Lipid assisted conversion

Abstract

A process for converting a bio-oil derived from lignocellulosic biomass to a fuel or fuel blend. The method can include contacting the bio-oil with a lipid or lipid derivative to form an organic phase comprising a phenolic compound and an aqueous phase. The organic phase is separated from the aqueous phase and hydrogenated and deoxygenated in a hydrotreating reactor to produce a hydrocarbon product, a gaseous product, and water. The hydrotreating reactor hydrocarbon product is fractionated into fuel products comprising gasoline and kerosene / diesel.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 63 / 339,260, filed on May 6, 2022, which is incorporated herein by reference in its entirety. Technical Field

[0003] The present technology generally relates to hydrocarbon fuels and more specifically to fuels having renewable content. More particularly, the technology relates to upgrading pyrolysis of bio-oil fractions into high-quality fuels by hydroprocessing. Background Art

[0004] As a renewable alternative to fossil fuels, biofuels have been embraced by consumers and policymakers alike as a potential key component of society's and government's climate change mitigation strategies. However, most biofuels used today are based on either sugar or lipid feedstocks. Long-term development of the biofuel industry requires diversification to more abundant lignocellulosic feedstocks, such as woody biomass.

[0005] Upgrading biomass to high-quality hydrocarbon fuels such as renewable diesel requires additional processing such as hydroprocessing. Because most hydrogen is still produced by steam reforming of fossil fuels, there is an incentive to minimize hydrogen consumption during the hydroprocessing stage.

[0006] Lignocellulosic biomass includes cellulose, hemicellulose, and lignin. Each of these components is a polymer with different building blocks, such as Figure 1 As shown. Bio-oil is formed by the depolymerization of these macromolecules, typically by thermochemical reactions disclosed in the prior art. One such method is pyrolysis. Pyrolysis generally refers to the high temperature conversion of carbonaceous feedstocks (typically solid) into liquids. To prevent combustion, pyrolysis is carried out in the absence of or complete absence of diatomic oxygen. In addition to liquids, pyrolysis products from lignocellulosic biomass include gases (mainly CO, CO2, hydrogen and non-condensable hydrocarbons) and char (carbon-rich solids). Liquid products referred to as pyrolysis oils or bio-oils typically include the following:

[0007] (1) Formation of C2-C4 oxygenated compounds by the breakdown of cellulose and hemicellulose; these include glycolaldehyde, acetal, and acetic acid and account for 8-26% of the bio-oil;

[0008] (2) Monophenols formed by depolymerization of lignin; these may also contain small amounts of furans and account for 2–7% of the bio-oil;

[0009] (3) Lignin-derived oligomers (also called "pyrolytic lignin"), which are insoluble in water and comprise 15-25% of the oil; and

[0010] (4) Sugars and anhydrosugars formed by the breakdown of cellulose and hemicellulose, which are typically soluble in water and form 10-20% of the bio-oil.

[0011] Bio-oil also includes water, which accounts for about 14 to 30% of its mass by weight. Typically, the bio-oil water exists as part of a stable emulsion. On a dry basis, bio-oil contains about 38 to 44% oxygen.

[0012] In some pyrolysis processes, condensable (i.e., liquid) products can be selectively recovered as fractions based primarily on their boiling points. In one such embodiment, fractions can typically be obtained such that water and C2-C4 oxygenates, monophenols, and lignin-derived oligomers and sugars can be recovered separately.

[0013] In some pyrolysis processes, gaseous and solid products are burned to provide fuel for the endothermic pyrolysis reaction.

[0014] The pyrolysis process can be designed to occur under a variety of conditions; such as temperature, residence time, reaction medium, and optional catalyst selection as examples, and all can be highly variable. Fast pyrolysis occurs at higher temperatures (>900°F, compared to 750-950°F for slow pyrolysis), and can be the preferred method to maximize bio-oil yield.

[0015] Pyrolysis can be carried out in many reactor configurations. A common fast pyrolysis system includes using a fluidized bed reactor on inert or catalytic solid particles. The fluidizing gas can be nitrogen, or as in some embodiments, the gas produced by pyrolysis itself (e.g., recirculated by a booster compressor). During the pyrolysis of wood chips, the ground wood is in close contact with the hot solid particles in the fluidized bed. When wood undergoes fast pyrolysis, the solid particles become coated with charcoal. These solid particles are subsequently regenerated in different containers by burning off charcoal or coke. When the hot regenerated solid particles return to the reactor, the heat of charcoal combustion provides heat for the endothermic pyrolysis reaction. In most such pyrolysis reactor systems, when the solid particles circulate between the reactor and the regenerator, the ground biomass is continuously fed to the pyrolysis reactor.

[0016] Pyrolysis can 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 reactors in an intermittent or continuous process. The solvent can be selected to improve process chemistry, or for more practical reasons, such as selecting water as a solvent to handle wet raw materials. Typically, solvent liquefaction includes mixing biomass with a solvent in a slurry reactor at a temperature between about 300 and 700 ° F and a pressure in the range of about 1-3000 psi. The residence time in the slurry reactor can vary significantly, but generally ranges from about 1-60 minutes. Gases and vapors can be discharged from the top of the slurry reactor, while solids and a portion of the liquid products are drawn out of the reactor by a solid removal step. Then, the condensable vapor and liquid products are further processed, and often fractionated to recover a portion of the solvent for recycling to the front of the process.

[0017] It is often difficult to prevent the polymerization of reactive compounds found in bio-oils. Lignin-derived liquids can be particularly susceptible to polymerization. This leads to problems in the processing, storage, transportation and use of the produced bio-oils.

[0018] Some bio-oil streams may be moderately hydrogenated prior to and during more extensive or complete hydroprocessing to improve stability and partially mitigate undesirable polymerization reactions.

[0019] In order to be useful as a drop-in fuel blend, bio-oils need to be hydrotreated, primarily to deoxygenate the oil. However, hydroprocessing of bio-oils has many unresolved challenges. These include poor deoxygenation performance and high heat release. Diluting bio-oils in hydrocarbons to address these issues is not practical because bio-oils do not form homogeneous solutions in most hydrocarbons, including petroleum middle distillates.

[0020] Prior art describes the production of paraffinic fuels by lipid hydroprocessing, including co-hydroprocessing of lipids with petroleum fractions. Several publications report parameters defining the optimal conditions for co-hydroprocessing of straight-run diesel or gasoline with lipids. Jerzy Walendziewski et al. described the co-hydroprocessing of 10% and 20% rapeseed oil with straight-run diesel / light gas oil (Fuel Processing Technology 90, 2009, 686-691). In a more recent study, P. Dhar et al. 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 extensively describe the chemical process of converting lipids containing mainly C16 and C18 fatty acids into normal paraffins in the C15-C18 range and highlight that the low temperature properties of the treated diesel (i.e., cloud point, CFPP, pour point) deteriorate with increasing feed lipid content.

[0021] Publications, patents, and patent applications are cited throughout this disclosure. All references cited herein are incorporated by reference.

[0022] In a paper titled "Hydrotreating in the production of green diesel" (PTQ, Q2; 2010), Rasmus Egeberg and colleagues provide a case history of converting a straight-run light gas oil mild hydrocracker to a hydrotreater for coprocessing up to 30% crude tall diesel (FAME produced from tall oil) with straight-run middle distillates. The paper also describes a multi-bed diesel hydrotreater in which a bottom bed of dewaxing catalyst is used to hydrocrack / isomerize the straight-chain paraffinic product of lipid hydroprocessing, thereby improving the low-temperature properties of the coprocessed diesel.

[0023] In summary, the prior art teaches co-hydroprocessing of lipids and lipid derivatives with straight-run petroleum fractions. However, methods for advantageously co-hydroprocessing lipids with bio-oil fractions from pyrolysis / liquefaction of lignocellulosic biomass have not been described previously in the prior art. Therefore, there remains an unmet need to improve biofuel feedstock diversity and fuel properties. Summary of the invention

[0024] The embodiments of the invention described below are not intended to be exhaustive or to limit the invention to the precise forms disclosed in the following detailed description. Rather, the embodiments are selected and described so that others skilled in the art can appreciate and understand the principles and practices of the invention.

[0025] One aspect of the present invention relates to contacting a bio-oil derived from lignocellulosic biomass with lipids (or lipid derivatives, such as biodiesel, and biodiesel production and vegetable oil processing byproducts) to (1) recover higher carbon content bio-oil components, (2) improve the stability of the bio-oil, (3) improve its miscibility with hydrocarbons, and (4) upgrade the bio-oil through a hydroprocessing reactor. Depending on the pyrolysis process and the properties of the bio-oil, the contacting can be performed at different points or stages in the bio-oil production and refining process. Due to the presence of polycyclic, cycloparaffinic and aromatic hydrocarbons, the hydrotreated fuel fractions of the present invention have advantages over conventional paraffinic renewable diesel, renewable paraffinic kerosene and renewable gasoline / naphtha. For diesel fuel, such advantages include better solubility of lower quality (e.g., undistilled) biodiesel when producing a renewable fuel blend that includes 100% biodiesel. For gasoline or naphtha, advantages include, for example, better octane rating. For kerosene, advantages include the presence of aromatic compounds required in the specifications or standards for use as jet fuel, e.g., see ASTM DI 655 and D7566, and a depression of the freezing point. One aspect of the present invention involves co-hydroprocessing a bio-oil having an effective H / C ratio of 0.3-1.0 with a lipid having an effective H / C ratio of 1.5-2.0, thereby reducing the hydrogen consumption requirements and processing challenges of upgrading the bio-oil to a high quality hydrocarbon fuel characterized by a high H / C ratio.

[0026] In an exemplary embodiment of the present invention, a method for converting bio-oil derived from lignocellulosic biomass into fuel or fuel blends is described, and the method includes the following steps: first contacting the bio-oil with a lipid or lipid derivative to form an organic phase and an aqueous phase comprising phenolic compounds. Next, the organic phase is separated from the aqueous phase, and then the organic phase is hydrogenated and deoxygenated in a hydroprocessing reactor to produce hydrocarbon products, gas products and water, and then the hydroprocessing reactor hydrocarbon products are fractionated into fuel products comprising gasoline and kerosene / diesel.

[0027] In another exemplary embodiment of the present invention, a method for converting bio-oil derived from lignocellulosic biomass into hydrocarbon fuel or fuel blend is provided, and the method comprises the following steps: first, the bio-oil is combined with lipids to produce a combined feed and then the combined feed is introduced into a hydroprocessing reactor to produce a reactor effluent. Next, the reactor effluent is separated into hydrocarbons, gases and water streams, and then the hydrocarbons are fractionated into a gasoline fraction and a kerosene / diesel fraction. The combined feed has a lipid content between about 16 volume % and about 90 volume % and the kerosene / diesel fraction has less than 0.1 weight % oxygen.

[0028] In yet another exemplary embodiment of the invention, a hydrocarbon fuel or blend is described and includes bio-oil and lipids to produce a combined feed. A reactor effluent produced by subjecting the combined feed to a hydroprocessing reactor is separated into hydrocarbons, gases and a water stream. A gasoline fraction and a kerosene / diesel fraction, wherein the combined feed has a lipid content between about 16% and about 90% by volume and the kerosene / diesel fraction has less than 0.1% oxygen by weight.

[0029] Other features and advantages of the present invention will become apparent to those skilled in the art from the following detailed description. However, it should be understood that the detailed description of various embodiments and specific examples, although indicating preferred and other embodiments of the present invention, are provided in an illustrative and non-limiting manner. Without departing from the spirit of the present invention, many changes and modifications may be made within the scope of the present invention, and the present invention includes all such modifications. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] These and other objects and advantages of the present invention will be more fully understood and appreciated by referring to the following more detailed description of exemplary embodiments of the present invention in conjunction with the accompanying drawings, in which:

[0031] Figure 1 is a representation of the polymer building blocks of cellulosic lignin biomass;

[0032] Figure 2 is a block diagram of the process flow of an embodiment of the present invention;

[0033] Figure 3 It is a schematic diagram of the process flow of the present invention for alternative implementation scheme;

[0034] Figure 4 is a graph of HDO product TAN as a function of the amount of lipid in the bio-oil; and

[0035] Figure 5 is a graph of HDO liquid yield as a function of the amount of lipid in the bio-oil. DETAILED DESCRIPTION OF THE INVENTION

[0037] The apparatus and method disclosed herein are described in detail by way of example and with reference to the accompanying drawings. Unless otherwise specified, the same numbers in the figures represent references to the same, similar or corresponding elements in the entire figure. It should be understood that the disclosed and described examples, arrangements, configurations, parts, elements, apparatus, methods, materials, etc. can be modified, and they can be desired for specific applications. In the present disclosure, any determination of a specific shape, material, technology, arrangement, etc. is either related to the specific instance presented, or is merely a general description of such a shape, material, technology, arrangement, etc. Unless specifically specified as such, the determination of specific details or examples is not intended to be and should not be interpreted as mandatory or restrictive. The following discloses and describes the selected examples of the apparatus and method in detail with reference to the accompanying drawings.

[0038] As used herein, "about", "approximately" or "approximately" will represent up to plus or minus 10% of a particular term. Unless otherwise indicated herein or clearly contradictory to the context, the terms "one" and "an" and "the" and similar indicators used in the context of describing this element (especially in the context of the following claims) should be interpreted as covering the singular and plural. Unless otherwise indicated herein, the recording of the numerical range herein is only intended to be used as a shorthand expression for referring to each individual value falling within the range individually, and each individual value is incorporated into the specification as if it is recorded individually in this article. Unless otherwise indicated herein or clearly contradictory to the context, all methods described herein can be performed in any suitable order. Unless otherwise required to indicate, any and all examples or exemplary language (such as "for example") provided herein are used only to better illustrate the embodiment, rather than to impose restrictions on the scope of the claims. The language in the specification should not be interpreted as indicating that any unclaimed element is necessary.

[0039] As used herein, an "alkyl" group includes both straight-chain and branched-chain 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-chain alkyl groups include, but are not limited to, isopropyl, sec-butyl, tert-butyl, neopentyl, and isopentyl groups. It will be understood that the phrase "C i -C j "Alkyl" such as C1-C4 alkyl means an alkyl group having a carbon number falling within the range ij.

[0040] The term "aromatic compound" as used herein is synonymous with "aromate" and both mean 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 substances with alkyl groups and cycloalkyl groups. Therefore, aromatic compounds include but are not limited to benzene, azulene, heptane, phenylbenzene, indacene, fluorene, phenanthrene, triphenylene, pyrene, naphthalene, chrysene, anthracene, indene, dihydroindene, pentalene and naphthalene, as well as alkyl and cycloalkyl substituted variants of these compounds. In some embodiments, the aromatic substance contains 6 to 14 carbons in the ring portion of the group, and 6 to 12 or even 6 to 10 carbon atoms in other. The phrase includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., dihydroindene, tetrahydroanthracene, etc.).

[0041] As used herein, "oxygenate" or "oxygenated hydrocarbon" means a carbon-containing compound containing at least one covalent bond to oxygen. Examples of functional groups encompassed by the term include, but are not limited to, carboxylic acids / esters, carboxylates, anhydrides, aldehydes, esters, ethers, ketones, and alcohols. Oxygenates may also be aromatic compounds, cycloalkanes, and oxygen-containing variants of alkanes as described herein. Fatty acids or glycerides are naturally occurring carboxylic acids or esters that define lipids.

[0042] As used herein, the term "alkane" means a non-cyclic, branched or unbranched alkane. An unbranched alkane is a normal alkane; a branched alkane is an isoalkane. A "cycloalkane" is a cyclic, branched or unbranched alkane.

[0043] The term "alkane" as used herein means an alkane or cycloalkane as defined above as well as hydrocarbon chains having regions of either branched or unbranched alkanes.

[0044] As used herein, the term "olefin" means a non-cyclic, branched or unbranched chain olefin. As used herein, the term "olefinic" means a cyclic, branched or unbranched mono- or di-unsaturated (ie, one or two double bonds) hydrocarbon.

[0045] Hydroprocessing as used herein describes different types of catalytic reactions that occur in the presence of hydrogen without limitation. Examples of the most common hydroprocessing reactions include, but are not limited to, hydrogenation, hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrotreating (HT), hydrocarbon cracking (HC), aromatic saturation or hydrodearomatization (HDA), hydrodeoxygenation (HDO), decarboxylation (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 thermodynamic (i.e., no catalyst is required) to catalytic. In describing the primary functions of a particular hydroprocessing unit (e.g., an HDO reaction system), it should be understood that the HDO reaction is only one of the primary reactions that occur, and that other reactions may also occur.

[0046] Decarboxylation (DCO) is understood to mean the hydrogenation of organic molecules, which removes carboxyl groups from them to give CO 2 , and decarbonylation, which leads to the formation of CO 2 .

[0047] Pyrolysis is understood to mean the thermochemical decomposition of carbonaceous materials in the presence of little or no diatomic oxygen or diatomic hydrogen during the thermochemical reaction. The product fractions obtained by pyrolysis are referred to as pyrolysis products.

[0048] Hydrotreating (HT) includes removing elements from Group IIIa, Group Va, Group VIa and / or Group VIIa of the Periodic Table of the Elements from organic compounds. Hydrotreating may also include hydrodemetallization (HDM) reactions. Thus, hydrotreating includes 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 to produce water as a by-product; similarly, hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) describe the removal of specified elements, respectively, by hydrotreating. Because the primary heteroatom removed during hydrotreating of biogenic feedstocks is oxygen, the terms hydrodeoxygenation or HDO are used interchangeably with hydrotreating in this disclosure.

[0049] Hydrogenation comprises hydrogen addition to organic molecules without molecular cleavage into subunits. Hydrogen addition to carbon-carbon or carbon-oxygen double bonds to produce singly-bound bonds is two non-limiting examples of hydrogenation. Partial hydrogenation and selective hydrogenation are terms used to refer to the partially saturated hydrogenation reactions that cause unsaturated raw materials. For example, the vegetable oil with high percentage of polyunsaturated fatty acids (such as linoleic acid) can experience partial hydrogenation to provide a hydrotreated product, wherein the polyunsaturated fatty acids are converted into monounsaturated fatty acids (such as oleic acid) and do not increase the percentage of undesirable saturated fatty acids (such as stearic acid). Although hydrogenation is different from hydrotreating, hydroisomerization and hydrocracking, hydrogenation can occur in these other reactions.

[0050] Hydrocracking (HC) is understood to mean the breaking of the carbon-carbon bonds of a molecule in the presence of hydrogen to form at least two molecules. Such a reaction is typically followed by a subsequent hydrogenation of the resulting double bonds.

[0051] Hydroisomerization (HI) is defined as the skeletal rearrangement of carbon-carbon bonds in the presence of hydrogen to form isomers. Hydrocracking is a competing reaction for most HI catalyzed reactions, and it is understood that the HC reaction pathway is included as a secondary reaction 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.

[0052] It will be understood that if a composition is referred to as comprising "C i -C j Hydrocarbons", such as C7-C 12 By normal alkane, it is meant that the composition comprises one or more alkanes having a carbon number falling within the ij range.

[0053] "Middle distillates" generally refers to the fraction of petroleum in the range of about 200°F (93°C) to about 800°F (427°C). This includes kerosene (about 200-520°F), diesel and light gasoline (about 400 to 650°F), and heavy gasoline (about 610-800°F).

[0054] As used herein, "lipid" refers to fats, oils, and greases and their fractions. Lipids mainly include C8-C 24 The lipids may be saturated and unsaturated fatty acids in a wide range, wherein the fatty acids may be in the form of glycerides (i.e., mono-, di- and tri-glycerides) or as free fatty acids (FFA). The lipids may also include minor components, such as fats or oils, such as sterols, sterol esters, sterol glucosides, terpenes, tocopherols, vitamins, proteins, waxes, etc.

[0055] The hydrogen-to-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 combination of several compounds, or a complex combination of many compounds. For hydrocarbons containing heteroatoms (including oxygen-containing compounds), the effective H / C ratio is H / C eff It can be calculated according to its empirical formula or its CHNOS molar composition according to Equation 1 shown below.

[0056] H / C eff = (H-2O-3N-2S) / C

[0057] For hydrocarbons that do not contain N, O, and S heteroatoms, the above equation simplifies to H / C. However, for oxygenated compounds such as lipids (where fatty acids can be considered as straight-chain hydrocarbons terminating in a carboxyl group), Equation 1 expresses the H / C ratio on an oxygen-free basis by taking into account the chemically dehydrated form of the oxygenated compound (where each oxygen atom is removed by two hydrogen atoms of the oxygenated hydrocarbon).

[0058] The empirical formula of a hydrocarbon or mixture of hydrocarbons and oxygenates can be determined mathematically from knowledge of the blend composition, or analytically by various limit analysis techniques or by ASTM D5291 analysis. In either case, knowing the C, H, N, O, and S values ​​of the complex composition, H / C eff The value can be calculated according to Equation 1.

[0059] It should be understood that the "volume percent" or "volume %" of a component in a composition or the volume ratio of different components in a composition is determined based on the initial volume of each individual component at room temperature (about 23°C) rather than the final volume of the combined components.

[0060] This technology

[0061] On the one hand, a method for producing high H / C ratio hydrocarbon fuel from the lignocellulose bio-oil of low H / C ratio is provided.The increase of H / C ratio is realized by co-processing bio-oil with lipid.Table I and Table II provide the typical effective H / C ratio of lipid and lignocellulose bio-oil respectively.As observed from these tables, lipid typically has the effective H / C ratio in the scope of 1.5 to 1.7, and lignocellulose bio-oil has 1 or less, typically in the scope of 0.2 to 1.0 and often in the scope of 0.0 to 1.0 effective H / C ratio.

[0062] Table I. Common lipid raw materials and corresponding hydrogen-to-carbon ratios

[0063] *Based on published fatty acid profiles

[0064] Table II. Typical components of lignocellulosic bio-oil

[0065] The method comprises the steps of first contacting bio-oil (e.g., pyrolysis product) with lipids and subjecting the mixed stream to temperature, hydrogen pressure, and catalyst to produce hydrocarbons having an effective H / C ratio higher than that of the bio-oil. In additional embodiments, the bio-oil and lipids are diluted with a hydrocarbon diluent that is substantially free of olefins.

[0066] Exemplary bio-oil feedstocks include, but are not limited to, bio-oil and bio-oil fractions produced by rapid 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, separated solid waste, food waste, sewage sludge, fertilizers, forestry residues (e.g., tree thinnings, sawdust, wood chips, etc.), renewable fuel residues, used filter media, pulp and paper residues (e.g., black liquor), agricultural residues (e.g., corn stalks, bean stalks, bagasse, etc.), herbaceous energy crops (e.g., switchgrass, miscanthus, 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.

[0067] Exemplary lipid raw materials include but are not limited to animal fat, animal oil, microbial oil, vegetable fat, vegetable oil, vegetable fat, vegetable oil, grease or any two or more mixtures thereof.Plant and / or vegetable oil and / or microbial oil include but are not limited to corn oil, distiller corn oil, inedible corn oil, babassu oil, golden fruit acid oil, soybean oil, rapeseed oil (canola oil), coconut oil, rapeseed oil, tall oil, tall oil fatty acid, palm oil, palm oil fatty acid distillate, palm sludge oil, jatropha oil, palm kernel oil, green pepper oil, sunflower oil, castor oil, camelina oil, archaeal oil, bacterial oil, fungal oil, protozoan oil, algae oil, algae oil, oil from halophilic bacteria, and any two or more mixtures thereof.According to pretreated level and residual phosphorus and metal content, these can be divided into rough, degumming and RBD (refining, bleaching and deodorizing) grade.But any in these grades can 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, flotation tallow, bleachable fine tallow, lard, industrial lard, selected white grease, poultry fat, poultry oil, fish fat, fish oil, and any two or more mixtures thereof. Grease may include but is not limited to yellow grease, brown grease, discarded vegetable oil, restaurant grease, from municipal such as oil trap (trap) grease of water treatment facilities and waste oil from industrial packaged food operations, and any two or more mixtures thereof. Depending on the level of pretreatment, such biorenewable lipid raw materials may contain phosphorus between about 1 wppm and about 800 wppm and total metals (mainly sodium, potassium, magnesium, calcium, iron and copper) between about 1 wppm and about 400 wppm. Lipid may also contain up to 100 wt % free fatty acids. The lipids can include 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 range including and / or between any two of these values ​​or other combinations of these values.

[0068] Thus, the lipid feedstock of any embodiment herein can include corn oil, non-edible corn oil, distiller's corn oil, babassu oil, arnica oil, soybean oil, rapeseed oil, coconut oil, rapeseed oil, tall oil, tall oil fatty acids, palm oil, palm oil fatty acid distillate, palm sludge oil, jatropha oil, palm kernel oil, green pepper oil, sunflower oil, castor oil, camelina oil, archaea oil, bacterial oil, fungal oil, protozoa oil, algae oil, algae oil, oil from halophiles, rendered fat, inedible tallow, edible tallow, industrial tallow, flotation tallow, bleachable fine tallow, lard, industrial lard, selected white grease, poultry fat, poultry oil, fish fat, fish oil, frying oil, yellow grease, brown grease, waste vegetable oil, restaurant grease, oil trap grease from municipalities such as water treatment facilities, and waste oil from industrial packaged food operations, or a mixture of any two or more thereof. In embodiments, derivatives of such lipids (e.g., alkyl esters formed by transesterification or esterification of lipids with alcohols) may be used in place of lipids. Examples include fatty acid methyl esters (FAME), the most common type of biodiesel. Other derivatives include free fatty acids (FFA) formed by lipid hydrolysis, or FAME produced by esterifying FFA with methanol.

[0069] Co-hydrogenation treatment implementation plan

[0070] The amount of lipid on a lipid plus bio-oil basis is between about 16% and about 90% by volume. The concentration of lipid plus bio-oil base can be about 18%, about 20%, about 22%, about 24%, about 26%, about 28%, about 30%, about 32%, about 34%, about 36%, about 38%, about 40%, 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 72%, about 74%, about 76%, about 78%, about 80%, about 82%, about 88%, or any range including and / or between any two of these values ​​or a combination of these values.

[0071] The volume ratio of lipid plus bio-oil to optional diluent is between 1: 1 and 1: 9. The ratio of lipid plus bio-oil to diluent 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 a combination of these values.

[0072] In any embodiment herein, lipid and bio-oil feedstock hydroprocessing is combined hydrotreater feed and optionally subsequently hydrocracking and / or hydroisomerization.The effective H / C ratio of the combined feed of lipid and bio-oil 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 includes and / or in these values ​​any scope between any two.For example, the effective H / C ratio of the combined feed of lipid and bio-oil is between 1.55 and 1.85.

[0073] In the present technology, the combined feed is hydrotreated in the presence of hydrogen in the presence of a persulfided form of a hydrogenation metal of Group VIB and Group VIII of the Periodic Table of the Elements. 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 typically purchased as metal oxides and sulfurized during startup. Hydrotreatment is carried out at a temperature falling within the WABT range of about 480°F (250°C) to about 700°F (370°C) and a pressure of about 1000 psig (69 barg) to about 4,000 psig (275 barg). WABT or weighted average bed temperature is commonly used in fixed bed adiabatic reactors to represent the "average" temperature of the reactor, which describes the nonlinear temperature distribution between the reactor inlet and outlet.

[0074]

[0075] In the above equation, T i 进 and T i 出 are the temperatures at the inlet and outlet of catalyst bed i, respectively. As shown, the WABT for a reactor system with N different catalyst beds can be calculated using the WABT for each bed (WABT i ) and the weight of catalyst in each bed (W ci The preferred hydrotreater WABT and pressure range of the present technology is 550-690°F and 1,000-3,000 psig.

[0076] Hydrodeoxygenation of pyrolysis bio-oils typically requires significantly higher hydrotreater temperatures, with WABT values ​​of about 700°F or higher. This is primarily due to the presence of more refractory oxygen compounds, such as phenol and guaiacol. Operating at such high temperatures results in an increase in the aromatic content of the product. The increase in aromatics is due to the hydrogenation-dehydrogenation equilibrium, which favors hydrogenation at lower temperatures (less than about 690°F) and dehydrogenation (higher aromatics) at higher temperatures (greater than about 690°F). Higher aromatic content accounts for a lower cetane number of the diesel product and an increased catalyst carbon accumulation rate. In the present technology, surprisingly lower hydrotreater temperatures are required to achieve deoxygenation. Due to the lower temperatures, more complete aromatic saturation is achieved.

[0077] According to any embodiment of the present invention, the kerosene / diesel fraction (that is, the hydrocarbon product in kerosene and / or diesel boiling range, and abbreviated as kerosene / diesel) of the product of lipid and bio-oil co-hydroprocessing has an oxygen content less than about 0.1 % by weight. Kerosene / diesel fraction can have an oxygen content of about 0.01 % by weight, about 0.02 % by weight, about 0.03 % by weight, about 0.04 % by weight, about 0.05 % by weight, about 0.06 % by weight, about 0.07 % by weight, about 0.08 % by weight, about 0.09 % by weight, about 0.1 % by weight, or include and / or in these values ​​any two between or lower than any scope of the combination of any or these values ​​in these values. Such low oxygen value can be detected by suitable analytical techniques, including but not limited to fast neutron activation analysis or instrument neutron activation analysis.

[0078] In any embodiments herein, the kerosene / diesel fraction of the product of co-hydroprocessing of lipids and bio-oils according to the present invention has a cetane number greater than about 40. The kerosene / 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 of these values ​​or a combination of these values.

[0079] The kerosene / diesel fraction of the product of co-hydroprocessing of lipids and bio-oils according to the present invention typically has 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 of these values ​​or a combination of these values.

[0080] The kerosene / diesel fraction of the product of co-hydroprocessing of lipids and bio-oils according to any embodiment of the present invention may include a cloud point from about 20° C. to about -50° C. The cloud point of the composition may be about 18° C., about 14° C., about 10° C., about 6° C., about 2° C., 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 of these values ​​or a combination of these values.

[0081] Bio-oil extraction by lipids followed by hydrotreatment of the extract containing solution

[0082] Figure 2 The block flow diagram in provides an embodiment of the present invention and is used to describe the present technology. Figure 2 , lignocellulosic biomass 101 is added to converter 110, to be converted into bio-oil, bio-based gas and charcoal.Biomass 101 can be agricultural residues (such as corn stalks), forestry residues (such as wood chips, tree thinning, sawdust, etc.), herbaceous plants (such as switchgrass) or woody plants (such as hybrid poplars).Biomass 101 is preferably dried and reduced in size to maximize the surface and volume ratio of heat transfer and mass transfer in the conversion process in converter 110.Converter can be intermittent or continuous.Continuous converter includes fluidized bed fast pyrolysis reactor, circulating fluidized bed reactor, spiral reactor, ablation reactor, rotary kiln reactor, rotating cone reactor, entrained flow reactor, free fall reactor and slurry liquefaction reactor as described above.The biomass barrel 101 subjected to slow pyrolysis is an example of an intermittent converter.Converter temperature and pressure are typically in the range of 350-1000 ° F and -10-3000 psig respectively.

[0083] Steam 102 and charcoal 103 leave the converter 110. Charcoal can be used to provide fuel for the endothermic biomass conversion reactor 110, or as a byproduct supply (for example, for soil improvement). In an embodiment of the present technology, steam 102 contacts lipid feed 104 in contactor 120. In addition to conversion products above its boiling point, steam 102 also contains droplets of lignin-derived oligomers, which exist as aerosols and are present in steam 102 by entrainment. The bio-oil vapor in the steam stream 102 condenses when contacting with the cold lipid stream 104, and the cold lipid stream enters the contactor 120 at a temperature in the range of about 60-300°F. In an embodiment, the steam stream 102 is precooled from the converter temperature to a temperature in the range of about 250-500°F before entering the contactor 120. Various process coolers known to those skilled in the art can be used for this hot steam precooling service, including fin fan air coolers and shell and tube exchangers. The shell and tube precooler can be heat integrated with the process stream that requires heating (e.g., a reboiler in the fractionation unit 150 described later herein) using an appropriate heat transfer fluid. In embodiments, the vapor stream 102 can also be subjected to an electrostatic precipitator or other aerosol collection method known to those skilled in the art to impinge on aerosols entrained in the stream 102.

[0084] Lipids 104 may be vegetable oils (e.g., soybean oil, rapeseed oil, corn oil, etc.), animal fats (e.g., tallow, lard, poultry oil, etc.), oils or greases from food processing or production operations (e.g., used cooking oil, yellow grease, brown grease, etc.), or any combination or portion 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) may be used as lipids 104. In embodiments, lipids 104 may also include water-soluble components, such as water or glycerol, which account for less than 20% by weight of lipids 104. In embodiments, the water-soluble components present in lipids 104 are byproducts of biodiesel production and may contain small amounts of impurities, such as alcohols, alkali metal alkoxides, alkali metal hydroxides, alkali metal chlorides, alkali metal citrates, alkali metal sulfates, enzymes, and other compounds found in biodiesel production known to those skilled in the art.

[0085] Contactor 120 is typically operated at a pressure between atmospheric pressure and about 600 psig in the range of about 100-300 ° F. The contactor can be continuous or batchwise. Examples include an absorption column (wherein vapor 102 rises through a packed column or tray column, where it contacts with a downwardly flowing lipid 104 countercurrently), an extraction column (wherein condensed bio-oil contacts with lipid countercurrently) or a mixer-settler (wherein streams 102 and 104 are mixed by stirring before phase separation without stirring). In all cases, the mass ratio of stream 104 to stream 102 varies between about 20:1 and 0.5:1.

[0086] A portion of stream 102 dissolves in the lipids upon contact, thereby providing three contactor 120 outlet streams: (1) an aqueous liquid phase 105, (2) an organic liquid phase 106, and (3) a gas phase 116. The aqueous liquid phase 105 contains primarily water, C2-C4 oxygenates, and sugars. In embodiments where stream 104 contains water-soluble components, the aqueous phase 105 also contains the water-soluble components introduced into stream 104. The organic liquid phase 106 contains primarily lipids, with 0.1-10% phenolic compounds and lignin-derived oligomers extracted from bio-oil (i.e., from the condensed stream 102). The gas phase 116 includes CO, CO2, H2, C1-C2 non-condensable hydrocarbons and oxygenates, as well as any other process gases added to the converter 110. Stream 116 can be used as fuel gas for the plant. For CO and H2 concentrations above 10 mol%, stream 116 can be used as synthesis gas for the production of methanol, oxo alcohols or Fischer-Tropsch hydrocarbons.

[0087] In various embodiments, aqueous phase 105 is directed to recover acetic acid, acetal, glycolaldehyde, and other chemicals from the aqueous phase. Depending on the chemical purity sought, various separation methods known to those skilled in the art may be employed, including distillation, membrane separation, and mole-sieve adsorption.

[0088] The organic liquid phase 106 includes lipids and phenolic bio-oil compounds and has an effective H / C ratio 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 a combination of these values. For example, the effective H / C ratio of the combined feed of lipids and bio-oil is between about 1.55 and 1.85.

[0089] The organic liquid phase 106 is then directed to a hydroprocessing reactor 130. The organic liquid phase has an effective H / C ratio of about 1.55 and 1.85, wherein the organic liquid is combined with a hydrogen-rich gas 107 and heated to a temperature between 450 and 700°F at a pressure between 1,000 and 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 hydroprocessing reactor 130. In a preferred embodiment, the temperature and pressure ranges are about 500-650°F (WABT) and about 1,600-3,200 psig, respectively. The hydroprocessing reactor is preferably a fixed bed reactor containing a catalyst that promotes hydrogenation and deoxygenation reactions. Typical catalysts are NiMo, CoMo, and NiW on a γ-alumina support. Preferred catalysts are sulfided molybdenum and tungsten, with nickel as a promoter. Preferred catalysts have Ni:Mo and Ni:W ratios between 1:3 and 1:5. Preferred catalysts have an average pore size of 180 angstroms or greater. Preferred catalysts (NiMo or NiW) and hydrogen pressures (>1600 psig) ensure that planar phenol molecules that are difficult to hydrodeoxygenate are first hydrogenated to cyclohexanol and / or cyclohexanone (which have more flexible "boat" and "chair" conformations) to better access the catalyst's hydrodeoxygenation sites.

[0090] In embodiments, the hydroprocessing reactor 130 also contains a catalyst that promotes hydrocracking and isomerization reactions. Typical hydrocracking / isomerization catalysts have amorphous or crystalline silica-alumina carriers. Preferred crystalline carriers contain zeolites. Hydrogen-active metals for hydrocracking / isomerization include precious metals and alkali metals, such as platinum, platinum / palladium, and nickel / tungsten. Typically, if H2S is expected to be present in the hydrogen-rich gas 107, NiW catalysts are selected), while Pt and Pt / Pd catalysts are specified for clean hydrogen-rich gases (i.e., when there is little or no H2S or NH3 in the gas). As appreciated by those skilled in the art, the product of the first hydroprocessing stage using sulfided NiMo or NiW catalysts needs to be stripped of H2S, H2O, and NH3 using steam, nitrogen, hydrogen, or another light gas before adding it to the second hydroprocessing stage containing Pt or Pt / Pd catalysts.

[0091] 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 can be a petroleum middle distillate or a partially recycled product of the hydroprocessing reactor (e.g., stream 117 described in more detail later herein).

[0092] The reactor effluent 108 is then cooled and separated in a 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 gaseous byproducts of the hydroprocessing reaction (including CO, CO2, H2S, NH3, and C1-C4 hydrocarbons). In an embodiment, a portion of the gas is treated by a membrane to separate C3+ hydrocarbons for recovery in a fractionation unit 150 (described later herein). In an embodiment, the gas product 109 is treated (e.g., by an amine scrubber) and combined with make-up hydrogen to provide a hydrogen-rich gas 107.

[0093] The hydrocarbon product stream 117 can be directed to a fractionation unit 150 where the products are fractionated according to boiling range. The gas fraction 112 includes butanes and lighter hydrocarbons used as "bio-based LPG" for transportation, heating and cooking. The gasoline fraction 113 in the C5-300°F boiling range includes aromatic and cycloalkanes formed by deoxygenation of monophenolic compounds from the bio-oil.

[0094] The kerosene / diesel fraction 114 in the boiling range of 300-650°F comprises C10-C24 hydrocarbons. In addition to alkanes formed from lipid fatty acid chains, the kerosene / diesel fraction also comprises cycloalkanes and aromatic compounds from lignin-derived phenolic dimers / oligomers and hydrocracking products therefrom. The kerosene / diesel fraction has an oxygen content of less than 1 wt. % and is very suitable for use in compression ignition engines either in pure form or in blends with petroleum and / or biodiesel.

[0095] Unlike blends with 100% lipid-based renewable diesel, the kerosene or diesel products of the present technology can solubilize biodiesel impurities that have low solubility in 100% lipid-based renewable diesel when blended with greater than 7% by volume biodiesel. In an embodiment, the jet fuel distillate is separated from the kerosene / diesel fraction 114 for use in aviation turbine fuel.

[0096] The bottoms fraction 115 comprises 650 F+ boiling range material in which most of the unconverted lignin derived oligomers are concentrated. These may be recycled back to the hydrotreating reactor 130 or directed to a different hydrocracking reaction (not shown) for conversion into lighter hydrocarbon products for combination with the LPG, gasoline, and kerosene / diesel products described above.

[0097] Liquefaction of biomass assisted by lipids and / or lipid derivatives

[0098] Figure 3 The block flow diagram in provides an embodiment of the present invention and is used to describe the present technology. Figure 3, lignocellulosic biomass 201 is added to converter 210, to be converted into bio-oil, bio-based gas and charcoal.Biomass 201 can be agricultural residues (such as corn stalks), forestry residues (such as wood chips, tree thinning, sawdust, etc.), herbaceous plants (such as switchgrass), woody plants (such as hybrid poplar) or two or more mixtures.In embodiments, biomass 201 can be composed of fractionated biomass, so that fractionated biomass is rich in lignin, cellulose or holocellulose.In preferred embodiments, biomass 201 can include the lignin extracted, such as lignin produced by Kraft method, organic solvent method, ammonia fiber explosion method, enzyme hydrolysis method and other such lignin extraction methods known to those skilled in the art.Biomass 201 is preferably dried and reduced in size, so that the surface and volume ratio of heat transfer and mass transfer in the conversion process in converter 210 is maximized.Biomass 201 can be fed to converter 210 by lock hopper, rotary airlock, extruder, pneumatic conveyor or other solid conveying devices known to those skilled in the art.

[0099] Solvent 202 is also pumped into converter 210 to promote thermal decomposition of biomass. Solvent 202 can be co-fed with biomass 201 as slurry or pumped into converter 210 as a separate stream. In the embodiment where solvent 202 and biomass 201 are pre-mixed and co-added to converter 210, the mixture can be added to converter 210 by using a centrifugal pump, a slurry pump, a slurry pump, an immersion pump, an extruder and other slurry conveying devices 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 as a solvent mainly according to its chemical properties, and some practical limitations, such as cost, ease of recovery and volatility are considered. Solvent 202 plays a key role in the dissolution of raw material 201 and desired products, making it easier to recover products that are easily dissolved in solvents and reducing participation in undesirable side reactions. Solvent also directly affects the decomposition of raw materials, so that for completely soluble solvents, some products can be produced in a higher yield than incompletely soluble solvents. In embodiments, solvent 202 may also provide hydrogen to the decomposition products from biomass 201 such that the decomposition products have a higher effective H / C ratio.

[0100] In a preferred embodiment, solvent 202 is a lipid such as soybean oil or used cooking oil, or a lipid derivative such as an alkyl ester produced by transesterification or esterification of lipids (i.e., biodiesel) or an alkane produced by hydrotreating lipids (i.e., renewable paraffinic kerosene, renewable diesel, etc.).

[0101] Converter 210 can be batch or continuous. Continuous converters include slurry liquefaction reactors, plug flow reactors, and countercurrent flow reactors. A stirred drum of biomass 201 mixed with solvent 202 and heated before removing contents is an example batch converter. Converter temperature and pressure are usually in the range of 350-1000 ° F and -10-3000 psig, respectively, wherein pressure is enough to maintain solvent 202 in a subcritical liquid phase or a supercritical liquid phase.

[0102] Steam 211 and heavy phase 212 leave converter 210. Steam 211 contains conversion products above its boiling point and non-condensable gases added to converter 210 for processing, such as nitrogen, natural gas, or compressed and recycled product gases from the present technology. Steam 211 is directed to a separator 220 for recovering condensable products. Separator 220 typically operates at a reduced temperature (e.g., 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 in the range of about 60-300°F before entering separator 220. Various process coolers known to those skilled in the art can be used for this hot vapor precooling service, including fin fan air coolers and shell and tube exchangers. Shell and tube precoolers can be integrated with the heat of the process stream that needs to be heated using an appropriate heat transfer fluid (e.g., a reboiler in the fractionation unit 240 described later herein). In an embodiment, the vapor stream 211 may also be subjected to an electrostatic precipitator or other aerosol collection methods known to those skilled in the art to impact aerosols entrained in the stream 211. The gas phase 222 includes CO, CO2, H2, C1-C2 non-condensable hydrocarbons and oxygenates, as well as any other process gas added to the converter 210. The stream 222 may be used as a fuel gas for the plant. For CO and H2 concentrations above 10 mol%, the stream 222 may be used as a synthesis gas for the production of methanol, oxo alcohols or Fischer-Tropsch hydrocarbons. In some embodiments, as previously described, the stream 222 may be compressed and recycled to the converter 210.

[0103] Condensate stream 221 contains decomposition products that are below their boiling points at the operating conditions of separator 220. In embodiments, stream 221 typically contains water, light oxygenates such as acetic acid, formic acid, propionic acid, formaldehyde, acetal, acetaldehyde, glycolaldehyde, and methanol, and any entrained aerosols from converter 210.

[0104] In embodiments, condensate 221 is directed to recover acetic acid, formic acid, propionic acid, acetal, glycolaldehyde and other chemicals from the aqueous phase. Depending on the chemical purity sought, various separation methods known to those skilled in the art may be employed, including distillation, membrane separation and molecular sieve adsorption.

[0105] The heavy phase 212 containing conversion products below its boiling point, solvent, unreacted raw materials and charcoal is directed to the separator 230 by pumping, gravity or pressure difference between the converter 210 and the separator 230. The separator 230 removes solid residue 232, typically unreacted raw materials and charcoal, heavy liquid 231 including high boiling point liquid products and solvent. The solid residue 232 can be used to provide fuel for the endothermic biomass conversion reactor 210, or as a by-product supply (for example, for soil improvement). The separator 230 can 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 blade filter or other solid-liquid separation devices known to those skilled in the art. In a preferred embodiment, the separator 230 is a settling tank, followed by a filtering device such as listed above. In an embodiment, a filter medium such as diatomaceous earth is used to enhance the removal of solid residue 232 from the heavy liquid 231. Separator 230 can be operated at a temperature lower than that of converter 210, but not at a temperature lower than about 200°F, to maintain the heavy phase 212 with a sufficiently low viscosity to facilitate removal of solid residue 232. In an embodiment, separator 230 is operated at a temperature in the range of 200-400°F. In an embodiment, a solid removal additive 235, such as an alcohol or a hydrocarbon, can be added to separator 230 to assist in solid removal by further reducing the viscosity of heavy phase 212. In an embodiment, solid removal additive 235 is a hydrocarbon produced by hydroprocessing of lipids and pyrolysis products. In an embodiment, solid removal additive 235 is a renewable paraffinic naphtha produced by hydroprocessing of lipids and pyrolysis products. Solid removal additive 235 leaves separator 230 primarily with heavy liquid 231.

[0106] The heavy liquid 231 is directed to contactor 240 where it contacts a wash stream 245. Contactor 240 is typically operated at about 100-300°F and at a pressure between about 1 and 500 psig. The contactor may be continuous or batch. Examples include an absorption column, an extraction column, a contact centrifuge, or a mixer-settler. In all cases, the mass ratio of stream 231 to stream 245 varies between about 20:1 and 1:1.

[0107] A portion of stream 231 dissolves in wash stream 245 upon contact, thereby providing two contactor 240 outlet streams: aqueous liquid phase 242 and organic liquid phase 241. Wash liquid 245 is a polar liquid suitable for washing away high boiling polar products, primarily from the decomposition of polysaccharides such as levoglucosan, levoglucosone, cellobiosaccharides, maltosaccharides, furfural, 5-methylfurfural, dimethoxytetrahydrofuran and other sugars and dehydrated sugars. In embodiments, wash liquid 245 is a liquid having a dielectric constant greater than about 10.0. In embodiments, wash liquid 245 is primarily water. In embodiments, wash liquid 245 is primarily glycerol. In embodiments, wash liquid 245 is a mixture of water and glycerol. In an embodiment, the wash liquor 245 is a byproduct of biodiesel production containing primarily water and glycerol, and may contain small amounts of impurities such as alcohols, alkali metal alkoxides, alkali metal hydroxides, alkali metal chlorides, alkali metal citrates, alkali metal sulfates, enzymes, and other compounds found in biodiesel production known to those skilled in the art. In an embodiment, the condensate 221 is used to constitute a portion or all of the wash liquor 245.

[0108] In embodiments, aqueous phase 242 can be combined with condensate 221 to form a blended composition containing aqueous phase 242 for subsequent processing. In embodiments, aqueous phase 242 is directed to the recovery of oligomeric and monosaccharides and anhydrosugars. Depending on the chemical purity sought, various separation methods known to those skilled in the art can be used, including distillation, membrane separation, and molecular sieve adsorption. In embodiments, aqueous phase 242 is suitable for anaerobic or aerobic digestion to produce biogas. In embodiments, aqueous phase 242 is suitable for fermentation to produce bioalcohol.

[0109] The organic aqueous phase 241 contains primarily the solvent 201 and the solid removal additive 235 together with phenolic compounds and soluble lignin-derived oligomers 201 produced from the biomass.

[0110] The organic liquid phase 241 comprising solvent, solid removal additive and phenolic bio-oil compounds has an effective H / C ratio 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 feed of lipids and bio-oil is between 1.55 and 1.85.

[0111] The organic liquid phase 241 is then directed to a hydroprocessing reactor 250, where the organic liquid is combined with a hydrogen-rich gas 255 and heated to a temperature between about 450 and 700°F at a pressure between 1,000 and 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 prior to introduction into the hydroprocessing reactor 250. In a preferred embodiment, the temperature and pressure ranges are about 500-650°F (WABT) and about 1,600-3,200 psig, respectively. The hydroprocessing reactor is preferably a fixed bed reactor containing a catalyst that promotes hydrogenation and deoxygenation reactions. Typical catalysts are NiMo, CoMo, and NiW on a γ-alumina support. Preferred catalysts are sulfided molybdenum and tungsten, with nickel as a promoter. Preferred catalysts have Ni:Mo and Ni:W ratios between 1:3 and 1:5. Preferred catalysts have an average pore size of 180 angstroms or greater. The preferred catalyst (NiMo or NiW) and hydrogen pressure (>1600 psig) ensure that the planar phenol molecules that are difficult to hydrodeoxygenate are first hydrogenated to cyclohexanol and / or cyclohexanone (which have more flexible "boat" and "chair" conformations) for better access to the hydrodeoxygenation sites of the catalyst.

[0112] In embodiments, the hydroprocessing reactor 250 also contains a catalyst that promotes hydrocracking and isomerization reactions. Typical hydrocracking / isomerization catalysts have amorphous or crystalline silica-alumina carriers. Preferred crystalline carriers contain zeolites. Hydrogen-active metals for hydrocracking / isomerization include precious metals and alkali metals, such as platinum, platinum / palladium, and nickel / tungsten. Typically, if H2S is expected to be present in the hydrogen-rich gas 255, NiW catalysts are selected), while Pt and Pt / Pd catalysts are specified for clean hydrogen-rich gas (i.e., when there is little or no H2S or NH3 in the gas). As appreciated by those skilled in the art, the product of the first hydroprocessing stage using sulfided NiMo or NiW catalysts needs to be stripped of H2S, H2O, and NH3 using steam, nitrogen, hydrogen, or another light gas before adding it to the second hydroprocessing stage containing Pt or Pt / Pd catalysts.

[0113] When the 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 can be a petroleum middle distillate or a partially recycled product of the hydroprocessing reactor (e.g., stream 261 described in more detail later herein).

[0114] The reactor effluent 251 is then cooled and separated into a gas product stream 263, a hydrocarbon product stream 261, and a water stream 262 by a separator 260. In an embodiment, the water stream 262 may be recycled back to contain all or a portion of the scrubbing liquid 245. The product gas stream is primarily unreacted hydrogen and gas phase byproducts of the hydroprocessing reaction (including CO, CO2, H2S, NH3, and C1-C4 hydrocarbons). In an embodiment, a portion of the gas is treated by a membrane to separate C3+ hydrocarbons for recovery in a fractionation unit 270 (described later herein). In an embodiment, the gas product 263 is treated (e.g., by an amine scrubber) and combined with make-up hydrogen to provide a hydrogen-rich gas 255.

[0115] The hydrocarbon product feed stream 261 can be directed to a fractionation unit 270 where the products are fractionated according to boiling range. The gas fraction 271 includes butane and lighter hydrocarbons used as "bio-based LPG" for transportation, heating and cooking. The gasoline fraction 272 in the C5-300F boiling range includes aromatic hydrocarbons and cycloalkanes formed by deoxygenation of monophenolic compounds from bio-oil. The gasoline fraction 272 can be recycled back to include all or a portion of the solid removal additive 235.

[0116] The kerosene / diesel fraction 273 in the boiling range of 300-650F comprises C10-C24 hydrocarbons. In addition to alkanes formed from lipid fatty acid chains, the kerosene / diesel fraction also comprises cycloalkanes and aromatic compounds from lignin-derived phenolic dimers / oligomers and hydrocracking products therefrom. The kerosene / diesel fraction has an oxygen content of less than 1 wt. % and is very suitable for use in compression ignition engines as a pure fuel or in a blend with petroleum and / or biodiesel.

[0117] Unlike blends with 100% lipid-based renewable diesel, the kerosene / diesel products of the present technology can be blended with more than 7% biodiesel having impurities that have low solubility in 100% lipid-based renewable diesel. In an embodiment, the jet fuel distillate is separated from the kerosene / diesel fraction 273 for use in aviation turbine fuel.

[0118] The bottoms fraction 274 includes 650 F+ boiling range material in which most of the unconverted lignin derived oligomers are concentrated. These can be recycled back to the hydrotreating reactor 250 or directed to a different hydrocracking reactor (not shown) for conversion into lighter hydrocarbon products for combination with LPG, gasoline, and the kerosene / diesel products described above. The bottoms fraction 274 can also be recycled back to contain all or a portion of the solvent 202, or it can be sold as a residual fuel oil product containing renewable content.

[0119]

[0046] The present technology thus generally described will be more readily understood by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present technology. Example

[0120] The following examples describe three experiments that were conducted to determine the feasibility and utility of the present invention.

[0121] All three experiments were conducted in a 1 liter autoclave bottom discharge reactor equipped with a Robinson-Mahoney fixed catalyst basket. The catalyst basket was loaded with a commercially available NiMo fixed bed hydroprocessing catalyst (sulfided prior to loading). The annulus of the catalyst basket contained a multi-impeller agitator, a submerged sparge tube at the bottom of the catalyst basket for hydrogen addition, an internal sample port at the bottom of the catalyst basket, a liquid feed fill tube at the top of the catalyst basket, a thermocouple well, and a gas outlet. The gas outlet was connected to a water-cooled heat exchanger for condensing components with a dew point greater than ~100°F.

[0122] The present invention is illustrated using pyrolysis oil produced by autothermal pyrolysis of softwood. Pyrolysis oil is collected in four fractions. Stage fraction 1 and stage fraction 2, referred to herein as "heavy tail fraction" or "bio-oil", are combined in a mass ratio approximately the same as their mass ratio produced by the pyrolysis experiment; the bio-oil is used as the reactive feed for the experiment. Heavy tail fractions are used because they contain most of the carbohydrate dehydration products, phenolic oligomers and phenolic monomers in the appropriate carbon number range, producing naphtha and distillate range hydrocarbons. Further details of the pyrolysis process for producing bio-oil can be found elsewhere (Sean A. Rollag, 2020).

[0123] Food grade rapeseed oil was used as the reactive feed (baseline) for the control test. The reactive feed for the lipid / bio-oil blend test was a mixture of ~60 wt % food grade rapeseed oil and ~40 wt % bio-oil heavy tail fraction. The final test was conducted with 100% bio-oil heavy tail fraction. Octadecane, a normal paraffin solvent, was added to the reactor so that the entire catalyst basket was submerged. Sulfiding agent TBPS-454 was also metered into the reactor at sufficient levels to maintain catalyst activity during the reaction. In each experiment, the reactive feed was added to the reactor to achieve a solvent and oil dilution of approximately 3: 1 by volume.

[0124] Hydrogen was supplied continuously throughout the duration of each experiment. The minimum hydrogen flow rate was calculated based on the reactive feed oxygen content and unsaturation. The flow rate used was at least twice the stoichiometric requirement to fully deoxygenate and hydrogenate the reactive feed within the duration of the 90 minute experiment. Therefore, the higher oxygen content of bio-oil results in a higher hydrogen demand than rapeseed oil. The flow rate for the 40 wt % bio-oil test was approximately twice the baseline flow rate, and the 100 wt % bio-oil test required nearly 3.2 times the amount of hydrogen.

[0125] After charging the reactor with the liquid input, the reactor 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, marking "time zero" of the reaction cycle.

[0126] Water vapor and other compounds that are volatile under reactor conditions are continuously flushed from the reactor. Those that are condensable at about 100°F are condensed in the aforementioned heat exchanger. Samples are also collected directly from the reactor through an internal sample port during the experiment. All liquid samples are cooled to ~100°F prior to collection to help prevent loss of volatile materials.

[0127] The reactor was shut down after reaching the desired cycle time or degree of conversion. Shutdown was achieved by shutting down the hydrogen supply and reducing the temperature set point to 140°F. After reaching 140°F and completing a thorough nitrogen purge, the reactor was completely emptied through the bottom drain. A nitrogen pressure of ~50 psig was maintained while the reactor was discharged. Only after all liquids from the previous run were discharged, fresh solvent, sulfiding agent and fresh reactive feed added to the reactor for subsequent runs. One catalyst loading was used for all reactions described in this example.

[0128] All experiments achieved high levels of reactant conversion, as indicated by total acid number (TAN) measurements (according to ASTM D664), as shown below. Error! No reference source was found. The baseline experiment was performed normally, with no signs of reduced catalyst activity and no reactor fouling. Similarly, the experiment with 40% bio-oil in rapeseed oil was performed in a manner similar to the baseline experiment, achieving complete conversion, no signs of reduced catalyst activity, and no reactor fouling. In contrast, the reactor product from the 100% bio-oil case had a product TAN value that was nearly four times higher than that observed from the two other experiments. Increased TAN is a major indicator of reduced hydroprocessing performance through reduced catalyst activity and / or coking fouling. In addition, when attempting to sample the reactor contents, it was found that the reactor contents sampling port had become clogged. Due to the blockage, no liquid sample was available throughout the experiment. Therefore, the experiment was run to completion, and the liquid reaction products were removed at this time through the vessel bottom drain.

[0129] After the 100% bio-oil experiment, when the reactor was opened after the experiment was completed, the reactor was found to contain a large amount of coke accumulation. No coke formation was observed in the experiments conducted with rapeseed oil or in the 40 wt% bio-oil experiment. Hu et al. (Xun Hu, 2020) summarized many of the latest experiments in the literature on the hydrodeoxygenation of bio-oil. Although some differences were observed between different catalysts and operating conditions, such as the 100% bio-oil experiment discussed here, it was found that biomass-derived bio-oil formed a large amount of coke in each instance. Carbohydrate-derived materials were observed to dehydrate, decarboxylate, and decarbonylate to produce unsaturated intermediate compounds, which combined and polymerized to form aromatic compounds, which further polymerized to form coke. Similarly, lignin-derived compounds that are already aromatic in nature further condense to form polycyclic aromatic compounds, which continue to polymerize and form coke.

[0130] As summarized by Hu et al. (Xun Hu, 2020), some researchers have also tried using water and low molecular weight alcohols as solvents for bio-oils. Some solvents help reduce the coking rate, however, the solvents used are unlikely to be practical for use on an industrial scale. As discussed in the present invention, using lipids that are already used to produce renewable diesel as solvents makes this approach more feasible.

[0131] It was observed that coke formation significantly reduced the liquid yield of the reactive feed, so much so that it was not feasible to process 100% bio-oil in this manner. As shown in 4, Error! No reference source was found, the 100% rapeseed oil sample resulted in a total liquid yield of about 85%. Due to the higher oxygen content of bio-oil, the addition of 40 wt% bio-oil to rapeseed reduced the total liquid yield to about 68% as expected. Assuming that the liquid yield would follow a linear trend, the 100% bio-oil experiment would be expected to produce about 40% liquid. However, due to the additional coke formation, the measured yield was only 15%.

[0132] In the case of 100% bio-oil, coke formation is such that it is reasonably expected to rapidly foul the catalyst and internals of the fixed bed system, rapidly reducing the life of the catalyst bed and making the process unfeasible on an industrial scale. In contrast, blending bio-oil with rapeseed oil (as exemplified herein at 40%) demonstrated significantly beneficial improvements in both final conversion and reduced coke formation.

[0133] The product materials from three experiments (100% rapeseed oil, 40% bio-oil / 60% rapeseed oil, and 100% bio-oil) were observed. Displaying the products side by side revealed significant visual differences associated with the products of the 100% bio-oil reaction. The product materials of 100% rapeseed oil and 40% bio-oil / 60% rapeseed oil were generally clear and similar in appearance. In contrast, the color of the 100% bio-oil product material was yellow. The color body and large amounts of insoluble material of the 100% bio-oil product material indicated non-alkane products.

[0134] Thus, it will be seen that according to the present invention there is provided a highly advantageous lipid-assisted conversion for hydrocarbon fuels, and more particularly fuels having renewable content. While the present invention has been described in conjunction 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 may be made thereto within the scope of the invention, which scope will be consistent with the broadest interpretation of the appended claims, thereby encompassing all equivalent structures and products.

Claims

1. A method for converting bio-oil derived from lignocellulosic biomass into hydrocarbon fuel or fuel blends, comprising the steps of: (a) combining the bio-oil and lipid to produce a combined feed; (b) introducing the combined feed into a hydroprocessing reactor to produce a reactor effluent; (c) separating the reactor effluent into hydrocarbon, gas, and water streams; and (d) fractionating hydrocarbons into a gasoline fraction and a kerosene / diesel fraction; Wherein the combined feed has a lipid content between about 16 vol% and about 90 vol% and the kerosene / diesel fraction has less than 0.1 wt% oxygen.

2. The process of claim 1, wherein the combined feed has an effective H / C ratio between 1.4 and 1.

8.

3. The method of claim 1, further comprising producing the bio-oil by at least one of fast pyrolysis, hydrothermal liquefaction, or solvent liquefaction, or a combination thereof.

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

5. The method of claim 1, wherein the lipids comprise between about 5% and 95% free fatty acids by weight.

6. The method of claim 1, wherein the hydroprocessing reactor comprises at least one of hydrotreating, hydrogenation, hydrocracking, and hydroisomerization.

7. The process of claim 1 wherein the hydrotreating reactor is operated at a WABT between about 550°F and 690°F and a pressure between about 1000 psig and 3,000 psig.

8. The process of claim 1 wherein the hydroprocessing reactor contains a catalyst comprising sulfided molybdenum, tungsten, or a combination thereof.

9. The method of claim 1, wherein the kerosene / diesel fraction has a cetane number greater than or equal to 40.

10. The method of claim 1 further comprising blending the kerosene / diesel fraction with biodiesel.

11. The method of claim 1, further comprising combining the bio-oil with the pre-lipid fractionated crude bio-oil in step (a) to produce the bio-oil.

12. The method of claim 11, wherein the bio-oil is fractionated based on boiling points greater than about 200°F.

13. The method of claim 11, wherein the bio-oil is fractionated based on boiling points greater than 250°F.

14. The method of claim 11, wherein the bio-oil is fractionated based on boiling points greater than 300°F.

15. The method of claim 11, further comprising fractionating the bio-oil according to solubility in water such that substantially all water-soluble compounds are removed and the bio-oil is substantially insoluble in water prior to combining with the lipid in step (a).

16. The method of claim 3, further comprising producing bio-oil solely by fluidized bed fast pyrolysis.

17. The method of claim 1, further comprising producing the bio-oil solely by solvent liquefaction.

18. The method of claim 17, wherein the solvent liquefaction method utilizes lipids or lipid derivatives as part or all of the primary reaction solvent.

19. A method for converting bio-oil derived from lignocellulosic biomass into a fuel or fuel blend comprising the steps of: (a) contacting the bio-oil with a lipid or a lipid derivative to form an organic phase comprising phenolic compounds and an aqueous phase; (b) separating the organic phase from the aqueous phase; (c) hydrogenating and deoxygenating the organic phase in a hydroprocessing reactor to produce hydrocarbon products, gaseous products and water; and (d) fractionating the hydrotreating reactor hydrocarbon products into fuel products comprising gasoline and kerosene / diesel.

20. A method for converting crude bio-oil derived from lignocellulosic biomass into a fuel or fuel blend comprising the steps of: (a) fractionating the crude bio-oil according to boiling point or solubility in water to produce refined bio-oil; (b) contacting the refined bio-oil with a lipid or a lipid derivative to form an organic phase comprising phenolic compounds and an aqueous phase; (b) separating the organic phase from the aqueous phase; (c) hydrogenating and deoxygenating the organic phase in a hydroprocessing reactor to produce hydrocarbon products, gaseous products and water; and (d) fractionating the hydrotreating reactor hydrocarbon product into a fuel product comprising a gasoline fraction and a kerosene / diesel fraction; Wherein the combined feed has a lipid content between about 16 vol % and about 90 vol % and the kerosene / diesel fraction has less than 0.1 wt % oxygen.

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