undried condition. In general, the solid seed feedstock may be provided as a raw biomass feedstock containing biomass components that have not been chemically processed or modified prior to being fed to the slurry hydroconversion reactor.

[0026] The solid seed feedstock fed to the hydroconversion reactor may undergo various reactions, including hydrocracking, hydrogenation, hydroisomerization and / or dewaxing, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenization, hydrodemetallization, hydrodechlorination, hydrodecarboxylation, hydrodecarbonylation, hydrodearomatization or a combination thereof.

[0027] The liquid feedstock may comprise a fossil, circular, and / or bio-derived component. The liquid feedstock may comprise one or more components having a boiling point of at least about 450°F, or 500°F, or 550°F, or 600°F, or 650°F, or 675°F, or 700°F, or 725°F, or 750°F. The amount of the liquid feedstock component (based on the total liquid and solid seed feedstocks) may up to about 90 wt.%, or 80 wt.%, or 70 wt.%, or 60 wt.%, or 50 wt.%, or 40 wt.%, or 30 wt.%, or 20 wt.%, or 10 wt.%, or in the range from about 1-90 wt.% or 1-80 wt.%, or 1-70 wt.%, or 1-60 wt.%, or 1-50 wt.%, or 1-40 wt.%, or 1- 30 wt.%, or 1-20 wt.%, or 10-90 wt.%, or 10-80 wt.%, or 10-70 wt.%, or 10-60 wt.%, -10-50 wt.%, or 10- 40 wt.%, or 10-30 wt.%, or 10-20 wt.%, or 20-90 wt.%, or 20-80 wt.%, or 20-70 wt.%, or 20-60 wt.%, 20-50 wt.%, or 20-40 wt.%, or 20-30 wt.%.0BtThc liquid feedstock may, e.g., comprise a renewable, circular, and / or fossil feedstock. For example, the liquid feedstock may comprise or be selected from plastic and / or wood pyrolysis oil, lipid, vegetable oil, a process recycle product, naphtha boiling range components, diesel boiling range components, vacuum gas oil, atmospheric and / or vacuum residue, or components derived therefrom, or a combination thereof.

[0028] The liquid feedstock may be, or may be combined with, a recycled hydroconversion reactor product before being fed to the hydroconversion reactor. All or part of any liquid product may also berecycled to the hydroconversion reactor. Any recycled liquid product may first be processed to reduce or eliminate the solids present in the recycle, e.g., by solid-liquid separation of the hydroconversion reactor liquid product. Typical means for separating solids from liquids may be utilized, e.g., including but not limited to settling, sieving, filtration (such as by use of a dead-end filter, cross-flow filtration, or a filter press), or centrifugation.

[0029] The hydroconversion catalyst, e.g., when used in slurry form, may generally be provided in the form of fine particulates dispersed within the reactor liquid reaction medium and may be a supported catalyst, an unsupported catalyst, or a combination thereof. The slurry catalyst typically comprises a metal selected from Group VIB, Group VIII, or Group IIB of the Periodic Table, or a combination thereof. The hydroconversion catalyst may be unsulfided or pre-sulfided before being added to the reactor. The catalyst may also be dispersed within an oil diluent. A sufficient amount of catalyst is typically fed to a reactor(s) for each reactor to have a catalyst concentration of from 100 wppm, or 300 wppm, or 500 wppm, up to about 3 wt.% (catalyst metal to feedstock ratio). The catalyst can comprise one or more different catalysts as a single combined feed stream or as separate feeds to the reactor.

[0030] In some cases, the hydroconversion catalyst comprises an unsupported catalyst selected from molybdenum sulfide, iron sulfide, nickel sulfide, zinc sulfide, iron zinc, or a combination thereof. The hydroconversion catalyst may also be provided in the form of a catalyst precursor comprising oil soluble Group VIB metal (e.g., molybdenum) compounds, aqueous Group VIB metal (e.g., molybdenum) compounds, aqueous Group VIB metal (e.g., molybdenum) trisulfide suspension or colloid, or a combination thereof. Additional catalyst metals may be included, e.g., non-noble Group VIII metals such as Fe, Ni, Co, or a combination thereof. The hydroconversion catalyst may comprise a supported catalyst wherein the support is selected from alumina, silica-alumina, transition metal oxides, activated carbon, zeolite, or a combination thereof.

[0031] Suitable catalysts, including slurry and slurry catalyst precursors, and the preparation of slurry catalysts are described in various patents, e.g., US 8,802,586, WO 2012 / 092006, US 2015 / 0329790A1, and the like. For example, suitable catalysts used in hydroprocessing systems may comprise at least one Group VIII metal (e.g., Ni and / or Co) most often in combination with at least one Group VIB metal (e.g., Mo) on a refractory inorganic oxide support such as alumina or silica. These supported catalysts generally contain from 0.5 to 10 wt.% of at least one Group VIII metal (calculated as metal oxide) and from 1 to 30 wt.% of the at least one Group VIB metal (calculated as metal oxide), and optionally with at least one Group IIB metal (e.g., Zn). Such supported catalysts are commonly produced as cylindrical pellets, spherical solids, or extrudates, and may be ground into fine powder for use as a slurry catalyst. In some cases, the slurry catalyst may be a multi-metallic 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.

[0032] The slurry catalyst may be of the formula (Mt)a(Xu)b(Sv)d(Cw)e(Hx)f(Oy)g(Nz)h, wherein M represents at least one Group VIB metal, such as Mo, W., etc., or a combination thereof, and X functionsas a promoter metal, representing 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 combinations thereof (X being a “Promoter Metal”). Superscripts t, u, v, w, x, y, and z represent the total charge for each of M, X, S, C, H, O and N, respectively; and wherein (ta+ub+vd+we+xf+yg+zh)=O. The subscript ratio of b to a has a value of from 0 to 5 (0 £ b / a £ 5). S represents sulfur with subscript d having a value of from (a+0.5b) to (5a+2b). C represents carbon with subscript e having a value of from 0 to 11 (a+b). H is hydrogen with subscript f having a value of from 0 to 7(a+b). O represents oxygen with subscript g having a value of from 0 to 5(a+b). N represents nitrogen with subscript h having a value of 0 to 0.5(a+b). Subscript b has a value of 0 in some embodiments, e.g., for a single metallic component catalyst such as a Mo only catalyst and having no promoter.

[0033] The slurry catalyst may be prepared from catalyst precursor compositions including organometallic complexes or compounds, e.g., oil soluble compounds or complexes of transition metals and organic acids. Examples of such compounds include naphthenates, pentanedionates, octoates, and acetates of Group VIB and Group VIII metals. In some cases, the slurry catalyst may be prepared from ground or recovered supported hydroprocessing catalyst powder in oil.

[0034] The slurry catalyst may have an average particle size of at least 0. 1 micron in a diluent. In one embodiment, the slurry catalyst has an average particle size of from 1 to 100 microns, e.g., from 2 to 10 microns. In some cases, the slurry catalyst particle may comprise aggregates of catalyst molecules and / or extremely small particles that are colloidal in size (i.e., less than 100 nm, less than about 10 nm, less than about 5 nm, or less than about 1 nm). In one embodiment, the slurry catalyst comprises aggregates of single layer MoS2 clusters of nanometer sizes, e.g., 5 to 10 nm on edge. The colloidal / nanometer sized particles may form aggregates in a hydrocarbon diluent forming a slurry catalyst with an average particle size of from 1 to 20 microns.

[0035] Suitable ebullated bed catalysts are generally particulate catalysts comprising one or more metals having hydroconversion activity affixed onto a porous refractory base (“a carrier” or “support”) comprising one or more of alumina, iron oxide, silica, magnesia, titania, zeolite, silica-aluminate, phosphorous, or various combinations thereof. Alumina in the base can be in several forms including amorphous, alpha, gamma, theta, boehmite, pseudo-boehmite, gibbsite, diaspore, bayerite, nordstrandite and corundum. In some cases, the alumina may comprise boehmite or pseudo-boehmite. The base may be an ore or mineral or waste product or a manufactured form of alumina. Carbon may also be used as a support. The metals present in the particulate catalyst include base metals or compounds thereof, e.g., Group VIB metals or Group VIII metals of the Periodic Table, or combinations thereof. Useful representative metals include one or more of the Group VIB metals, such as chromium, molybdenum and tungsten, and one or more of the Group VIII metals, such as iron, cobalt and nickel. Ebullated bed particulate catalysts may be multi-metal composites, e.g., of a Group VI metal or compound thereof and a Group VIII metal or compound thereof.

[0036] The ebullated bed catalyst metals or metal compounds, e.g., metal oxide, metal hydroxide, metal sulfide, and combinations thereof, are supported on the porous refractory base. Exemplary particulate catalysts include but are not limited to catalysts comprising molybdenum, cobalt molybdenum, nickel sulfide, nickel tungsten, cobalt tungsten, and nickel molybdenum on the aforementioned supports. In some embodiments, the particulate catalyst may comprise from about 1 wt. % to 20 wt.% Group VIB metal(s).

[0037] Ebullated bed particulate catalysts typically have a nominal particle size of at least about 0.65 mm, or typically having a diameter of about 1 mm and a length of about 2-5 mm. The particulate catalyst may be in the form of various shapes, e.g., a spherical shape having a particle diameter of at least 0.65 mm, e.g., about 1 mm, or be in the form of pellets or grains that are 1-1.5, or 1-5 mm, or 25 mm in size (e.g., length) to facilitate suspension by the liquid phase in an ebullated bed reactor. In some cases, the particulate catalyst may have a cylindrical shape having a cross sectional diameter in the range from 1.0 mm to 10 mm, and a length normal to the cross-sectional diameter such that the length to diameter ratio is in the range from 2 to 8. Suitable catalysts may also have an irregular shape. While uniform dimensions are desirable, particulate catalysts may also have dimensions that fall outside of these ranges.

[0038] Suitable ebullated bed particulate catalysts typically have a high surface area and a high pore volume (e.g., as measured by nitrogen adsorption method). The surface area of the particulate catalyst is generally greater than about 100 m2 / g, e.g., in the range from 100 to 350 m2 / g, or in the range from 150 to 350 m2 / g. In general, the pore volume of the particulate catalyst is greater than about 0.4 cm3 / g, e.g., in the range from 0.4 cm3 / g to 1.2 cm3 / g. In some cases, the pore volume of the ebullated bed particulate catalyst may be in the range from 0.4 cm3 / g to 1.0 cm3 / g.

[0039] Details concerning ebullated bed particulate catalysts and methods for making such catalysts can be found in a number of patent publications, e.g., U.S. Pat. Nos. 7,803,266; 7,185,870; 7,449,103; 8,024,232; 7,618,530; 6,589,908; 6,667,271; 7,642,212; 7,560,407, 6,030,915, U.S. Pat. No. 5,980,730, U.S. Pat. No. 5,968,348, U.S. Pat. No. 5,498,586, and US Patent Publication Nos. 2011 / 0226667, 2009 / 0310435, 2011 / 0306490.

[0040] A block process schematic according to an embodiment of the disclosure is shown in FIG. 1. Hydroconversion reactor 10 (e.g., a slurry or ebullated bed reactor) may be separately fed with solid seed feedstock 12 and with liquid feedstock 14. The solid seed biomass feedstock may be fed directly or combined with a liquid feedstock, liquid carrier, recycle or other reactor feed, and may be fed to the reactor in slurry form. As shown catalyst is fed to the reactor, either directly 16a or pre-combined with the liquid feedstock 16b before being fed to the reactor. The hydroconversion process within the reactor produces gas and liquid products 18. An optional product recycle feed may also be directly fed to the hydroconversion reactor 22a and / or pre-combined with the liquid feedstock 22b before being fed to the reactor. Although shown as separate feeds to the reactor, the solid seed feedstock 12, the liquid feedstock 14, the catalyst 16a, catalyst / liquid feedstock combination 16b, and recycle 22a, 22b may be combined in any combination. Liquid product containing catalyst and other solids is removed from the reactor instream 24 and fed to a solid-liquid separation stage 20. Solids 26 are separated from the liquid product, with the liquid optionally recycled to the reactor 22a and / or the liquid feedstock 22b before being fed to the reactor. Liquid stream 28 may be optionally withdrawn from stage 20.EXAMPLES

[0041] Experimental studies and reactor case study simulations were carried out to assess the performance of solid seed feed hydroprocessing. Solid seed feedstocks were used and an autoclave reactor was used to assess slurry or ebullated bed catalyst hydrocracker performance.Example 1 - Feed property evaluation of ash produced from solid seed

[0042] Solid seed was evaluated to determine moisture, oxygen, and ash content. The moisture level was measured in a Mettler Toledo™ HC103 Halogen Moisture Analyzer, Fast-Neutron Activation Analysis (FNAA) was used to determine oxygen level in the samples per ASTM E385-11 or E385-16. Thermogravimetric Analysis (TGA) was used for ash determination. An STA7200 Thermal Analyzer from Hitachi High Technologies was used for the TGA tests. About 15 mg of sample was placed in a platinum or aluminum pan and then onto a balance beam. The pan and beam were moved into a furnace. A dry air flow was established at 100 ml / min and then the sample was heated from room temperature to 700°C at a 10°C / min ramp rate. The weight loss of the sample was monitored with increasing temperature, and the final sample weight was used to calculate the ash content. Moisture, oxygen, and ash content results are shown in Table 1 for certain solid seed varieties.Table 1 r, 1 • • Trophy . . .Camehna Chia „ , Mustard SoybeanRape seedMoisture x content,o„ , „ , , , _ , 8.0 6.7 6.5 5.3 5.11 wt.%Oxen contentExample 2 - Hydroconversion of solid seed and soybean oil using slurry catalyst

[0043] 100 g of whole soybean seeds was added into a 1 -liter autoclave slurry reactor with 400 g of liquid soybean oil and 24 g slurry catalyst. The slurry catalyst contains self-supported M0S2 and NiS catalyst, with Mo and Ni content at about 5 wt.% in total. The feedstock was processed in the autoclave reactor by heating the reactor up to 700°F in H2gas flowing at 3.6 scf / hr at 1400 psig. After two hours at 700°F, the reactor was cooled down to ambient temperature to recover product. The reactor slurry contained product, catalyst, and coke. The solids from the slurry phase were separated by filtration andanalyzed. The ash content was determined from Example 1. The conversion of solid seeds was calculated as follows:Solid Seed Conversion = 1- (Weight of Coke from Solid Seed) / [Weight of Solid Seed - ASH (wt.)]

[0044] At the end of the trial, solids were collected that originated from the solid seed feedstock. The corresponding solid seed conversion was 99 wt.%.Example 3 - Hydroconversion of solid seed and soybean oil using ebullated bed hydrocracking catalyst

[0045] 300 g of whole camelina seeds was added into a 1 -liter autoclave slurry reactor with 200 g of liquid soybean oil and 4.4 g commercial -grade ebullated bed (EB) hydrocracking catalyst. The catalyst was an alumina supported catalyst containing Mo and Ni in oxide form. It was ground into powders passing through a 400-mesh sieve. During temperature ramping up, the active metals were sulfided into M0S2 and NiS with dimethyl disulfide (DMDS) and hydrogen. The feedstock was processed in the autoclave reactor by heating the reactor up to 725 °F in H2gas flowing at 1.7 scf / hr at 2000 psig. After one hour at 725°F, the reactor was cooled down to ambient temperature to recover product. The reactor contained product, catalyst, and coke. The solids were separated by filtration and analyzed. The particle size of the solids in the product was less than 100 microns. The ash content was determined from Example 1. The conversion of solid seeds was calculated as follows:Solid Seed Conversion = 1- (Weight of Coke from Solid Seed) / [Weight of Solid Seed - ASH (wt.)]

[0046] At the end of the trial, solids were collected that originated from the solid seeds. The corresponding solid seed conversion was 99 wt.%.

[0047] Similar evaluations were conducted with other solid seeds, including camelina, black chia, and trophy rapeseed, at 1400 psig and 750°F for 1 hr. A conversion of 99-100% was achieved for the biomass portion in the whole seeds. The liquid carrier oil used was either fossil hydrocarbon or renewable liquid. The foregoing results demonstrate that solid seed feedstock may be processed using a slurry or ebullated bed hydroconversion process to near complete conversion of the solid seed feedstock. High solid seed feed content is possible, including up to 100% renewable feed content (e.g., with recycle or with liquid renewable feedstock).

[0048] For the avoidance of doubt, the present disclosure is directed to the subject-matter described in the following numbered paragraphs:1. A solid seed hydroconversion process, which is useful for producing renewable products, the process comprising: feeding solid seed feedstock, a liquid feedstock, and hydrogen to a hydroconversion reactor; wherein the hydroconversion reactor comprises a hydroconversion catalyst; contacting the solid seed and liquid feedstocks with the hydroconversion catalyst for a sufficient time under hydroconversion process conditions in the presence of hydrogen to produce hydroconversion product from the solid seed feedstock; and withdrawing the hydroconversion product from the reactor.2. The process of paragraph 1, wherein the process provides a renewable fuel or a hydroconversion product useful to make a renewable fuel or a middle distillate product, such as naphtha, jet and diesel products, and / or a product used as, or to make, a lube oil product.3. The process of paragraph 1 or 1, wherein the process provides a gas product comprising ammonia.4. The process of any of paragraphs 1-3, wherein the hydroconversion reactor comprises a slurry reactor, an ebullated bed reactor, or a combination thereof.5. The process of any of paragraphs 1-4, wherein the solid seed feedstock and the liquid feedstock are separately fed to the hydroconversion reactor.6. The process of any of paragraphs 1-4, wherein the solid seed feedstock and the liquid feedstock are combined before being fed to the hydroconversion reactor.7. The process of any of paragraphs 1-6, wherein the liquid feedstock comprises or is a liquid carrier, optionally, wherein the liquid carrier is from a fossil or renewable source.8. The process of any of paragraphs 1-7, wherein the hydroconversion catalyst or a precursor thereof is separately fed to the hydroconversion reactor or is combined with liquid feedstock and the combination fed to the hydroconversion reactor.9. The process of any of paragraphs 1-8, wherein the solid seed feedstock is at least about 5 wt.%, or 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.%, or less than about 5 wt.%, or 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.%, or in the range of 2-100 wt.%, or 2-90 wt.%, or 2-80 wt.%, or 2-70 wt.%, or 2-60 wt.%, or 2-50 wt.%, or 2-40 wt.%, or 2-30 wt.%, or 2-20 wt.%, or 2-10 wt.%, 10-100 wt.%, or 10-90 wt.%, or 10-80 wt.%, or 10-70 wt.%, or 10-60 wt.%, or 10-50 wt.%, or 10-40 wt.%, or 10-30 wt.%, or 10-20 wt.%, of the total of the solid seed and liquid feedstocks fed to the hydroconversion reactor.10. The process of any of paragraphs 1-9, wherein the liquid feedstock comprises a renewable, fossil, or circular economy feedstock.11. The process of any of paragraphs 1-10, wherein the liquid feedstock comprises or is selected from plastic and / or wood pyrolysis oil, lipid, vegetable oil, a process recycle product, naphtha boiling range components, diesel boiling range components, vacuum gas oil, atmospheric and / or vacuum residue, or components therefrom, or a combination thereof.12. The process of any of paragraphs 1-11, wherein the liquid feedstock comprises a component having a boiling point of at least about 600°F in an amount of up to about 100 wt.%, or 98 wt.%, or 90 wt.%, or 80 wt.%, or 70 wt.%, or 60 wt.%, or 50 wt.%, or 40 wt.%, or 30 wt.%, or 20 wt.%, or 10 wt.%, or in the range from about 10-100 wt.%, or 10-98 wt.%, or 10-90 wt.%, or 10-80 wt.%, or, 10-70 wt.%, or 10-60 wt.%, or 10-50 wt.%, or 10-40 wt.%, or 10-30 wt.%, or 20-100 wt.%, or 20-90 wt.%, or 20-80 wt.%, or, 20-70 wt.%, or 20-60 wt.%, or 20-50 wt.%, or 20-40 wt.%, or 20-30 wt.%.13. The process of any of paragraphs 1-12, wherein the solid seed feedstock comprises or is selected from pennycress, soybean, camelina, rapeseed, canola, carinata, grape, weedseed, coconut, sunflower, palm kernel, peanut, linseed (flax), colza, com, rice bran, castor, jatropha (curcas), jojoba, olive, hempseed, cottonseed, safflower, mustard, cuphea, crambe, babassu, or a combination thereof; optionally, wherein the solid seed feedstock is provided in a form comprising stems, roots, leaves, shells, skins, stalks, pods, or a combination thereof.14. The process of any of paragraphs 1-13, wherein the solid seed feedstock comprises or is obtained from a plant family selected from Brassicaceae, Cruciferaceae, Limnanthaceae, Simmondsiaceae, Tropaeolaceae, Olocaceae, or a combination thereof; optionally, wherein the solid seed feedstock is provided in a form comprising stems, roots, leaves, shells, skins, stalks, pods, or a combination thereof.15. The process of any of paragraphs 1-14, wherein the hydroconversion catalyst comprises a slurry hydroconversion catalyst in the form of fine particulates dispersed within the reactor liquid reaction medium and is a supported catalyst, an unsupported catalyst, or a combination thereof.16. The process of any of paragraphs 1-15, wherein the hydroconversion catalyst is an ebullating bed catalyst in extrudate, pellet, or spherical form.17. The process of any of paragraphs 1-16, wherein the hydroconversion catalyst is unsulfided or presulfided before being added to the reactor, optionally dispersed within a hydrocarbon oil diluent, and wherein the catalyst comprises a metal selected from Group VIB, Group VIII, or Group IIB of the Periodic Table, or a combination thereof.18. The process of any of paragraphs 1-17, wherein the hydroconversion catalyst comprises molybdenum sulfide, iron sulfide, nickel sulfide, cobalt sulfide, tungsten sulfide, zinc sulfide, or a combination thereof.19. The process of any of paragraphs 1-18, wherein the hydroconversion catalyst is provided in the form of a catalyst precursor comprising oil soluble Group VIB metal compounds, aqueous Group VIB metal compounds, aqueous Group VIB metal trisulfide suspension or colloid, or a combination thereof, optionally comprising a Group VIII metal, such as Fe, Ni, Co, or a combination thereof.20. The process of any of paragraphs 1-19, wherein the hydroconversion catalyst comprises a supported catalyst wherein the support is selected from alumina, silica-alumina, zeolite, or a combination thereof.21. The process of any of paragraphs 1 -20, wherein one or more of the hydroconversion catalyst, the solid seed feedstock, the liquid feedstock, and hydrogen are fed to the hydroconversion reactor as separate feedstreams to the reactor.22. The process of any of paragraphs 1-20, wherein one or more of the hydroconversion catalyst, the solid seed feedstock, the liquid feedstock, and hydrogen are fed to the hydroconversion reactor are premixed in any combination before being fed to the reactor.23. The process of paragraphs 21 or 22, wherein the solid seed feedstock is fed to the reactor in the form of a slurry feed.24. The process of any of paragraphs 1-23, wherein the solid seed feedstock fed to the hydroconversion reactor undergoes hydrocracking, hydrogenation, hydroisomerization and / or dewaxing, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenization, hydrodemetallization, hydrodechlorination, hydrodecarboxylation, hydrodecarbonylation, hydrodearomatization, or a combination thereof.25. The process of any of paragraphs 1-24, wherein the liquid feedstock comprises product from the hydroconversion reactor or a product derived from the hydroconversion reactor product.

[0049] The present disclosure is not to be limited in terms of the particular embodiments described in this application, which are intended as illustrations of various aspects. Many modifications and variations can be made without departing from its spirit and scope, as may be apparent. Functionally equivalent methods and systems within the scope of the disclosure, in addition to those enumerated herein, may be apparent from the foregoing representative descriptions. Such modifications and variations are intended to fall within the scope of the appended representative claims. The present disclosure is to be limited only by the terms of the appended representative claims, along with the full scope of equivalents to which such representative claims are entitled. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0050] The foregoing description, along with its associated embodiments, has been presented for purposes of illustration only. It is not exhaustive and does not limit the invention to the precise form disclosed. Those skilled in the art may appreciate from the foregoing description that modifications and variations are possible in light of the above teachings or may be acquired from practicing the disclosed embodiments. For example, in some cases, the steps described need not be performed in the same sequence discussed or with the same degree of separation. Likewise various steps may be omitted, repeated, or combined, as necessary, to achieve the same or similar objectives. Accordingly, the invention is not limited to the above-described embodiments, but instead is defined by the appended claims in light of their full scope of equivalents.

[0051] In the preceding specification, various preferred embodiments have been described with references to the accompanying drawings. It may, however, be evident that various modifications and changes may be made thereto, and additional embodiments may be implemented, without departing from the broader scope of the invention as set forth in the claims that follow. The specification and drawings are accordingly to be regarded as an illustrative rather than restrictive.Where permitted, all publications, patents and patent applications cited in this application are incorporated by reference herein in their entirety, to the extent such disclosure is not inconsistent with the present invention.

Claims

WHAT IS CLAIMED IS:

1. A solid seed hydroconversion process, which is useful for producing renewable products, the process comprising: feeding solid seed feedstock, a liquid feedstock, and hydrogen to a hydroconversion reactor; wherein the hydroconversion reactor comprises a hydroconversion catalyst; contacting the solid seed and liquid feedstocks with the hydroconversion catalyst for a sufficient time under hydroconversion process conditions in the presence of hydrogen to produce hydroconversion product from the solid seed feedstock; and withdrawing the hydroconversion product from the reactor.

2. The process of claim 1, wherein the process provides a renewable fuel or a hydroconversion product useful to make a renewable fuel or a middle distillate product, such as naphtha, jet and diesel products, and / or a product used as, or to make, a lube oil product.

3. The process of claim 1 or 1, wherein the process provides a gas product comprising ammonia.

4. The process of any of claims 1-3, wherein the hydroconversion reactor comprises a slurry reactor, an ebullated bed reactor, or a combination thereof.

5. The process of any of claims 1-4, wherein the solid seed feedstock and the liquid feedstock are separately fed to the hydroconversion reactor.

6. The process of any of claims 1-4, wherein the solid seed feedstock and the liquid feedstock are combined before being fed to the hydroconversion reactor.

7. The process of any of claims 1-6, wherein the liquid feedstock comprises or is a liquid carrier, optionally, wherein the liquid carrier is from a fossil or renewable source.

8. The process of any of claims 1-7, wherein the hydroconversion catalyst or a precursor thereof is separately fed to the hydroconversion reactor or is combined with liquid feedstock and the combination fed to the hydroconversion reactor.

9. The process of any of claims 1-8, wherein the solid seed feedstock is at least about 5 wt.%, or 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.%, or less than about 5 wt.%, or 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.%, or in the range of 2-100 wt.%, or 2-90 wt.%, or 2-80 wt.%, or 2-70 wt.%, or 2-60 wt.%, or 2-50 wt.%, or 2-40 wt.%, or 2-30 wt.%, or 2-20 wt.%, or 2-10 wt.%, 10-100 wt.%, or 10-90 wt.%, or 10-80 wt.%, or 10-70 wt.%, or 10-60 wt.%, or 10-50 wt.%, or 10-40 wt.%, or 10-30 wt.%, or 10-20 wt.%, of the total of the solid seed and liquid feedstocks fed to the hydroconversion reactor.

10. The process of any of claims 1-9, wherein the liquid feedstock comprises a renewable, fossil, or circular economy feedstock.

11. The process of any of claims 1-10, wherein the liquid feedstock comprises or is selected from plastic and / or wood pyrolysis oil, lipid, vegetable oil, a process recycle product, naphtha boiling rangecomponents, diesel boiling range components, vacuum gas oil, atmospheric and / or vacuum residue, or components therefrom, or a combination thereof.

12. The process of any of claims 1-11, wherein the liquid feedstock comprises a component having a boiling point of at least about 600°F in an amount of up to about 100 wt.%, or 98 wt.%, or 90 wt.%, or 80 wt.%, or 70 wt.%, or 60 wt.%, or 50 wt.%, or 40 wt.%, or 30 wt.%, or 20 wt.%, or 10 wt.%, or in the range from about 10-100 wt.%, or 10-98 wt.%, or 10-90 wt.%, or 10-80 wt.%, or, 10-70 wt.%, or 10-60 wt.%, or 10-50 wt.%, or 10-40 wt.%, or 10-30 wt.%, or 20-100 wt.%, or 20-90 wt.%, or 20-80 wt.%, or, 20-70 wt.%, or 20-60 wt.%, or 20-50 wt.%, or 20-40 wt.%, or 20-30 wt.%.

13. The process of any of claims 1-12, wherein the solid seed feedstock comprises or is selected from pennycress, soybean, camelina, rapeseed, canola, carinata, grape, weedseed, coconut, sunflower, palm kernel, peanut, linseed (flax), colza, com, rice bran, castor, jatropha (curcas), jojoba, olive, hempseed, cottonseed, safflower, mustard, cuphea, crambe, babassu, or a combination thereof; optionally, wherein the solid seed feedstock is provided in a form comprising stems, roots, leaves, shells, skins, stalks, pods, or a combination thereof.

14. The process of any of claims 1-13, wherein the solid seed feedstock comprises or is obtained from a plant family selected from Brassicaceae, Cruciferaceae, Limnanthaceae, Simmondsiaceae, Tropaeolaceae, Olocaceae, or a combination thereof; optionally, wherein the solid seed feedstock is provided in a form comprising stems, roots, leaves, shells, skins, stalks, pods, or a combination thereof.

15. The process of any of claims 1-14, wherein the hydroconversion catalyst comprises a slurry hydroconversion catalyst in the form of fine particulates dispersed within the reactor liquid reaction medium and is a supported catalyst, an unsupported catalyst, or a combination thereof.

16. The process of any of claims 1-15, wherein the hydroconversion catalyst is an ebullating bed catalyst in extrudate, pellet, or spherical form.

17. The process of any of claims 1-16, wherein the hydroconversion catalyst is unsulfided or presulfided before being added to the reactor, optionally dispersed within a hydrocarbon oil diluent, and wherein the catalyst comprises a metal selected from Group VIB, Group VIII, or Group IIB of the Periodic Table, or a combination thereof.

18. The process of any of claims 1-17, wherein the hydroconversion catalyst comprises molybdenum sulfide, iron sulfide, nickel sulfide, cobalt sulfide, tungsten sulfide, zinc sulfide, or a combination thereof.

19. The process of any of claims 1-18, wherein the hydroconversion catalyst is provided in the form of a catalyst precursor comprising oil soluble Group VIB metal compounds, aqueous Group VIB metal compounds, aqueous Group VIB metal trisulfide suspension or colloid, or a combination thereof, optionally comprising a Group VIII metal, such as Fe, Ni, Co, or a combination thereof.

20. The process of any of claims 1-19, wherein the hydroconversion catalyst comprises a supported catalyst wherein the support is selected from alumina, silica-alumina, zeolite, or a combination thereof.

21. The process of any of claims 1-20, wherein one or more of the hydroconversion catalyst, the solid seed feedstock, the liquid feedstock, and hydrogen are fed to the hydroconversion reactor as separate feedstreams to the reactor.

22. The process of any of claims 1-20, wherein one or more of the hydroconversion catalyst, the solid seed feedstock, the liquid feedstock, and hydrogen are fed to the hydroconversion reactor are pre-mixed in any combination before being fed to the reactor.

23. The process of claims 21 or 22, wherein the solid seed feedstock is fed to the reactor in the form of a slurry feed.

24. The process of any of claims 1-23, wherein the solid seed feedstock fed to the hydroconversion reactor undergoes hydrocracking, hydroisomerization and / or dewaxing, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenization, hydrodemetallization, hydrodechlorination, hydrodecarboxylation, hydrodecarbonylation, hydrodearomatization, or a combination thereof.

25. The process of any of claims 1-24, wherein the liquid feedstock comprises product from the hydroconversion reactor or a product derived from the hydroconversion reactor product.

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