Lipid-assisted conversion

Abstract

A method for converting bio-oil derived from lignocellulosic biomass into a fuel or fuel blend stock. The method may include contacting the bio-oil with a lipid or lipid derivative to form an organic phase containing phenolic compounds and an aqueous phase. The organic phase is separated from the aqueous phase and subjected to hydrogenation and deoxygenation in a hydrotreating reactor to produce a hydrocarbon product, a gas product, and water. The hydrocarbon products of the hydrotreating reactor are fractionated into fuel products including gasoline and kerosene / diesel.

Description

[Technical field]

[0001] This application claims priority to U.S. Provisional Application No. 63 / 339,260, filed May 6, 2022, which is incorporated by reference in its entirety.

[0002] The present technology relates generally to hydrocarbon fuels, and more specifically to fuels having renewable content. More specifically, the present technology relates to upgrading pyrolysis bio-oil fractions to premium fuels via hydroprocessing. [Background technology]

[0003] As renewable alternatives to fossil fuels, biofuels have been embraced by consumers and policymakers alike as a potential key component of societal and governmental climate change mitigation strategies. However, the majority of biofuels in use today are based on either sugar or lipid feedstocks. Long-term growth of the biofuel industry requires diversification to more abundant lignocellulosic feedstocks, such as woody biomass.

[0004] Additional processing, such as hydroprocessing, is required to upgrade biomass to premium hydrocarbon fuels, such as renewable diesel. Since most hydrogen is still produced from steam reforming of fossil fuels, there is an incentive to minimize hydrogen consumption during the hydroprocessing step(s).

[0005] Lignocellulosic biomass includes cellulose, hemicellulose, and lignin. Each of these constituents is a polymer with different building blocks, as shown in Figure 1. Bio-oil is formed by the depolymerization of these macromolecules, typically via thermochemical reactions as disclosed in the prior art. One such process is pyrolysis. Pyrolysis generally refers to the high temperature conversion of carbonaceous feedstocks, typically solids, into primarily liquids. To prevent combustion, pyrolysis is carried out in the near or complete absence of diatomic oxygen. In addition to liquids, pyrolysis products from lignocellulosic biomass include gases (mainly CO, CO 2 The liquid products, called pyrolysis oil or bio-oil, typically include: (1) C2-C4 oxygenates formed by the fragmentation of cellulose and hemicellulose; these include hydroxyacetaldehyde, acetals, and acetates, accounting for 8-26% of bio-oil; (2) monophenols formed by depolymerization of lignin; these may contain small amounts of furans and account for 2–7% of bio-oil; (3) lignin-derived oligomers (also known as "pyrolytic lignin"); these are water-insoluble and account for 15-25% of the oil; and (4) Sugars and anhydrosugars formed by fragmentation of cellulose and hemicellulose; these are typically water soluble and form 10-20% of the bio-oil.

[0006] Bio-oil further contains water, which accounts for about 14-30% by weight of its mass. Typically, the water in bio-oil is present as part of a stable emulsion. On a dry basis, bio-oil contains around 38-44% oxygen.

[0007] In some pyrolysis processes, the condensable (i.e., liquid) products can be selectively recovered as fractions primarily according to their boiling points. In one such embodiment, the fractionation can be achieved such that water and C2-C4 oxygenates, monophenols, lignin-derived oligomers, and sugars can generally be recovered separately.

[0008] In some pyrolysis processes, the gas and solid products are combusted to fuel the endothermic pyrolysis reaction.

[0009] Pyrolysis processes can be designed to run under a variety of conditions, such as, for example, temperature, residence time, reaction medium, and optional catalyst selection, all of which can vary widely. Fast pyrolysis is run at higher temperatures (>900°F compared to 750-950°F for slow pyrolysis) and can be the preferred process for maximizing bio-oil yields.

[0010] Pyrolysis may be carried out in multiple reactor configurations. One common fast pyrolysis system involves the use of a fluidized bed reactor on inert or catalytic solid particles. The fluidizing gas may be nitrogen or, as in some embodiments, gas produced by the pyrolysis itself (e.g., recycled through a booster compressor). During pyrolysis of wood chips, the pulverized wood is in intimate contact with hot solid particles in the fluidized bed. As the wood is fast pyrolyzed, the solid particles become coated with char. These solid particles are subsequently regenerated by char or coke burnoff in a different vessel. The heat of combustion of the char provides heat for the endothermic pyrolysis reaction when the hot regenerated solid particles are returned to the reactor. In most such pyrolysis reactor systems, pulverized biomass is continuously fed to the pyrolysis reactor while the solid particles are circulated between the reactor and the regenerator.

[0011] Pyrolysis may also be carried out in a liquid reaction medium in a process called "solvent liquefaction". Solvent liquefaction is typically carried out in one or more liquid slurry reactor(s) as either a batch or continuous process. The solvent may be selected to enhance the process chemistry or for more practical reasons, such as selecting water as the solvent to process wet feedstocks. Typically, solvent liquefaction involves mixing the biomass with a solvent in a slurry reactor at temperatures between about 300-700°F and pressures ranging from around 1-3000 psi. Residence times in the slurry reactor can vary considerably, but generally range from around 1-60 minutes. Gases and vapors can be released from the top of the slurry reactor, while some portion of the solids and liquid products are conducted out of the reactor through a solids removal step. The condensable vapors and liquid products are then further processed and often fractionated, with some portion of the solvent being recovered for recycling earlier in the process.

[0012] Polymerization of reactive compounds found in bio-oil is often difficult to prevent. Lignin-derived liquids can be particularly prone to polymerization. This creates problems in the processing, storage, transportation, and use of the bio-oil produced.

[0013] Certain bio-oil streams can be mildly hydrogenated prior to and during more extensive or complete hydroprocessing to improve stability and partially mitigate undesirable polymerization reactions.

[0014] To be useful as a drop-in fuel blendstock, bio-oil needs to be hydrofinished, primarily to deoxygenate the oil. However, there are many unsolved challenges in hydrofinishing bio-oil. These include poor deoxygenation performance and high heat release. Bio-oil does not form a homogeneous solution in most hydrocarbons (including petroleum middle distillates), so diluting bio-oil with hydrocarbons to address this problem is not practical.

[0015] The prior art describes the production of paraffinic hydrocarbon fuels via hydrotreating lipids, including co-hydrotreating lipids with petroleum fractions. Few publications report parameters that define the optimum conditions for co-hydrotreating straight-run diesel or gas oil with lipids. Co-hydrotreating of 10% and 20% rapeseed oil with straight-run diesel / gas oil has been described by Jerzy Walendziewski and co-workers (Fuel Processing Technology 90, 2009, 686-691). In a more recent study, P. Dhar and co-workers reported the co-processing of 5-15% palm oil and jatropha oil with straight-run gas oil (Hydrocarbon Processing, January 2018; 25-28). These studies broadly describe the conversion chemistry of lipids with primarily C16 and C18 fatty acids to n-paraffins in the C15-C18 range and highlight that as the feed lipid content increases, the low temperature properties of the processed diesel (i.e., cloud point, CFPP, pour point) deteriorate.

[0016] Publications, patents, and patent applications are referenced throughout this disclosure. All references cited herein are hereby incorporated by reference.

[0017] In a paper entitled "Hydrotreating in the production of green diesel" (PTQ, Q2; 2010), Rasmus Egeberg and co-workers provide a case history on the conversion of a straight-run gas oil mild hydrocracking unit into a hydrotreater for co-processing up to 30% of crude tall diesel (FAME produced from tall oil) with straight-run middle distillates. The paper also describes a multi-bed diesel hydrotreater, where a bottom bed of dewaxing catalyst is used for hydrocracking / isomerization of the normal paraffinic product of lipid hydrotreating, thereby improving the low temperature properties of the co-processed diesel.

[0018] In summary, the prior art teaches the co-hydroprocessing of lipids and lipid derivatives with straight-run petroleum fractions. However, no method has been described in the prior art to advantageously co-hydroprocess lipids with bio-oil fractions from pyrolysis / liquefaction of lignocellulosic biomass. Thus, there remains an unmet need for biofuel feedstock diversity and enhanced fuel properties. Summary of the Invention

[0019] The embodiments of the present invention described below are not intended to be exhaustive or to limit the invention to the precise forms disclosed in the following detailed description, but rather the embodiments are chosen and described so that others skilled in the art can appreciate and understand the principles and practices of the present invention.

[0020] Aspects of the invention include contacting lignocellulosic biomass-derived bio-oil with lipids (or lipid derivatives, e.g., biodiesel and by-products of biodiesel production and vegetable oil processing) to (1) recover higher carbon content bio-oil components, (2) improve the stability of the bio-oil, (3) improve miscibility with hydrocarbons, and (4) upgrade the bio-oil through a hydrotreating reactor. Depending on the pyrolysis process and bio-oil properties, the contacting may be performed at various times or stages of the bio-oil production and refining process. The hydrotreated fuel fractions of the invention have advantages over conventional paraffinic renewable diesel, renewable paraffinic kerosene, and renewable gasoline / naphtha due to the presence of polycyclic, naphthenic, and aromatic hydrocarbons. In the case of diesel fuel, such advantages include better solubility of low-quality (e.g., undistilled) biodiesel when producing 100% renewable fuel blends with biodiesel. In the case of gasoline or naphtha, advantages include, for example, better octane number. In the case of kerosene, advantages include the presence of aromatics required by specifications or standards for use as jet fuel (see, e.g., ASTM D1655 and D7566) and a reduction in the freezing point. One aspect of the invention involves co-hydroprocessing a bio-oil having an effective H / C ratio of 0.3 to 1.0 with a lipid having an effective H / C ratio of 1.5 to 2.0, thereby reducing the hydrogen consumption requirements and processing challenges for upgrading the bio-oil to premium hydrocarbon fuels characterized by high H / C ratios.

[0021] In one exemplary embodiment of the present invention, a method for converting bio-oil derived from lignocellulosic biomass into a fuel or fuel blend stock is described, the method comprising first contacting the bio-oil with a lipid or lipid derivative to form an organic phase containing phenolic compounds and an aqueous phase, then separating the organic phase from the aqueous phase, then subjecting the organic phase to hydrogenation and deoxygenation in a hydrotreating reactor to produce hydrocarbon products, gas products, and water, and then fractionating the hydrocarbon products of the hydrotreating reactor into fuel products including gasoline and kerosene / diesel.

[0022] In yet a further exemplary embodiment of the present invention, a method for converting bio-oil derived from lignocellulosic biomass to a hydrocarbon fuel or fuel blend stock is provided, the method comprising first combining the bio-oil with lipids to produce a combined feed, then directing the combined feed to a hydrotreating reactor to produce a reactor effluent. The reactor effluent is then separated into hydrocarbon, gas, and water streams, and the hydrocarbons are then fractionated into a gasoline cut and a kerosene / diesel cut. The combined feed has a lipid content between about 16 vol.% and about 90 vol.%, and the kerosene / diesel cut has less than 0.1 wt.% oxygen.

[0023] In yet another exemplary embodiment of the present invention, a hydrocarbon fuel or blend stock is described that includes bio-oil and lipids to produce a combined feed. The combined feed is subjected to a hydrotreating reactor to produce a reactor effluent separated into a hydrocarbon, gas, and water stream. A gasoline cut and a kerosene / diesel cut, where the combined feed has a lipid content between about 16 vol.% and about 90 vol.%, and the kerosene / diesel cut has less than 0.1 wt.% oxygen.

[0024] Other features and advantages of the present invention will become apparent to those skilled in the art from the following detailed description. It should be understood, however, that the detailed description and specific examples of the various embodiments indicate preferred and alternative embodiments of the invention and are presented by way of illustration and not limitation. Many modifications and changes may be made within the scope of the present invention without departing from the spirit thereof, and the invention includes all such modifications.

[0025] These, as well as other objects and advantages of the present invention will be more fully understood and appreciated by reference to the following more particular description of illustrative embodiments of the invention taken in conjunction with the accompanying drawings. [Brief description of the drawings]

[0026] [Figure 1] FIG. 1 is a diagram depicting the polymeric building blocks of lignocellulosic biomass. [Diagram 2] FIG. 2 is a block diagram of a process flow for an embodiment of the present invention. [Diagram 3] FIG. 2 is a schematic diagram of a process flow for an alternative embodiment of the present invention. [Figure 4] 1 is a graph of the TAN of the HDO product as a function of the amount of lipid in the bio-oil. [Diagram 5] 1 is a graph of HDO liquid yield as a function of the amount of lipid in the bio-oil. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] The apparatus and methods disclosed herein will now be described in detail, by way of example, with reference to the figures. Unless otherwise specified, like numbers in the figures refer to the same, similar, or corresponding elements throughout the figures. It will be understood that changes can be made to the disclosed and described embodiments, arrangements, configurations, components, elements, apparatus, methods, materials, etc., and such changes may be desired for particular applications. In this disclosure, any specification of specific shapes, materials, techniques, arrangements, etc., is either related to the embodiment presented or is merely a general description of such shapes, materials, techniques, arrangements, etc. Specific details or specification of the embodiment are not intended to be, and should not be, interpreted as mandatory or limiting, unless specifically so indicated. Selected embodiments of the apparatus and methods are disclosed hereinafter and described in detail with reference to the figures.

[0028] As used herein, "about," "around," or "approximately" is intended to mean up to plus or minus 10% of the particular term. The use of the terms "a," "an," and "the" and similar referents in the context of describing elements (especially in the context of the appended claims) should be construed to encompass both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The recitation of ranges of values ​​herein is intended only to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated herein as if it were individually set forth herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or exemplary language (e.g., "such as") provided herein is intended only to better clarify the embodiments, and does not impose limitations on the appended claims, unless otherwise indicated. No language in the specification should be construed as indicating any non-claimed element as essential.

[0029] As used herein, "alkyl" groups include straight-chain and branched alkyl groups. Examples of straight-chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, sec-butyl, t-butyl, neopentyl, and isopentyl groups. i ~C j The term "alkyl", e.g. C 1 ~C 4 Alkyl will be understood to mean an alkyl group having a carbon number falling within the range i to j.

[0030] The term "aromatic compound" as used herein is synonymous with "aromatics" and refers to both cyclic aromatic hydrocarbons and heterocyclic aromatic compounds that do not contain heteroatoms. The term includes monocyclic, bicyclic, and polycyclic ring systems. The term also includes aromatic species having alkyl and cycloalkyl groups. Thus, aromatic compounds include, but are not limited to, benzene, azulene, heptalene, phenylbenzene, indacene, fluorene, phenanthrene, triphenylene, pyrene, naphthacene, chrysene, anthracene, indene, indane, pentalene, and naphthalene, as well as alkyl and cycloalkyl substituted variations of these compounds. In some embodiments, the aromatic species contains between 6-14 carbons, and in other embodiments 6-12, or even 6-10 carbon atoms in the ring portion of the group. The phrase includes groups that contain fused rings, such as aromatic-aliphatic fused ring systems (e.g., indane, tetrahydronaphthene, etc.).

[0031] "Oxygenates" or "oxygenated hydrocarbons" as used herein refer to carbon-containing compounds that contain at least one covalent bond to oxygen. Examples of functional groups encompassed by this term include, but are not limited to, carboxylic acids / esters, carboxylates, anhydrides, aldehydes, esters, ethers, ketones, and alcohols. Oxygenates may also be oxygen-containing variants of aromatics, cycloparaffins, and paraffins described herein. Fatty acids or glycerides are the naturally occurring carboxylic acids or esters that define lipids.

[0032] The term "paraffin" as used herein means an acyclic, branched, or unbranched alkane. Unbranched paraffins are n-paraffins; branched paraffins are iso-paraffins. "Cycloparaffins" are cyclic, branched, or unbranched alkanes.

[0033] The term "paraffinic" as used herein refers to both paraffins and cycloparaffins as defined above, as well as chains that are primarily hydrocarbons with regions that are either branched or unbranched alkanes.

[0034] The term "olefin" as used herein means acyclic, branched or unbranched alkenes. The term "olefinic" as used herein means both mono- or di-unsaturated (i.e., one or two double bonds) hydrocarbons that are either cyclic, branched or unbranched.

[0035] Hydroprocessing, as used herein, refers to, but is not limited to, various types of catalytic reactions that take place in the presence of hydrogen. Examples of the most common hydroprocessing reactions include, but are not limited to, hydrogenation, hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrotreating (HT), hydrocracking (HC), aromatic saturation or hydrodearomatization (HDA), hydrodeoxygenation (HDO), decarbonation (DCO), hydroisomerization (HI), hydrodewaxing (HDW), hydrodemetallization (HDM), decarbonylation, methanation, and reforming. Depending on the type of catalyst, reactor configuration, reactor conditions, and feedstock composition, multiple reactions can occur, ranging from purely thermal reactions (i.e., no catalyst required) to catalytic reactions. When describing the main functions of a particular hydroprocessing unit, e.g., HDO reaction system, it is understood that the HDO reaction is only one of the main reactions occurring, and other reactions can also occur.

[0036] Decarboxylation (DCO) is the process in which a carboxyl group is removed from an organic molecule to form CO 2 is understood to mean the hydrogenation of organic molecules to produce

[0037] Pyrolysis is understood to mean the thermochemical decomposition of a carbonaceous material in which little or no diatomic oxygen or diatomic hydrogen is present during the thermochemical reaction. The product fractions obtained by pyrolysis are called heat-modified products.

[0038] Hydrofinishing (HT) involves the removal of elements of groups IIIa, Va, VIa, and / or VIIa of the periodic table from organic compounds. Hydrofinishing may also include hydrodemetallization (HDM) reactions. Thus, hydrofinishing involves the removal of heteroatoms such as oxygen, nitrogen, sulfur, and combinations of any two or more thereof by hydrotreating. For example, hydrodeoxygenation (HDO) is understood to mean the removal of oxygen by a catalytic hydrotreating reaction that produces water as a by-product; similarly, hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) refer to the removal of the respective indicated elements by hydrotreating. Since the main heteroatom removed during hydrofinishing of biological feedstocks is oxygen, the term hydrodeoxygenation or HDO is used interchangeably with hydrofinishing in this disclosure.

[0039] Hydrogenation involves the addition of hydrogen to an organic molecule without breaking the molecule into subunits. Adding hydrogen to a carbon-carbon or carbon-oxygen double bond to produce a single bond are two non-limiting examples of hydrogenation. Partial hydrogenation and selective hydrogenation are terms used to refer to hydrogenation reactions that result in partial saturation of an unsaturated feedstock. For example, vegetable oils with a high percentage of polyunsaturated fatty acids (e.g., linoleic acid) can undergo partial hydrogenation to produce a hydroprocessed product in which the polyunsaturated fatty acids are converted to monounsaturated fatty acids (e.g., oleic acid) without increasing the percentage of undesirable saturated fatty acids (e.g., stearic acid). Hydrogenation is distinct from hydrofinishing, hydroisomerization, and hydrocracking, although hydrogenation can occur during these other reactions.

[0040] Hydrogenolysis (HC) is understood to mean the cleavage of a carbon-carbon bond of a molecule in the presence of hydrogen to form at least two molecules. In such reactions, the resulting double bond typically subsequently undergoes hydrogenation.

[0041] Hydroisomerization (HI) is defined as the skeletal rearrangement of carbon-carbon bonds to form isomers in the presence of hydrogen. It is understood that hydrocracking is a competing reaction for most HI catalyzed reactions, and the secondary HC reaction pathway is included in the use of the term HI. Hydrodewaxing (HDW) is a specific form of hydrocracking and hydroisomerization designed to improve the low temperature properties of hydrocarbon fluids.

[0042] Composition is C 7 ~C 12 n-paraffin etc. i ~C j If it is said that the composition comprises "hydrocarbons," it will be understood that this means that the composition comprises one or more paraffins having carbon numbers falling within the range i to j.

[0043] "Middle distillates" generally refers to petroleum fractions within the range of about 200° F. (93° C.) to about 800° F. (427° C.), including kerosene (about 200-520° F.), diesel and gas oil (about 400-650° F.), and heavy gas oil (about 610-800° F.).

[0044] "Lipids" as used herein refers to fats, oils, and greases, and fractions thereof. Lipids are primarily derived from C 8 ~C 24 Lipids contain saturated and unsaturated fatty acids in the range of 0.1 to 1.0, and in lipids the fatty acids may be present in the form of esters of glycerol (i.e., as mono-, di-, and triglycerides) or as free fatty acids (FFAs). Lipids may also contain minor constituents such as fats or oils like sterols, steryl esters, steryl glucosides, terpenes, tocopherols, vitamins, proteins, waxes, etc.

[0045] Hydrogen-carbon molar ratio, or "H / C ratio" for short, refers to the molar ratio of hydrogen to carbon (i.e., the ratio of hydrogen atoms to carbon atoms) in a compound, a simple composition of a few compounds, or a complex composition of many compounds. For hydrocarbons containing heteroatoms, including oxygenates, the effective H / C ratio, H / C effcan be calculated from its empirical formula or its CHNOS molar composition according to Equation 1 shown below. H / C eff =(H-2O-3N-2S) / C

[0046] For hydrocarbons that do not contain N, O, and S heteroatoms, the above equation will be H / C. However, for oxygenates such as lipids (where fatty acids can be considered as straight chain hydrocarbons terminated with carboxyl groups), Equation 1 will represent the H / C ratio on an oxygen-free basis by considering the chemically dehydrated form of the oxygenate (where each oxygen atom is removed with two of the hydrogen atoms of the oxygenated hydrocarbon).

[0047] The empirical formula of a mixture of hydrocarbons or mixtures of hydrocarbons and oxygenates may be determined mathematically by knowing the composition of the blend, or may be determined analytically by various elemental analysis techniques or via ASTM D5291 analysis. In either case, the H / C ratio can be determined by knowing the C, H, N, O, and S values ​​of the complex composition. eff The value can be calculated according to Equation 1.

[0048] It should be understood that the "volume percent" or "vol. %" of a component in a composition, or the volume ratio of different components in a composition, is determined based on the initial volume of the individual components, not the final volume of the components combined, at room temperature (about 23° C.).

[0049] TECHNOLOGY OF THE PRESENT ART In one aspect, a method is provided for producing high H / C ratio hydrocarbon fuels from low H / C ratio lignocellulosic bio-oil. The increased H / C ratio is achieved by co-processing the bio-oil with lipids. Tables I and II show typical effective H / C ratios for lipids and lignocellulosic bio-oil, respectively. As can be seen from these tables, lipids typically have effective H / C ratios in the range of 1.5-1.7, whereas lignocellulosic bio-oil has effective H / C ratios below 1, typically in the range of 0.2-1.0, and often in the range of 0.0-1.0. [Table I] [Table II]

[0050] The method includes first contacting a bio-oil (e.g., heat-denatured) with a lipid, and subjecting the combined stream to a temperature, a hydrogen pressure, and a catalyst to produce hydrocarbons having a higher effective H / C ratio than the bio-oil. In an additional embodiment, the bio-oil and lipid are diluted with a hydrocarbon diluent that is substantially free of olefins.

[0051] Exemplary bio-oil feedstocks include, but are not limited to, bio-oils and bio-oil fractions produced by fast pyrolysis, solvent liquefaction, hydrothermal liquefaction, and catalytic cracking of carbonaceous feedstocks. Carbonaceous feedstocks include, but are not limited to, coal, crude oil, petroleum fractions, municipal solid waste, plastic waste, sorted solid waste, food waste, sewage sludge, fertilizer, forestry residues (e.g., thinnings, sawdust, wood chips, etc.), renewable fuel residues, spent filter media, pulp and paper residues (e.g., black liquor), agricultural residues (e.g., corn stover, bean stover, sugar cane bagasse, etc.), herbaceous energy crops (e.g., switchgrass, thatch, etc.), woody energy crops (e.g., hybrid poplar, southern yellow pine, etc.), aquatic energy crops (e.g., algae, seaweed, etc.), and mixtures of any two or more thereof.

[0052] Exemplary lipid feedstocks include, but are not limited to, animal fats, animal oils, microbial oils, vegetable fats, vegetable oils, vegetable fats, vegetable oils, greases, or mixtures of any two or more thereof. Vegetable and / or vegetable oils and / or microbial oils include, but are not limited to, corn oil, distilled corn oil, non-edible corn oil, babassu oil, carinata oil, soybean oil, canola oil, coconut oil, rapeseed oil, tall oil, tall oil fatty acids, palm oil, palm oil fatty acid distillates, palm sludge oil, jatropha oil, palm kernel oil, shepherd's purse oil, sunflower oil, castor oil, camelina oil, archaeal oil, bacterial oil, fungal oil, protozoan oil, algae oil, seaweed oil, oils derived from halophilic organisms, and mixtures of any two or more thereof. These can be classified into crude, degummed, and RBD (refined, bleached, and deodorized) grades depending on the level of pretreatment and residual phosphorus and metal content. However, any of these grades may be used in the present technology. Animal fats and / or oils as used above include, but are not limited to, inedible tallow, edible tallow, industrial tallow, floating tallow, bleachable fancy tallow, lard, industrial lard, choice white grease, poultry fat, poultry oil, fish fat, fish oil, and mixtures of any two or more thereof. Grease can include, but is not limited to, yellow grease, brown grease, waste vegetable oil, restaurant grease, trap grease from municipalities such as water treatment plants, and used oil from industrial packaged food operations, and mixtures of any two or more thereof. Depending on the level of pretreatment, such bio-renewable lipid feedstocks may contain between about 1 wppm and about 800 wppm phosphorus, and between about 1 wppm and about 400 wppm total metals (mainly sodium, potassium, magnesium, calcium, iron, and copper). The lipids may also contain up to 100 wt.% free fatty acids.The lipids may comprise about 5 wt.%, about 10 wt.%, about 15 wt.%, about 20 wt.%, about 25 wt.%, about 30 wt.%, about 35 wt.%, about 40 wt.%, about 45 wt.%, about 50 wt.%, about 55 wt.%, about 60 wt.%, about 65 wt.%, about 70 wt.%, about 75 wt.%, about 80% wt.%, about 85% wt.%, about 90% wt.%, about 95% wt.%, or any two of these values ​​including and / or any range therebetween or other combinations of these values.

[0053] Thus, the lipid feedstock for any embodiment herein may include corn oil, non-edible corn oil, distilled corn oil, babassu oil, carinata oil, soybean oil, canola oil, coconut oil, rapeseed oil, tall oil, tall oil fatty acids, palm oil, palm oil fatty acid distillates, palm sludge oil, jatropha oil, palm kernel oil, shepherd's purse oil, sunflower oil, castor oil, camelina oil, archaeal oil, bacterial oil, fungal oil, protozoan oil, algal oil, seaweed oil, halophilic organism derived oil, maltose ... oils, rendered fats, inedible tallow, edible tallow, industrial tallow, floating tallow, bleachable fancy tallow, lard, industrial lard, choice white grease, poultry fat, poultry oil, fish fat, fish oil, frying oil, yellow grease, brown grease, waste vegetable oil, restaurant grease, trap grease from municipalities such as water treatment plants, and used oils from industrial packaged food operations, or mixtures of any two or more thereof. In embodiments, derivatives of such lipids, such as alkyl esters formed via transesterification or esterification of lipids with alcohols, may be used in place of lipids. Examples include fatty acid methyl esters (FAMEs), which are the most common type of biodiesel. Other derivatives include free fatty acids (FFAs) formed by hydrolysis of lipids, or FAMEs produced by esterification of FFAs with methanol.

[0054] Co-hydroprocessing embodiments The amount of lipid based on lipid+bio-oil is between about 16 vol.% and about 90 vol.%. The concentrations based on lipid+bio-oil are about 18 vol.%, about 20 vol.%, about 22 vol.%, about 24 vol.%, about 26 vol.%, about 28 vol.%, about 30 vol.%, about 32 vol.%, about 34 vol.%, about 36 vol.%, about 38 vol.%, about 40 vol.%, about 42 vol.%, about 44 vol.%, about 46 vol.%, about 48 vol.%, about 50 vol.%, about 52 vol.%, about 54 vol.%. , about 56 vol.%, about 58 vol.%, about 60 vol.%, about 62 vol.%, about 64 vol.%, about 66 vol.%, about 68 vol.%, about 70 vol.%, about 72 vol.%, about 74 vol.%, about 76 vol.%, about 78 vol.%, about 80 vol.%, about 82 vol.%, about 88 vol.%, or any range including and / or between any two of these values ​​or combinations of these values.

[0055] The volume ratio of lipid+bio-oil to any diluent is between 1:1 and 1:9. The lipid+bio-oil to diluent ratio can be about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, 1:7, and 1:8, or any range including and / or between any two of these values ​​or combinations of these values.

[0056] In any embodiment herein, the lipid and bio-oil feedstock is hydrofinished as a combined hydrofiner feed, and optionally subsequently hydrocracked and / or hydroisomerized. The effective H / C ratio of the combined lipid and bio-oil feed is greater than 1.40. The effective H / C ratio of the combined feed can be about 1.45, about 1.50, about 1.55, about 1.60, about 1.65, about 1.70, about 1.75, about 1.80, about 1.85, about 1.90, and about 1.95, or any range including and / or between any two of these values. For example, the effective H / C ratio of the combined lipid and bio-oil feed is between 1.55 and 1.85.

[0057] In this technique, the combined feed is subjected to hydrofinishing in the presence of hydrogen over hydrogenation metals from Groups VIB and VIII of the periodic table in sulfided form. Examples of suitable monometallic, bimetallic, and trimetallic catalysts include Mo, Ni, Co, W, CoMo, NiMo, NiW, NiCoMo. These catalysts may be supported on alumina or alumina modified with oxides of silicon and / or phosphorus. These catalysts may be purchased in the form of reduced sulfides or, more commonly, may be purchased as metal oxides and sulfided during start-up. Hydrofinishing is carried out at temperatures falling within the WABT range of about 480°F (250°C) to about 700°F (370°C) and at pressures of about 1000 psig (69 barg) to about 4,000 psig (275 barg). WABT, or weighted average bed temperature, is commonly used for fixed-bed, adiabatic reactors to represent the "average" temperature of the reactor taking into account the non-linear temperature profile between the inlet and outlet of the reactor.

number

[0058] Hydrodeoxygenation of pyrolysis bio-oil typically requires a significantly higher hydrofiner temperature, with WABT values ​​of about 700°F or higher. This is mainly due to the presence of more heat-resistant oxygen compounds, such as phenols and guaiacols. Operating at such high temperatures increases the aromatic content of the product. The increase in aromatics is due to a hydrogenation-dehydrogenation equilibrium, where at lower temperatures (below about 690°F) hydrogenation dominates and at higher temperatures (above about 690°F) dehydrogenation dominates (more aromatics). Higher aromatics content reduces the cetane number of the diesel product and increases the rate of carbon build-up on the catalyst. With this technology, the hydrofiner temperature required to reach deoxygenation is surprisingly low. Lower temperatures achieve more complete aromatic saturation.

[0059] The kerosene / diesel fraction of the product of the co-hydroprocessing of lipids and bio-oils according to embodiments of the present invention (i.e., hydrocarbon products within the kerosene and / or diesel boiling range, abbreviated as kero / diesel) has an oxygen content of less than about 0.1 wt.%. The kerosene / diesel fraction may have an oxygen content of less than about 0.01 wt.%, about 0.02 wt.%, about 0.03 wt.%, about 0.04 wt.%, about 0.05 wt.%, about 0.06 wt.%, about 0.07 wt.%, about 0.08 wt.%, about 0.09 wt.%, about 0.1 wt.%, or any range including and / or between any two of these values, or less than any one of these values, or combinations of these values. Such low oxygen values ​​can be detected by appropriate analytical techniques, including, but not limited to, fast neutron activation analysis or instrumental neutron activation analysis.

[0060] In any embodiment herein, the kero / diesel fraction of the product of co-hydroprocessing of lipids and bio-oil according to the present invention has a cetane number greater than about 40. The kero / diesel fraction may have a cetane number of about 42, about 44, about 46, about 48, about 50, about 52, about 54, about 56, about 58, about 60, about 62, about 64, about 66, about 68, about 70, about 80, or any range including and / or between any two of these values, or greater than any one of these values, or combinations of these values.

[0061] The kerosene / diesel fraction of the product of co-hydroprocessing of lipids and bio-oil according to the present invention may typically have a 60° F. density of less than about 0.88 kg / L, and may have a density of about 0.86 kg / L, about 0.85 kg / L, about 0.84 kg / L, about 0.83 kg / L, about 0.82 kg / L, about 0.81 kg / L, about 0.80 kg / L, about 0.79 kg / L, about 0.78 kg / L, or any range including and / or between any two of these values ​​or less than any one of these values ​​or combinations of these values.

[0062] The product kerosene / diesel fraction of the co-hydroprocessing of lipids and bio-oil according to any embodiment herein may comprise a cloud point of about 20°C to about -50°C. The cloud point of the composition can be about 18C, about 14C, about 10C, about 6C, about 2C, about -2°C, about -4°C, about -6°C, about -8°C, about -10°C, about -12°C, about -14°C, about -16°C, about -18°C, about -20°C, about -22°C, about -24°C, about -26°C, about -28°C, about -30°C, about -32°C, about -34°C, about -36°C, about -38°C, about -40°C, about -42°C, about -44°C, about -46°C, about -48°C, about -50°C, or any range including and / or between any two of these values ​​or less than any one of these values ​​or combinations of these values.

[0063] Bio-oil extraction with lipids followed by hydrorefining of the extract-containing solution To illustrate the technology, an embodiment of the invention is shown as a block flow diagram in FIG. 2. Referring to FIG. 2, lignocellulosic biomass 101 is fed to a converter 110 for conversion to bio-oil, bio-based gas, and char. The biomass 101 may be agricultural residues (e.g., corn stover), forestry residues (e.g., wood chips, thinnings, sawdust, etc.), herbaceous (e.g., switchgrass), or woody (e.g., hybrid poplar). The biomass 101 is preferably dried and compacted to maximize the surface area to volume ratio for heating and mass transfer during conversion inside the converter 110. The converter may be batch or continuous. Continuous converters include fluidized bed fast pyrolysis reactors, circulating fluidized bed reactors, auger reactors, ablative reactors, rotary kiln reactors, rotating cone reactors, entrained bed reactors, free fall reactors, and slurry liquefaction reactors as described above. It is an example of a batch converter that subjects a can of biomass 101 to slow pyrolysis. Converter temperatures and pressures are typically in the range of 350-1000°F and -10-3000 psig, respectively.

[0064] Steam 102 and char 103 exit the converter 110. The char may be used to fuel the endothermic biomass conversion reactor 110 or may be provided as a by-product (e.g., for soil improvement). In an embodiment of the present technology, the steam 102 is contacted with the lipid feed 104 in the contactor 120. In addition to the conversion products above the boiling point, the steam 102 also contains droplets of lignin-derived oligomers present as aerosols present in the steam 102 due to entrainment. The bio-oil vapor in the steam stream 102 condenses upon contact with the cool lipid stream 104, which enters the contactor 120 at a temperature in the range of approximately 60-300°F. In an embodiment, the steam stream 102 is pre-cooled from the converter temperature to a temperature in the range of approximately 250-500°F before entering the contactor 120. A variety of process coolers known to those skilled in the art can be used for this hot vapor pre-cooling task, including air-cooled heat exchangers and shell-and-tube heat exchangers. Shell-and-tube pre-coolers may utilize a heat transfer fluid suitable for heat integration with the process stream requiring heating (e.g., the reboiler in fractionation unit 150 described later herein). In an embodiment, vapor stream 102 may also be subjected to an electrostatic precipitator or other means of aerosol collection known to those skilled in the art to collect aerosols entrained in stream 102.

[0065] The lipids 104 may be vegetable oils (e.g., soybean oil, canola oil, corn oil, etc.), animal fats (e.g., tallow, lard, poultry oil, etc.), oils or greases from food processing or manufacturing operations (e.g., used cooking oil, yellow grease, brown grease, etc.), or any combination of fractions thereof. In embodiments, derivatives of these lipids may be used in place of the lipids themselves; for example, fatty acid alkyl esters (biodiesel) derived from lipid feedstocks (e.g., soybean oil or used cooking oil, etc.) may be used as the lipids 104. In embodiments, the lipids 104 may also include water-soluble components, such as water or glycerin, present in the lipids 104 at less than 20 wt.%. In embodiments, the water-soluble components present in the lipids 104 are by-products of biodiesel production and may contain trace amounts of impurities, such as alcohols, alkali alkoxides, alkali hydroxides, alkali chlorides, alkali citrates, alkali sulfates, enzymes, and other compounds known to those skilled in the art found in biodiesel production.

[0066] The contactor 120 typically operates in the range of around 100-300°F at pressures between atmospheric and approximately 600 psig. The contactor may be continuous or batch. Examples include an absorber (where vapor 102 rises through a packed or trayed column where it is in countercurrent contact with the falling lipids 104), an extraction column (where condensed bio-oil is in countercurrent contact with the lipids), or a mixer / settler (where streams 102 and 104 are mixed via agitation and then allowed to phase separate without agitation). In all cases, the mass ratio of stream 104 to stream 102 varies between around 20:1 and 0.5:1.

[0067] A portion of stream 102 dissolves into lipids upon contact, resulting in three exit streams from contactor 120: (1) aqueous liquid phase 105, (2) organic liquid phase 106, and (3) gas phase 116. Aqueous liquid phase 105 contains primarily water, C2-C4 oxygenates, and sugars. In embodiments where stream 104 contains water soluble components, aqueous phase 105 also contains the water soluble components introduced into stream 104. Organic liquid phase 106 contains primarily lipids, with 0.1-10% phenolic compounds and lignin-derived oligomers extracted from the bio-oil (i.e., from condensed stream 102). Gas phase 116 contains CO, CO 2 , H 2 , C1-C2 non-condensable hydrocarbons and oxygenates, and any other process gases added to converter 110. Stream 116 may be used as fuel gas for the plant. CO and H 2 If the concentration is greater than 10 mol.%, stream 116 may be used as synthesis gas to produce methanol, oxo-alcohols, or Fischer-Tropsch hydrocarbons.

[0068] In various embodiments, the aqueous phase 105 is directed to the recovery of acetic acid, acetals, hydroxyacetaldehyde, and other chemicals from the aqueous phase. Depending on the purity required for the chemicals, various separation methods known to those skilled in the art can be used, including distillation, membrane separation, and molecular sieve adsorption.

[0069] The organic liquid phase 106 includes lipids and phenolic bio-oil compounds and has an effective H / C ratio of greater than 1.40. The effective H / C ratio of the combined feed can be about 1.45, about 1.50, about 1.55, about 1.60, about 1.65, about 1.70, about 1.75, about 1.80, about 1.85, about 1.90, and about 1.95, or any range including and / or between any two of these values ​​or combinations of these values. For example, the effective H / C ratio of the combined lipid and bio-oil feed is between about 1.55 and 1.85.

[0070] The organic liquid phase 106 is subsequently conducted to the hydrotreating reactor 130. The organic liquid phase has an effective H / C ratio between about 1.55 and 1.85, where the organic liquid is combined with hydrogen-rich gas 107 and heated to a temperature between 450-700°F under a pressure of 1,000-4,000 psig. In an embodiment, the organic liquid phase 106 may be subjected to a drying step to remove water and other light oxygenates before being introduced into the hydrotreating reactor 130. In a preferred embodiment, the temperature and pressure ranges are around 500-650°F (WABT) and about 1,600-3,200 psig, respectively. The hydrotreating reactor is preferably a fixed bed reactor containing a catalyst that promotes the hydrogenation and deoxygenation reactions. Typical catalysts are NiMo, CoMo, and NiW on a gamma-alumina support. A preferred catalyst is sulfided molybdenum and tungsten with nickel as a promoter. The Ni:Mo and Ni:W ratios of the preferred catalysts are between 1:3 and 1:5. The preferred catalysts have an average pore size of 180 Angstroms or greater. The preferred catalysts (NiMo or NiW) and hydrogen pressures (>1600 psig) ensure that the difficult-to-hydrodeoxygenate planar phenol molecules are first hydrogenated to cyclohexanol and / or cycloxanone (which have more mobile "boat" and "chair" conformations), allowing better access to the hydrodeoxygenation sites of the catalyst.

[0071] In an embodiment, the hydrotreating reactor 130 also contains a catalyst that promotes the hydrocracking and isomerization reactions. Typical hydrocracking / isomerization catalysts have a silica-alumina support that is either amorphous or crystalline. Preferred crystalline supports contain zeolites. Hydroactive metals for hydrocracking / isomerization include both precious and base metals, such as platinum, platinum / palladium, and nickel / tungsten. Typically, H 2 If S is expected to be present in the hydrogen-rich gas 107, a NiW catalyst is selected, whereas if a clean hydrogen-rich gas (i.e., no H in the gas) is desired, a NiW catalyst is selected. 2 S or NH 3As will be appreciated by those skilled in the art, the product of a first hydroprocessing stage using sulfided NiMo or NiW catalysts may be hydrotreated using steam, nitrogen, hydrogen, or another light gas to reduce H before being fed to a second hydroprocessing stage containing a Pt or Pt / Pd catalyst. 2 S, H 2 O, and NH 3 It seems necessary to remove it.

[0072] When the hydroprocessing reactor 130 is an adiabatic fixed bed reactor, a hydrocarbon diluent is preferably used to mitigate the temperature rise associated with the exothermic hydrogenation reaction. The hydrocarbon diluent may be a petroleum middle distillate or a partially recycled product of the hydroprocessing reactor (e.g., stream 117, described in more detail later in this specification).

[0073] The reactor effluent 108 is subsequently cooled and separated in separator 140 into a gas product stream 109, a hydrocarbon product stream 117, and a water stream 111. The product gas stream is primarily unreacted hydrogen and gas phase by-products of the hydrotreating reaction, including CO, CO 2 , H 2 S, N.H. 3 , and C1-C4 hydrocarbons. In an embodiment, a portion of this gas is processed through a membrane to separate the C3+ hydrocarbons and recovered in fractionation unit 150 (described later herein). In an embodiment, the gas product 109 is processed (e.g., through an amine scrubber) and combined with make-up hydrogen to provide the hydrogen-rich gas 107.

[0074] The hydrocarbon product stream 117 can be directed to a fractionation unit 150 where the products are fractionated according to boiling range. The gas cut 112 includes butane and lighter hydrocarbons for use as "bio-based LPG" for transportation, heating, and cooking. The gasoline cut 113 in the C5-300°F boiling range includes aromatic and naphthenic hydrocarbons formed by deoxygenation of monophenolic compounds from the bio-oil.

[0075] Kerosene / diesel cut 114 within the boiling range of 300-650°F contains C10-C24 hydrocarbons. In addition to paraffins formed from lipid fatty acid chains, the kerosene / diesel cut contains naphthenic and aromatic compounds from lignin-derived phenolic dimers / oligomers and their hydrocracking products. The kerosene / diesel cut has an oxygen content of less than 1 wt.% and is well suited for use in compression ignition engines either as is or blended with petroleum and / or biodiesel.

[0076] Unlike blends with 100% lipid-based renewable diesel, the kerosene or diesel product of the present technology, when blended with greater than 7 vol.% biodiesel, can solubilize biodiesel impurities that are less soluble in 100% lipid-based renewable diesel. In an embodiment, a jet fuel distillate is separated from the kerosene / diesel cut 114 for use in aviation turbine fuel.

[0077] The bottoms fraction 115 contains 650F+ boiling material, concentrated with most of the unconverted lignin-derived oligomers, which may be recycled back to the hydrotreating reactor 130 or directed to different hydrocracking reactions (not shown) to be converted to lighter hydrocarbon products for combination with the LPG, gasoline, and kerosene / diesel products described above.

[0078] Lipid and / or lipid derivative assisted biomass liquefaction To illustrate the technology, an embodiment of the invention is shown as a block flow diagram in FIG. 3. Referring to FIG. 3, lignocellulosic biomass 201 is fed to a converter 210 for conversion to bio-oil, bio-based gas, and char. Biomass 201 may be agricultural residues (e.g., corn stover), forestry residues (e.g., wood chips, thinnings, sawdust, etc.), herbaceous (e.g., switchgrass), woody (e.g., hybrid poplar), or a mixture of two or more. In an embodiment, biomass 201 may include biomass that has been fractionated to be enriched in lignin, cellulose, or holocellulose. In a preferred embodiment, biomass 201 may include extracted lignin, such as lignin produced by kraft, organosolv, ammonia explosion, enzymatic hydrolysis, and other such lignin extraction processes known to those skilled in the art. Biomass 201 is preferably dried and reduced in size to maximize the surface area to volume ratio for heating and mass transfer during conversion inside converter 210. Biomass 201 may be fed to converter 210 by a lock hopper, rotary airlock, extruder, pneumatic conveyor, or other means of transporting solids known to those skilled in the art.

[0079] Solvent 202 is also fed into converter 210 to facilitate pyrolysis of the biomass. Solvent 202 may be fed with biomass 201 as a slurry or may be fed into converter 210 as a separate stream. In embodiments where solvent 202 and biomass 201 are premixed and fed together into converter 210, the mixture may be fed into converter 210 by using centrifugal pumps, pulp pumps, slurry pumps, macerator pumps, extruders, and other slurry transport means known to those skilled in the art. In all cases, the mass ratio of solvent 202 to biomass 201 is between 20:1 and 0.5:1. Solvent 202 should be selected primarily for its chemical properties as a solvent, with some consideration of practical constraints such as cost, ease of recovery, and volatility. Solvent 202 plays an essential role in solubilizing feedstock 201 and the desired products, such that products that are readily soluble in the solvent are easier to recover and less likely to participate in undesirable side reactions. The solvent also has a direct effect on the decomposition of the feedstock, such that certain products are produced in higher yields in solvents in which they are completely soluble than in solvents in which they are not. In an embodiment, the solvent 202 can also donate hydrogen to the decomposition products from the biomass 201, increasing the effective H / C ratio of the decomposition products.

[0080] In a preferred embodiment, the solvent 202 is a lipid, such as soybean oil or used edible oil, or a lipid derivative, such as alkyl esters produced from transesterification or esterification of lipids (i.e., biodiesel), or paraffinic hydrocarbons produced from hydrotreated lipids (i.e., renewable paraffinic kerosene, renewable diesel, etc.).

[0081] Converter 210 may be batch or continuous. Continuous converters include slurry liquefaction reactors, plug flow reactors, and countercurrent reactors. An exemplary batch converter is one in which agitated biomass 201 is mixed with solvent 202 and the contents are removed after heating. Converter temperatures and pressures are typically in the range of 350-1000°F and -10-3000 psig, respectively, where the pressure is sufficient to maintain the solvent 202 in a sub- or supercritical liquid phase.

[0082] Converter 210 exits with vapor 211 and heavy phase 212. Vapor 211 contains the conversion products above their boiling points and non-condensable gases fed to converter 210 for processing, such as nitrogen, natural gas, or compressed, recycled product gas from the technology. Vapor 211 is directed to separator 220 where condensable products are recovered. Separator 220 is typically operated at a subcritical temperature, such as between about 60-300°F, and at the same pressure as converter 210. In an embodiment, vapor stream 211 is cooled from the converter temperature to a temperature within the range of about 60-300°F prior to entering separator 220. A variety of process coolers known to those skilled in the art can be utilized for this hot vapor pre-cooling task, including air-cooled heat exchangers and shell-and-tube heat exchangers. The shell-and-tube precooler may utilize a heat transfer fluid suitable for heat integration with process streams requiring heating (e.g., a reboiler in fractionation unit 240 described later herein). In an embodiment, vapor stream 211 may also be subjected to an electrostatic precipitator or other means of aerosol collection known to those skilled in the art to collect aerosols entrained in stream 211. The gas phase 222 is a mixture of CO, CO 2 , H 2 , C1-C2 non-condensable hydrocarbons and oxygenates, and any other process gases added to converter 210. Stream 222 may be used as fuel gas for the plant. CO and H 2If the concentration is greater than 10 mol.%, stream 222 may be used as synthesis gas to produce methanol, oxo alcohols, or Fischer-Tropsch hydrocarbons. In some embodiments, stream 222 may be compressed and recycled to converter 210, as previously described.

[0083] Condensate stream 221 contains decomposition products below their boiling point at the operating conditions of separator 220. In an embodiment, stream 221 typically contains water, light oxygenates such as acetic acid, formic acid, propionic acid, formaldehyde, acetals, acetaldehyde, hydroxyacetaldehyde, and methanol, and any entrained aerosols from converter 210.

[0084] In an embodiment, the condensate 221 is directed to the recovery of acetic acid, formic acid, propionic acid, acetals, hydroxyacetaldehyde, and other chemicals from the aqueous phase. Depending on the purity required for the chemicals, various separation methods known to those skilled in the art can be used, including distillation, membrane separation, and molecular sieve adsorption.

[0085] The heavy phase 212, which includes the conversion products below its boiling point, solvent, unreacted feedstock, and char, is directed to the separator 230 by pumping, gravity, or differential pressure between the converter 210 and the separator 230. The separator 230 removes the solid residue 232, which is typically the unreacted feedstock and char, and the heavy liquid 231, which includes the high boiling liquid products and solvent. The solid residue 232 may be used to fuel the endothermic biomass conversion reactor 210 or may be supplied as a by-product (e.g., for soil improvement). The separator 230 may be at least one of a settling tank, a hydrocyclone, a centrifuge, a sintered metal filter, a bag filter, a packed bed filter, a pressurized leaf filter, or other solid-liquid separation means known to those skilled in the art. In a preferred embodiment, the separator 230 is a settling tank followed by a filtration device as listed above. In an embodiment, a filter medium such as diatomaceous earth is used to enhance the removal of the solid residue 232 from the heavy liquid 231. Separator 230 may operate at a temperature below that of converter 210, but not below about 200° F. to maintain heavy phase 212 at a low enough viscosity to facilitate removal of solid residue 232. In an embodiment, separator 230 operates at a temperature in the range of 200-400° F. In an embodiment, solids removal additive 235, e.g., alcohol or hydrocarbons, may be added to separator 230 to further reduce the viscosity of heavy phase 212 and thereby aid in solids removal. In an embodiment, solids removal additive 235 is a hydrocarbon produced from hydrotreating lipids and heat modified products. In an embodiment, solids removal additive 235 is a renewable paraffinic naphtha produced from hydrotreating lipids and heat modified products. Solids removal additive 235 exits separator 230 primarily with heavy liquids 231.

[0086] Heavy liquid 231 is directed to contactor 240 where it is contacted with wash stream 245. Contactor 240 typically operates at around 100-300°F at pressures between about 1-500 psig. The contactor may be continuous or batch type. Examples include absorber towers, extractor towers, contacting centrifuges, or mixer / settler tanks. In all cases, the mass ratio of stream 231 to stream 245 varies between about 20:1 and 1:1.

[0087] A portion of stream 231 dissolves in wash stream 245 upon contact, resulting in two exit streams from contactor 240: aqueous liquid phase 242, and organic liquid phase 241. Wash liquid 245 is a polar liquid suitable for washing off high boiling polar products from the decomposition of polysaccharides, such as levoglucosan, levoglucosenone, cellobiosan, maltosan, furfural, 5-methylfurfural, dimethoxytetrahydrofuran, and other sugars and anhydrosugars. In an embodiment, wash liquid 245 has a dielectric constant greater than about 10.0. In an embodiment, wash liquid 245 is primarily water. In an embodiment, wash liquid 245 is primarily glycerol. In an embodiment, wash liquid 245 is a mixture of water and glycerol. In an embodiment, the wash solution 245 is a by-product of biodiesel production that contains primarily water and glycerol and may contain trace amounts of impurities such as alcohols, alkali alkoxides, alkali hydroxides, alkali chlorides, alkali citrates, alkali sulfates, enzymes, and other compounds known to those skilled in the art found in biodiesel production. In an embodiment, the condensate 221 is used to create some or all of the wash solution 245.

[0088] In an embodiment, the aqueous phase 242 can be combined with the condensate 221 to form a blended composition of the aqueous phase 242 for further processing. In an embodiment, the aqueous phase 242 is directed to the recovery of oligosaccharides and monosaccharides and anhydrosugars. Depending on the purity required for the chemicals, various separation methods known to those skilled in the art can be used, including distillation, membrane separation, and molecular sieve adsorption. In an embodiment, the aqueous phase 242 is suitable for anaerobic or aerobic digestion to produce biogas. In an embodiment, the aqueous phase 242 is suitable for fermentation to produce bioalcohol.

[0089] The organic liquid phase 241 contains primarily the solvent 201 and the solids removal additive 235, and has phenolic compounds and soluble lignin-derived oligomers produced from the biomass 201.

[0090] The organic liquid phase 241, which includes the solvent, solids removal additive, and phenolic bio-oil compounds, has an effective H / C ratio of greater than 1.40. The effective H / C ratio of the organic liquid phase 241 can be about 1.45, about 1.50, about 1.55, about 1.60, about 1.65, about 1.70, about 1.75, about 1.80, about 1.85, about 1.90, and about 1.95, or any range including and / or between any two of these values. For example, the effective H / C ratio of the combined lipid and bio-oil feed is between 1.55 and 1.85.

[0091] The organic liquid phase 241 is then conducted to the hydrotreating reactor 250 where the organic liquid is combined with the hydrogen-rich gas 255 and heated to a temperature between about 450-700°F under a pressure of 1,000-4,000 psig. In an embodiment, the organic liquid phase 241 may be subjected to a drying step to remove water and other light oxygenates before being introduced into the hydrotreating reactor 250. In a preferred embodiment, the temperature and pressure ranges are around 500-650°F (WABT) and about 1,600-3,200 psig, respectively. The hydrotreating reactor is preferably a fixed bed reactor containing a catalyst that promotes the hydrogenation and deoxygenation reactions. Typical catalysts are NiMo, CoMo, and NiW on a gamma-alumina support. A preferred catalyst is sulfided molybdenum and tungsten with nickel as a promoter. The Ni:Mo and Ni:W ratios of the preferred catalysts are between 1:3 and 1:5. The preferred catalysts have an average pore size of 180 Angstroms or greater. The preferred catalysts (NiMo or NiW) and hydrogen pressures (>1600 psig) ensure that the difficult-to-hydrodeoxygenate planar phenol molecules are first hydrogenated to cyclohexanol and / or cyclohexanone (which have more mobile "boat" and "chair" conformations), allowing better access to the hydrodeoxygenation sites of the catalyst.

[0092] In an embodiment, the hydrotreating reactor 250 also contains a catalyst that promotes the hydrocracking and isomerization reactions. Typical hydrocracking / isomerization catalysts have a silica-alumina support that is either amorphous or crystalline. Preferred crystalline supports contain zeolites. Hydroactive metals for hydrocracking / isomerization include both precious and base metals, such as platinum, platinum / palladium, and nickel / tungsten. Typically, H 2 If S is expected to be present in the hydrogen-rich gas 255, a NiW catalyst is selected, whereas if a clean hydrogen-rich gas (i.e., no H in the gas) is desired, a NiW catalyst is selected. 2 S or NH 3As will be appreciated by those skilled in the art, the product of a first hydroprocessing stage using sulfided NiMo or NiW catalysts may be hydrotreated using steam, nitrogen, hydrogen, or another light gas to reduce H before being fed to a second hydroprocessing stage containing a Pt or Pt / Pd catalyst. 2 S, H 2 O, and NH 3 It seems necessary to remove it.

[0093] When hydroprocessing reactor 250 is an adiabatic fixed bed reactor, a hydrocarbon diluent is preferably used to mitigate the temperature rise associated with the exothermic hydrogenation reaction. The hydrocarbon diluent may be a petroleum middle distillate or a partially recycled product of the hydroprocessing reactor (e.g., stream 261, described in more detail later in this specification).

[0094] The reactor effluent 251 is then cooled and separated by separator 260 into a gas product stream 263, a hydrocarbon product stream 261, and a water stream 262. In an embodiment, the water stream 262 may be recycled back in all or a portion of the wash liquid 245. The product gas stream is primarily unreacted hydrogen and gas phase by-products of the hydrotreating reaction, including CO, CO 2 , H 2 S, N.H. 3 , and C1-C4 hydrocarbons. In an embodiment, a portion of this gas is processed through a membrane to separate the C3+ hydrocarbons and recovered in fractionation unit 270 (described later herein). In an embodiment, gas product 263 is processed (e.g., through an amine scrubber) and combined with make-up hydrogen to provide hydrogen-enriched gas 255.

[0095] The hydrocarbon product stream 261 may be directed to a fractionation unit 270 where the products are fractionated according to boiling range. The gas cut 271 includes butane and lighter hydrocarbons for use as "bio-based LPG" for transportation, heating, and cooking. The gasoline cut 272 in the boiling range of C5-300F includes aromatic and naphthenic hydrocarbons formed by deoxygenation of monophenolic compounds from the bio-oil. The gasoline cut 272 may be recycled back to include all or a portion of the solids removal additive 235.

[0096] Kerosene / diesel cuts 273 within the boiling range of 300-650F contain C10-C24 hydrocarbons. In addition to paraffins formed from lipid fatty acid chains, the kerosene / diesel cuts contain naphthenic and aromatic compounds from lignin-derived phenolic dimers / oligomers and their hydrocracking products. The kerosene / diesel cuts have an oxygen content of less than 1 wt.% and are well suited for use in compression ignition engines as a neat fuel or blended with petroleum and / or biodiesel.

[0097] Unlike blending with 100% lipid-based renewable diesel, the kerosene or diesel product of the present technology can be blended with greater than 7% biodiesel, which has impurities that have low solubility in 100% lipid-based renewable diesel. In an embodiment, a jet fuel distillate is separated from the kerosene / diesel cut 273 for use in aviation turbine fuel.

[0098] Bottoms fraction 274 contains 650F+ boiling material, concentrated with most of the unconverted lignin-derived oligomers, which may be recycled back to hydrotreating reactor 250 or directed to different hydrocracking reactions (not shown) to be converted to lighter hydrocarbon products for combination with the LPG, gasoline, and kerosene / diesel products described above. Bottoms fraction 274 may also be recycled back in all or part of solvent 202 or sold as a residual fuel oil product containing renewable content.

[0099] The present technology thus generally described will be more readily understood by reference to the following examples, which are provided as illustrations and are not intended to limit the present technology. EXAMPLES

[0100] The following examples set forth three experiments conducted to determine the feasibility and usefulness of the present invention.

[0101] All three experiments were carried out in a 1 liter autoclave bottom drain reactor equipped with a Robinson-Mahoney type fixed catalyst basket. The catalyst basket was loaded with a commercial NiMo fixed bed hydrotreating catalyst that was sulfided prior to loading. The annular portion of the catalyst basket contained a multi-impeller agitator, a submerged gas dispersion tube for adding hydrogen located at the bottom of the catalyst basket, an internal sample port located at the bottom of the catalyst basket, a liquid feed injection tube located at the top of the catalyst basket, a thermowell, and a gas outlet. The gas outlet was connected to a water-cooled heat exchanger used to condense components with dew points above about 100°F.

[0102] Pyrolysis oil produced from autothermal cracking of softwood was used to illustrate the present invention. Pyrolysis oil was collected in four fractions. Stage fraction 1 and stage fraction 2, referred to herein as the "high boiling fraction" or "bio-oil", were combined in approximately the same mass ratio as produced from the pyrolysis experiment, and this bio-oil was used as the reaction feed for this experiment. The high boiling fractions were used because they contain the majority of carbohydrate dehydration products, phenolic oligomers, and phenolic monomers in the correct carbon number range to produce naphtha and distillate range hydrocarbons. Further details of the pyrolysis process used to produce bio-oil can be found elsewhere (Sean A. Rollag, 2020).

[0103] Food grade canola oil was used as the reaction feed for the control test (baseline). The reaction feed for the lipid / bio-oil blend test was a mixture of about 60 wt.% food grade canola oil and about 40 wt.% bio-oil heavy fraction. The final test was performed with 100% bio-oil heavy fraction.

[0104] Octadecane, a normal paraffinic solvent, was added to the reactor such that the entire catalyst basket was submerged. A sulfiding agent, TBPS-454, was also dosed to the reactor at a level sufficient to maintain catalytic activity during the reaction. In each run, the reaction feed was added to the reactor such that the dilution of solvent to oil was approximately 3:1 by volume.

[0105] Hydrogen was fed continuously throughout the duration of each experiment. The minimum hydrogen flow rate was calculated based on the oxygen content and degree of unsaturation of the reaction feed. The flow rate used was at least twice the amount stoichiometrically required to completely deoxygenate and hydrogenate the reaction feed throughout the 90 minute duration of the experiment. Thus, the higher oxygen content of the bio-oil resulted in a higher hydrogen requirement than that of canola oil. The flow rate used for the 40 wt.% bio-oil test was approximately twice the baseline, while the 100% bio-oil test required nearly 3.2 times the amount of hydrogen.

[0106] After the reactor was filled with the liquid charge, it was purged with nitrogen, pressurized to approximately 1000 psig, and heated to 640° F. Once the reactor temperature reached 640° F., it was further pressurized to 1660 psig with 99.99% hydrogen and continuous hydrogen flow was initiated, designated "time zero" of the reaction cycle.

[0107] Water vapor and other compounds that were volatilized at reactor conditions were continuously flushed from the reactor. Those condensable at approximately 100° F. were condensed in the heat exchanger described above. Samples were also collected directly from the reactor through an internal sample port during the experiment. All liquid samples were cooled to approximately 100° F. prior to collection to help prevent loss of volatile species.

[0108] After the desired cycle time or degree of conversion was reached, the reactor was shut down. Shutdown was accomplished by turning off the hydrogen supply and lowering the temperature set point to 140° F. After reaching 140° F. and completing a full nitrogen purge, the reactor was completely emptied through the bottom drain port. Nitrogen pressure of about 50 psig was maintained while draining the reactor. Only after all the liquid from the previous run had been drained were fresh solvent, sulfiding agent, and fresh reactant feed charged to the reactor for the subsequent run. One catalyst charge was used for all reactions described in this example.

[0109] All runs achieved high levels of reactant conversion as indicated by measured Total Acid Number (TAN) values ​​(per ASTM D664) as shown below (Error! Reference source not found). The baseline run proceeded normally with no signs of catalytic activity degradation and reactor fouling. Similarly, the 40% bio-oil in canola run proceeded similarly to the baseline run, achieving full conversion with no signs of catalytic activity degradation and reactor fouling. Conversely, the reactor product from the 100% bio-oil case had a product TAN value nearly four times higher than observed from the other two runs. Elevated TAN is a major indicator of poor hydrofinishing performance due to catalytic activity degradation and / or fouling from coking. Furthermore, an attempt was made to sample the reactor contents, but the reactor contents sample port was found to be clogged. Due to this clogging, no liquid samples could be obtained throughout this run. Therefore, this run was run to completion at which point the liquid reaction product was removed through the bottom drain of the vessel.

[0110] After the 100% bio-oil experiment, when the reactor was opened after the experiment was completed, it was found to contain a significant amount of coke accumulation. Coke formation was not observed in the experiments conducted with canola oil or the 40 wt.% bio-oil experiment. Hu et al. (Xun Hu, 2020) review many of the most recent studies in the literature on bio-oil hydrodeoxygenation. Although some differences were observed between different catalysts and operating conditions, it was found that the biomass-derived bio-oil formed significant amounts of coke in each example, similar to the 100% bio-oil experiments discussed herein. Carbohydrate-derived materials were observed to dehydrate, decarboxylate, and decarbonylate to produce unsaturated intermediate compounds that combined and polymerized to form aromatic compounds, which further polymerized to form coke. Similarly, lignin-derived compounds that were already actually aromatic further condensed to form polycyclic aromatic compounds, which continued to polymerize and form coke.

[0111] As reviewed by Hu et al. (Xun Hu, 2020), some researchers have also tried using water and low molecular weight alcohols as solvents for bio-oil. Some of the solvents helped to reduce the coking rate, but the solvents used are unlikely to be practical for use on an industrial scale. Using lipids, which are already being used to produce renewable diesel, as the solvent as discussed in this invention makes the process more feasible.

[0112] Coke formation was observed to reduce the liquid yield from the reactor feed considerably to the point where this method does not appear to be feasible for processing 100% bio-oil. The 100% canola oil sample, as shown in (Error! Reference not found) 4, resulted in a total liquid yield of around 85%. Addition of 40 wt% bio-oil to canola reduced the total liquid yield to around 68%, as expected due to the higher oxygen content of the bio-oil. Assuming that the liquid yield follows a linear trend, the 100% bio-oil experiment would be expected to produce around 40% liquid. However, the yield was measured to be only 15% due to the additional coke formation.

[0113] Coke formation during the 100% bio-oil case was such that it would be reasonably expected that the catalyst and the internals of the fixed bed system would rapidly foul, thereby rapidly reducing the catalyst bed life and making the process unfeasible on an industrial scale. In contrast, blending bio-oil with canola oil (at 40% as exemplified herein) demonstrates substantial favorable improvements in both final conversion and reduced coke formation.

[0114] The products from three experiments (100% canola oil, 40% bio-oil / 60% canola oil, and 100% bio-oil) were observed. A side-by-side display of the products revealed significant visual differences associated with the products of the 100% bio-oil reaction. The 100% canola oil and 40% bio-oil / 60% canola oil products were generally clear and similar in appearance. In contrast, the 100% bio-oil product was yellow in color. The color bodies and significant amount of insoluble material in the 100% bio-oil product are indicative of a non-paraffinic product.

[0115] It can thus be seen that the present invention provides a highly advantageous lipid-assisted conversion for hydrocarbon fuels, and more particularly for fuels having renewable content. While the present invention has been described in connection with what are presently considered to be the most practical and preferred embodiments, it will be apparent to those skilled in the art that the invention is not limited to the disclosed embodiments, and that numerous modifications and equivalent arrangements are possible within the scope of the present invention, and that the scope of the appended claims should be accorded the broadest interpretation so as to encompass all equivalent structures and products.

Claims

1. A method for converting bio-oil derived from lignocellulose biomass into hydrocarbon fuel or fuel blend raw material, (a) A step of combining the bio-oil vapor flow with lipids in a contactor and condensing the bio-oil vapor flow to produce an organic liquid phase; (b) A step of inducing the organic liquid phase into a hydrogenation reactor to produce reactor effluent; (c) A step of separating the reactor effluent into hydrocarbons, gases, and water streams; and (d) A process of fractional distillation of hydrocarbons into gasoline cut and kerosene / diesel cut. Includes, Moreover, the bio-oil vapor flow has a boiling point temperature, and, At a temperature below the boiling point of the bio-oil vapor flow, lipids are supplied to the contactor, helping to condense the bio-oil vapor flow into an organic liquid phase. The above method.

2. The method according to claim 1, wherein the organic liquid phase has an effective H / C ratio between 1.4 and 1.

8.

3. The method according to claim 1, further comprising generating a bio-oil vapor flow by at least one of rapid pyrolysis, hydrothermal liquefaction, or solvent liquefaction.

4. The method according to claim 1, wherein the lipid comprises animal fat, vegetable oil, grease, or a mixture thereof.

5. The method according to claim 1, wherein the lipids contain free fatty acids in an amount between approximately 5 wt.% and 95 wt.%.

6. The method according to claim 1, wherein the hydrogenation reactor includes at least one of hydrogenation purification, hydrogenation, hydrogenolysis, and hydrogen isomerization.

7. The method according to claim 1, wherein the hydrogenation reactor operates at a WABT between approximately 550°F and 690°F and a pressure between approximately 1,000 psig and 3,000 psig.

8. The method according to claim 1, wherein the hydrogenation reactor contains a catalyst comprising sulfurized molybdenum, tungsten, or a combination thereof.

9. The method according to claim 1, wherein the kerosene / diesel cut has a cetane number of 40 or more.

10. The method according to claim 1, further comprising blending kerosene / dieselcut with biodiesel.

11. The method according to claim 1, further comprising fractional distillation of crude bio-oil to generate a bio-oil vapor flow before combining the bio-oil vapor flow with lipids in step (b).

12. The method according to claim 11, wherein the bio-oil vapor stream is fractionally distilled according to its boiling point above approximately 200°F.

13. The method according to claim 11, wherein the bio-oil vapor stream is fractionally distilled according to its boiling point above 250°F.

14. The method according to claim 11, wherein the bio-oil vapor stream is fractionally distilled according to its boiling point above 300°F.

15. The method according to claim 11, further comprising fractionating the bio-oil vapor stream according to its solubility in water so that substantially all water-soluble compounds are removed and the bio-oil vapor stream is substantially water-insoluble before combining it with lipids in step (b).

16. The method according to claim 3, further comprising generating the bio-oil vapor flow solely from fluidized bed high-speed pyrolysis.

17. The method according to claim 1, further comprising generating a bio-oil vapor flow solely from solvent liquefaction.

18. The method according to claim 17, wherein the solvent liquefaction process utilizes a lipid or lipid derivative as part or all of the primary reaction solvent.

19. A method for converting bio-oil derived from lignocellulosic biomass into fuel or fuel blend raw material, (a) A process of supplying lignocellulosic biomass to a converter for conversion into bio-oil vapor flow and char flow; (b) A step of bringing a bio-oil vapor flow into contact with a lipid or lipid derivative in a contactor to condense the bio-oil vapor flow and form an organic liquid phase containing a phenol compound and an aqueous phase; (c) A step of separating the organic liquid phase from the aqueous phase; (d) A step of subjecting the organic liquid phase to hydrogenation and deoxygenation in a hydrogenation reactor to produce hydrocarbon products, gaseous products, and water; and (e) A process of fractionating the hydrocarbon products from the hydrogenation reactor into fuel products including gasoline and kerosene / diesel. The above method, including.

20. The method according to claim 1, wherein the contactor operates at a pressure between approximately atmospheric pressure and approximately 600 psig and at a temperature between approximately 100 and 300°F.

21. The contactor is one of an absorption tower, an extraction tower, and a mixer / sedimentation tank, In the case of an absorption tower, the bio-oil vapor flow comes into countercurrent contact with the lipids. In the case of an extraction column, the bio-oil vapor flow comes into countercurrent contact with the lipids. In the case of a mixer / sedimentation tank, the bio-oil vapor flow and lipid flow are mixed by agitation. The method according to claim 1.

22. The method according to claim 1, wherein the mass ratio of lipids to the bio-oil vapor flow is about 20:1 to 0.5:1.

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