Hydroprocessing of Bio-Crude Oil Using Vegetable and / or Fatty Substances

Abstract

The present invention relates to a method for producing a hydrocarbon feedstock, comprising the following steps: providing a biocrude feedstock containing more than 10% by mass of oxygen (O); feeding the biocrude feedstock to a stabilization step in a stabilization reactor to produce a stabilized biocrude feedstock having less O than the biocrude feedstock; feeding the stabilized biocrude feedstock to a hydrodeoxygenation or deoxygenation (HDO / DO) step in an HDO / DO reactor to produce a partially deoxygenated biocrude feedstock containing 2 to 10% by mass of oxygen (O) and having less O than the stabilized biocrude feedstock; providing a vegetable oil and / or fatty substance feedstock; and producing the hydrocarbon feedstock by combining the partially deoxygenated biocrude feedstock with the vegetable oil and / or fatty substance feedstock. The hydrocarbon feedstock can be further hydroprocessed into a hydrocarbon fuel.

Description

Technical Field

[0001] The present invention relates to a method and a plant for hydroprocessing a bio-crude oil feed produced from the pyrolysis of a solid feed stream, together with a vegetable feed and / or a fatty feed.

Background Art

[0002] The co-processing of hydrocarbon fuel feeds by combining fossil fuel feeds such as petroleum feeds and vegetable oil feeds in hydroprocessing is well known. However, crude oils produced by pyrolysis, e.g., the pyrolysis, hydrothermal liquefaction (HTL), or solvolysis of solid renewable feeds such as lignocellulosic biomass, are immiscible with fats and oils, generally vegetable oils and / or fatty acids, and thus the co-processing of these feeds in hydrogenation steps such as hydrodeoxygenation (HDO) has been an important problem to overcome heretofore.

[0003] Stummann et al. “Hydrotreatment of Catalytic Fast Pyrolysis Oil to Renewable Fuels”, NAM27, The 27 th North American Catalysis Society Meeting, May 22-27, 2022 New York, NY discloses a study of combining catalytic fast pyrolysis (CFP) oil with vegetable oil (soybean oil here) in a stirred batch reactor.

Prior Art Documents

Non-Patent Documents

[0004]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Nevertheless, the applicant has found that industrial use is very difficult because vegetable oil does not mix with most untreated catalytic pyrolysis oils. The hydrocracking reactor for treating the co-feed clogs after a few days when operated under industrially appropriate conditions.

[0006] Vegetable oil does not mix with catalytic and non-catalytic pyrolysis oils, as well as hydrothermal liquefaction (HTL) biocrude, but has been found to mix with partially deoxygenated biocrude having an oxygen content of 2 to 10 wt% oxygen (O), such as 2 to 8 wt% O, or 2 to 7 wt% O, such as partially deoxygenated catalytic pyrolysis oil.

Means for Solving the Problems

[0007] Accordingly, in a general embodiment according to a first aspect of the present invention, a method for producing a hydrocarbon feedstock is provided, comprising the following steps: - providing a biocrude feedstock containing more than 10 wt% oxygen (O), such as up to 70 wt% O or up to 60 wt% O; - feeding the biocrude feedstock to a stabilization step in a stabilization reactor to produce a stabilized biocrude feedstock having less O than the biocrude feedstock; - Feeding the stabilized bio-crude oil feedstock to a hydrodeoxygenation or deoxygenation (HDO / DO) step in an HDO / DO reactor to produce a bio-crude oil feedstock that is partially deoxygenated (partially upgraded) and contains less oxygen (O) than the stabilized bio-crude oil feedstock, with 2 to 10 wt% oxygen (O); - Providing a vegetable oil and / or fatty substance feedstock; - Combining the partially deoxygenated bio-crude oil feedstock with the vegetable oil and / or fatty substance feedstock to produce the hydrocarbon feedstock.

[0008] For example, a separate bio-crude oil feedstock containing more than 10 wt% oxygen (O) can be provided, or a separate bio-crude oil feedstock can be combined into a single bio-crude oil feedstock containing more than 10 wt% oxygen (O).

[0009] For example, the partially deoxygenated bio-crude oil feedstock can be combined with a vegetable oil feedstock, or the partially deoxygenated bio-crude oil feedstock can be combined with a fatty substance feedstock such as an animal fat feedstock.

[0010] For example, the partially deoxygenated bio-crude oil feedstock can first be combined with a vegetable oil feedstock and then with a fatty substance feedstock such as an animal fat feedstock. Optionally, an additional feedstock may be provided.

[0011] In one embodiment, the feedstock of vegetable oil and / or fatty substance is a feedstock of non-hydroprocessed vegetable oil and / or fatty substance. Thus, this feedstock has not undergone a prior hydroprocessing step such as hydrodeoxygenation (HDO).

[0012] Therefore, first, the bio-crude oil feed is stabilized, then partially deoxygenated, and then mixed with vegetable oil and / or fatty substances. By stabilizing the bio-crude oil and further removing its oxygen content to the specific range of 2 to 10% by mass, it is now possible to combine it with the vegetable oil and / or fatty substance feed without the risk of clogging any of the HDO / DO reactors or any associated units such as pumps and heat exchangers. Further, the vegetable oil serves to cool the effluent from the HDO / DO reactor, i.e., the partially deoxygenated bio-crude oil feed, or as a coolant between the catalyst beds (catalyst beds) in the HDO reactor. Further, the formation of the heavy fraction in the downstream separation section is reduced, thereby increasing, for example, the production of hydrocarbon fuels such as diesel fuel. An oxygen (O) content of less than 2% by mass in the bio-crude oil feed may contribute to miscibility with vegetable oil and / or fatty substances, but such low levels of oxygen tend to be associated with a low aromatic content. As will be further explained below, the presence of aromatic compounds is desirable because it can reduce the formation of heavy fractions when producing and / or separating downstream hydrocarbon products such as diesel and / or jet fuels. The present invention provides a partial deoxygenation with a moderately heavy bio-crude oil feed, i.e., the oxygen content of the thus partially deoxygenated (partially upgraded) bio-crude oil feed is 2 to 10% by mass of O, while maintaining aromatic compounds therein. For example, the aromatic content may be 20 to 60% by mass of aromatics (total) as measured according to ASTM D6591.

[0013] For the purposes of the present application, the term "first aspect of the present invention" relates to the method. The term "second aspect of the present invention" means a process plant, i.e., a plant. The terms "the present invention" and "the present application" are used interchangeably. The term "consisting of" means "consisting only of", i.e., including "consisting of". The term "appropriately" is used interchangeably with the term "optionally", i.e., any embodiment. The term "partially deoxygenated biocrude feed" can be used interchangeably with the term "partially produced biocrude feed".

[0014] The term "biocrude feed" refers to the liquid oil product of the pyrolysis step in a pyrolysis unit. The biocrude feed can also be understood as "advanced biocrude". The pyrolysis unit is a pyrolysis unit, a hydrothermal liquefaction (HTL) unit, or a solvolysis unit. The term "unit" is understood here as a "reactor".

[0015] The term "vegetable oil feed and / or fatty substance" includes vegetable oils such as soybean oil and fatty substances such as animal fats. Fatty substances include fatty acids.

[0016] The term "section", for example, "hydroprocessing section", means a physical area including a unit or a combination of units for performing one step and / or sub-step for producing a hydroprocessed feed.

[0017] The term "hydroprocessing" includes hydrotreatment and thus includes hydrodeoxygenation or deoxygenation (HDO / DO). The term "hydroprocessing" also includes hydroisomerization (HDI), or hydrocracking (HCR), or hydrodearomatization (HDA). Hydroprocessing steps such as HDO / DO steps are understood to be carried out in a hydroprocessing reactor such as an HDO / DO reactor or in the catalyst bed of a hydroprocessing reactor such as in the catalyst bed of an HDO / DO reactor. The hydroprocessing reactor can include one or more catalyst beds. Other definitions will be described later in connection with one or more embodiments of the present invention.

[0018] In one embodiment, the biocrude feed contains at least 15% by mass of O, or at least 30% by mass of O, for example, 35 to 70% by mass of O, 40 to 60% by mass of O, or 40 to 50% by mass of O.

[0019] As a general rule, the higher the oxygen (O) content, the higher the reactivity of the bio-crude oil feedstock, which in turn increases the tendency to form solid particles or polymerize, clogging the HDO / DO reactor and related units. For example, the bio-crude oil feedstock may have a composition of 45 wt% C, 9 wt% H, and 46 wt% O typical of pyrolysis oil, while a typical vegetable oil such as soybean oil may have a composition of 79 wt% C, 12 wt% H, and 12 wt% O.

[0020] In one embodiment, the bio-crude oil feedstock contains 40 - 60 wt% O, and the stabilized bio-crude oil feedstock contains 20 - 55 wt% O.

[0021] Therefore, it is appropriate that the oxygen content in the stabilized bio-crude oil feedstock is -5% or -10% or -20% relative to the oxygen content of the bio-crude oil feedstock. For example, the bio-crude oil feedstock can have 45 wt% O, and the stabilized bio-crude oil feedstock can have 40 wt% O or 35 wt% O or 25 wt%.

[0022] Suitably, in the combining step, the mass ratio (A:B) of the partially upgraded (partially deoxygenated) bio-crude oil (A) to the vegetable oil and / or fatty substance feedstock (B) is in the range of 9:1, i.e., 90:10 wt% ratio to 1:9, i.e., 10:90 wt% ratio; for example, 4:1, i.e., 80:20 wt% ratio, 3:1, i.e., 75:25 wt% ratio, 2:1, i.e., 66.6:33.3 wt% ratio, 1:1, i.e., 50:50 wt% ratio, 1:2, i.e., 33.3:66.6 wt%, 1:3, i.e., 25:75 wt%, 1:4, i.e., 20:80 wt% ratio, 1:5, i.e., 17:83 wt%, 1:6, i.e., 15:85 wt% ratio.

[0023] In one embodiment, the stabilization step is carried out in a fixed bed reactor in continuous operation mode, in the presence of any of the following; in the presence of a Ni-Mo, Co-Mo, Ni-Cu, Mo, Pt, Pd, Ru, or Ni-based catalyst, at 20 - 240 °C, a pressure of 100 - 200 barg, optionally 0.1 - 1.1 h -1 of liquid hourly space velocity (LHSV), and a hydrogen-to-liquid oil ratio defined as the volume ratio of hydrogen to the liquid oil flow (bio-crude feed) of 1000 - 6000 NL / L, for example 2000 - 5000 NL / L, including feeding the bio-crude feed together with hydrogen, thereby forming a stabilized bio-crude feed.

[0024] For example, the catalyst is a Ni-Mo-based catalyst, or a Co-Mo-based catalyst, or a Ru / TiO₂-based catalyst (ruthenium supported on titania), or a Pt / TiO₂-based catalyst.

[0025] The terms "Ni-Mo-based catalyst", "Co-Mo-based catalyst", etc. mean that Ni-Mo is the active element of the catalyst.

[0026] Suitably, Ni-Mo, Co-Mo, or Mo is in the sulfided form, for example NiMoS. Optionally, Ni is in the sulfided or reduced form.

[0027] The term "stabilization" means converting the carbonyl groups present in compounds of liquid oil, such as aldehydes, ketones and acids, into alcohols. Other molecules such as sugars and furans may also be converted in the stabilization step. For example, this stabilization step can be carried out by a NiMo-based catalyst, as disclosed in Shumeico et al. “Efficient one-stage bio-oil upgrading over sulfide catalysts”, ACS Sustainable Chem.Eng.2020, 8, 15149-15167. 2020, 8, 15149-15167. Appropriately, stabilization is carried out according to the method disclosed in European patent application 21152117.4 (corresponding to international application PCT / EP2022 / 050877) co-pending with the applicant.

[0028] The term "stabilization" or "stabilization step" as used herein is also well-known in the art and is a step carried out in a stabilization reactor, but for example, to avoid the formation of solid particles or polymerization that would clog downstream HDO / DO units and related equipment, the oxygen content in the bio-crude oil feed is reduced. As already mentioned, the oxygen content (O content as mass %) in the stabilized bio-crude oil feed is, for example, -5% or -10% or -20% relative to the bio-crude oil feed.

[0029] The applicant has found that, for example, when combining a low-oxygen-content bio-crude oil feed produced from catalytic fast pyrolysis (CFP) having an oxygen content of about 14 mass % O with a typical vegetable oil having an essentially low oxygen content, e.g. about 11 mass % O, in a small hydrotreating unit (HDO unit), even after a few days the unit becomes clogged, and thus some stabilization is required before the catalytic pyrolysis oil is stable enough to be further hydrodeoxygenated.

[0030] Furthermore, for example, enabling appropriate miscibility between vegetable oil and bio-crude oil is very difficult because there is no direct relationship such as miscibility with the oxygen content of bio-crude oil. For example, as shown in the following example (Example 1), the bio-crude oil samples that initially appear to be easily miscible with vegetable oil are those with the highest oxygen content (Samples C and E).

[0031] In one embodiment, this method further includes the following: - A step of supplying a hydrocarbon feed to a subsequent HDO / DO step for producing a first hydroprocessed feed, wherein the subsequent HDO / DO step is: A step carried out in a downstream catalyst bed of the HDO / DO reactor for producing the partially deoxygenated bio-crude oil feed, or in a downstream HDO / DO reactor.

[0032] The term "first hydroprocessed feed" can be used interchangeably with the term "hydrotreated feed" and means an effluent stream from an HDO / DO reactor that processes a composite feed (simultaneous feed). Strictly speaking, deoxygenation (DO) does not exist, for example, by the addition of hydrogen for the purposes of this application, but it is understood that it is still considered a hydroprocessing step.

[0033] Therefore, several layouts have been proposed: for example, - Providing at least two HDO / DO reactors, where the oxygen content is reduced to 2 - 10% by mass for pyrolysis oil and 2 - 8% by mass for HTL oil or solvent-decomposed oil (solvolysis oil), then mixing the vegetable oil with the product from the first HDO / DO reactor and sending the mixture to the next (second) HDO / DO reactor. - Providing only one HDO / DO reactor and co-processing the vegetable oil by supplying it to the lower bed of the HDO / DO reactor.

[0034] This application enables the co-processing of fatty substances such as vegetable oils and / or fatty acids with HTL oil or pyrolysis oil or solvolysis oil, which is not possible by other methods. Further, for example, the vegetable oil is used to cool the product from the first HDO / DO reactor or as inter-bed cooling within the first HDO reactor. Further, for example, the effluent from a partially deoxygenated biocrude feed containing 2-10% by weight of O in HTL's HDO / DO, i.e., can be highly aromatic, while the product from the HDO of vegetable oil is highly paraffinic. Thus, co-processing leads to a better quality diesel oil compared to the HDO of HTL oil alone, or pyrolysis oil alone, or solvolysis oil alone.

[0035] In one embodiment, the method further includes the following: - Feeding a first hydroprocessed feed, e.g., a hydrotreated feed, to subsequent hydroprocessing steps in a downstream hydroprocessing section; e.g., a hydroisomerization (HDI) section in an HDI reactor, and / or a hydrocracking (HCR) step in an HCR reactor, and / or a hydrodearomatization (HDA) step in an HDA reactor to produce a second hydroprocessed feed.

[0036] Thus, the subsequent hydroprocessing steps include treating the hydrotreated feed in one or more additional catalytic hydrotreating units such as a third catalytic hydrotreating unit or a cracking section under the addition of hydrogen. For example, if hydrocarbon products boiling in the jet fuel range are desired, it is understood that, for example, a hydrocracking (HCR) unit is suitably used before passing such a hydrotreated stream to HDI.

[0037] Typically, pyrolysis oil contains a large amount of oxygen compounds and unsaturated hydrocarbons. During the hydrotreating of this feedstock, oxygen is mainly removed as H2O, and a fuel mainly composed of naphthenes and aromatic compounds is obtained. This is called the hydrodeoxygenation (HDO) pathway. Oxygen can also be removed by a decarboxylation pathway that produces CO2 instead of H2O: [Chem.] Furthermore, typically, decarbonylation is not dominant in the HDO of triglycerides in typical renewable feedstocks, but it can be more dominant in the HDO of pyrolysis oil: Decarbonylation pathway: RCH2COH + H2 <-> RCH3 + CO

[0038] Materials having catalytic activity in HDO (which can be used interchangeably with the term hydrotreating as used herein) typically include an active metal (sulfided base metals such as nickel, cobalt, tungsten and / or molybdenum, but also including elemental precious metals such as platinum and / or palladium if possible) and a refractory support (such as alumina, silica or titania, or a combination thereof).

[0039] HDO conditions include a temperature between 250 and 400 °C, a pressure between 30 and 150 bar, and a liquid hourly space velocity (LHSV) between 0.1 and 2, and optionally include intermediate cooling by cold hydrogen, quenching of the feedstock or product.

[0040] Materials having catalytic activity in hydroisomerization HDI typically include an active metal (elemental precious metals such as platinum and / or palladium, or sulfided base metals such as nickel, cobalt, tungsten and / or molybdenum), an acidic support (typically a molecular sieve having a topology such as MOR, FER, MRE, MWW, AEL, TON and MTT, showing high shape selectivity), and a refractory support (alumina, silica or titania, or a combination thereof).

[0041] The HDI conditions include a temperature between 250 and 400 °C, a pressure between 20 and 100 bar, and a liquid hourly space velocity (LHSV) in the interval of 0.5 to 8.

[0042] Materials having catalytic activity in hydrocracking (HCR) have properties similar to those of materials having catalytic activity in isomerization, which typically include an active metal (elemental noble metals such as platinum and / or palladium, or sulfided base metals such as nickel, cobalt, tungsten and / or molybdenum), an acidic support (typically a molecular sieve having a topology such as MFI, BEA and FAU, showing high cracking activity), and a refractory support (such as alumina, silica or titania, or a combination thereof). The difference from materials having catalytic activity in isomerization is typically the nature of the acidic support, which may be of different structures (even amorphous silica-alumina) and may have different acidities, such as by the silica:alumina ratio.

[0043] The HCR conditions include a temperature between 250 and 400 °C, a pressure between 30 and 150 bar, and a liquid hourly space velocity (LHSV) between 0.5 and 8, optionally including intermediate cooling by cold hydrogen, quenching of the feed or product.

[0044] Materials having catalytic activity in HDA typically include an active metal (elemental noble metals such as platinum and / or palladium, but may also include sulfided base metals such as nickel, cobalt, tungsten and / or molybdenum) and a refractory support (such as including amorphous silica-alumina, alumina, silica or titania).

[0045] The HDA conditions include a temperature between 200 and 350 °C, a pressure between 20 and 100 bar or between 20 and 200 bar, and a liquid hourly space velocity (LHSV) between 0.5 and 8.

[0046] In one embodiment, the method includes the following: - further comprising feeding the first hydrogenated feed or the second hydrogenated feed to a separation step in a separation section to produce a hydrocarbon product, wherein the hydrocarbon product is any one of naphtha, diesel, jet fuel, marine (ship) fuel as a heavy fraction, or a combination thereof.

[0047] Thus, the marine (ship) fuel is suitably taken out as a heavy fraction.

[0048] According to one embodiment, the mass ratio (A:B) of the partially upgraded (partially deoxygenated) biocrude oil feed (A) to the vegetable oil and / or fatty substance feed (B) is in the range of 1:1, i.e., 50:50% by mass (i.e., 1:1) to 10:90% by mass (i.e., 1:9), for example 20:80% by mass (i.e., 1:4) or 15:85% by mass (1:5.7), and optionally, the subsequent HDO / DO step is carried out in continuous mode under conditions of 250 - 400 °C, for example 350 - 380 °C, a pressure of 50 - 150 bar, for example 100 bar, and a fixed bed catalyst where the catalyst is NiMoS and / or MoS.

[0049] At the above mass ratio (A:B), the best results are obtained in terms of cetane index and compliance with the standard (EN590 standard). Further, for example, by loading the MoS catalyst at the upper part of the HDO / DO reactor, the formation of heavy fractions is further reduced.

[0050] It will be understood that the temperature of a given reactor refers to the inlet temperature in an adiabatic fixed bed reactor or the reaction temperature in an isothermal reactor.

[0051] Suitably, any of the stabilization reactor and the hydroprocessing reactors such as the HDO / DO reactor or the HDI reactor or the HCR reactor or the HDA reactor is an adiabatic fixed bed reactor.

[0052] Certain combinations of co-processing, suitably in these mass ratios, and, as described above, by providing NiMoS and / or MoS catalysts in subsequent HDO / DO steps, enable a reduction in the heavy fraction (C18+ formation). Thus, the diesel yield, which is in the C15 - C18 range, increases.

[0053] Downstream of the desired hydrocarbon product is, in an embodiment, diesel as the hydrocarbon product boiling in the transport fuel range, which is suitably represented by C15 - C18 hydrocarbons. Hydrocarbons with a carbon number greater than 18 (C18+) may be taken up downstream of the separation section as the heavy fraction (also referred to herein as the heavy ends), but it would be desirable to reduce this heavy fraction in order to increase the yield of the C15 - C18 fraction and thus the yield of diesel fuel. Co-feeding a partially deoxygenated biocrude provides, for example, lower production of the heavy fraction when provided in a mass range (50:50 mass% to 10:90 mass%) as described above, while still maintaining proper miscibility of the feed. Without being bound by any theory, it is thought that aromatics in the partially deoxygenated biocrude feed act as hydrogen donors, thereby reducing heavy fraction formation. A conventional approach when dealing with heavy fractions is to hydrocrack the heavier portion of the product, thereby removing the heavy fraction. However, hydrocracking results in yield losses. Thus, minimizing heavy fraction formation increases the overall yield of the process, particularly the diesel yield.

[0054] In another embodiment, the mass ratio (A:B) of the partially upgraded (partially deoxygenated) biocrude feed (A) to the vegetable oil and / or fatty substance feed (B) is in the range of 50:50 mass% to 90:10 mass%, and optionally, any of the HDO / DO steps is carried out in continuous mode at a pressure of 50 - 150 bar (bara) using a fixed bed catalyst where the catalyst is NiMoS and / or MoS, under conditions of 250 - 400 °C, for example 340 - 400 °C.

[0055] Thus, the mass ratio (A:B) of the partially deoxygenated biocrude oil feed (A) to the vegetable oil and / or fatty substance feed (B) is in the range of 50:50% by mass to 90:10% by mass, for example 80:20% by mass or 75:25% by mass. For example, a mixture of 80% by volume of hydrotreated catalytic pyrolysis oil as the partially deoxygenated biocrude (A) has an oxygen (O) content of about 2% by mass and 20% by volume of soybean oil as the vegetable oil (B), and reduces the cloud point and pour point of the mixture compared to the stand-alone hydrotreatment of soybean oil. This conveys the advantage that there is less need for hydroisomerization (HDI), and thus the associated yield loss during hydroisomerization is reduced. Thereby, the associated capital cost (CAPEX) and operating expenses (OPEX) for isomerization are also reduced.

[0056] As is well known in the art, the cloud point of any petroleum product is an indicator of how well hydrocarbon products, such as diesel, function under cold weather conditions. The pour point, which is the opposite of the cloud point, refers to the lowest temperature at which the movement of the oil can be observed so that the diesel can be pumped.

[0057] Suitably, the next HDO / DO step is carried out in continuous mode, for example at 250 - 400 °C, for example 350 - 380 °C, a pressure of 50 - 150 bar, for example 100 bar, and a fixed bed catalyst where the catalyst is NiMoS and / or MoS.

[0058] At the above mass ratio (A:B), for example, by combining hydrotreated waste tire pyrolysis oil and hydrotreated vegetable oil, such as HVO, the resulting diesel oil shows desirable results with respect to the cetane index and compliance with the specification (EN590 standard), and improved low-temperature flow properties are obtained also with respect to the cloud point. Furthermore, for example, by loading a MoS catalyst at the top of the HDO / DO reactor, the formation of heavy fractions can be further reduced.

[0059] In an embodiment, the pyrolysis unit (pyrolysis reactor) further includes a pyrolysis step of a solid feed stream in a pyrolysis unit selected from a pyrolysis step in the pyrolysis unit and a hydrothermal liquefaction (HTL) step in the HTL unit, or a solvolysis step in a solvolysis unit, thereby producing a bio-crude oil stream containing more than 10% by mass of O.

[0060] In an embodiment, the pyrolysis step is a pyrolysis step, for example, a fast pyrolysis step.

[0061] As is well known in the art, the pyrolysis step can include the use of a pyrolysis unit such as a fluidized bed, a transport bed, or a circulating fluidized bed. For example, the pyrolysis step can include the use of a pyrolysis unit (also referred to herein as a pyrolysis reactor), the use of a cyclone to remove particulate solids such as carbon, and thereby the use of a cooling unit to produce a first off-gas stream (i.e., pyrolysis off-gas) and a first liquid oil stream, i.e., condensed pyrolysis oil. This first off-gas stream contains light hydrocarbons such as C1-C4 hydrocarbons, CO, and CO2. The first liquid oil stream, also called pyrolysis oil or bio-oil, is typically a liquid substance rich in a mixture of molecules consisting of more than 200 different compounds including other compounds such as aldehydes, ketones, and / or furfural having a carbonyl group, and is due to the depolymerization of the products treated by pyrolysis.

[0062] For the purposes of the present invention, the pyrolysis step is preferably fast pyrolysis, also known as flash pyrolysis. Fast pyrolysis means the thermal decomposition of a solid renewable feedstock in the absence of oxygen, at a temperature in the range of 350 to 650 °C, for example about 500 °C, with a reaction time of less than 10 seconds, for example 5 seconds or less, for example about 2 seconds; that is, the vapor residence time is 10 seconds or less, for example less than 2 seconds, that is 2 seconds. Conventionally, fast pyrolysis could also be carried out, for example, by autothermal operation in a fluidized bed reactor. The latter is also called auto-pyrolysis or is characterized by the use of a mixture of air and an inert gas or recycle gas. Thereby, the partial oxidation of the pyrolysis compounds produced in the pyrolysis reactor (autothermal reactor) supplies the energy for the pyrolysis and at the same time improves heat transfer. For details on auto-pyrolysis, see, for example, "Heterodoxy in Fast Pyrolysis of Biomass" by Robert Brown: https: / / dx.doi.org / 10.1021 / acs.energyfuels.0c03512.

[0063] Accordingly, in an embodiment of the present application, as a specific embodiment for carrying out fast pyrolysis, auto-pyrolysis, that is, the use of auto-pyrolysis, is provided, that is, the pyrolysis step is carried out by auto-pyrolysis.

[0064] There are several types of fast pyrolysis in which a catalyst is used. In a pyrolysis apparatus (pyrolysis reactor), an acid catalyst such as a zeolite catalyst is sometimes used to upgrade the pyrolysis vapor; this technique is called catalytic fast pyrolysis (CFP) and can be operated in both an internal mode (in-situ mode, where the catalyst is located inside the pyrolysis apparatus) and an external mode (ex-situ mode, where the catalyst is placed in a separate reactor. That is, the pyrolysis gas is sent to a deoxygenation (DO) reactor to catalytically deoxygenate it before condensing the pyrolysis oil as described above). More specifically, in in-situ catalytic fast pyrolysis, the catalyst is located inside the pyrolysis unit and deoxygenation occurs inside the pyrolysis reactor (through decarboxylation, decarboxylation by an acid-based catalyst such as a zeolite catalyst) immediately after the pyrolysis vapor is formed. Suitable catalysts for CFP include alumina and all types of zeolite catalysts commonly used for hydrocracking (HCR) and cracking in purification processes such as HZSM-5. A more extensive list of catalyst materials for HCR is described later in this application.

[0065] Similarly, in internal (in-situ) HDO (also called reactive catalytic fast pyrolysis, RCFP), a hydrodeoxygenation (HDO) catalyst is located in the pyrolysis unit and hydrodeoxygenation occurs in the pyrolysis reactor immediately after the pyrolysis vapor is formed. Suitable catalysts for HDO are metal-based catalysts, including, for example, reduced Ni, Mo, Co, Pt, Pd, Re, Ru, Fe, such as CoMo or NiMo catalysts, preferably in sulfide form: CoMoS, NiS, NiMoS, NiWS, NiWS, RuS. The catalyst support is the same as in conventional HDO in the purification step and can typically be a refractory support such as alumina, silica or titania, or a combination thereof. Note that the HDO conditions are also described further below in this application.

[0066] In the ex-situ mode of deoxygenation (DO), the steam is deoxygenated in a separate DO reactor located after the pyrolysis unit. Thus, in external catalytic fast pyrolysis, the steam is deoxygenated using an acid catalyst such as a zeolite catalyst.

[0067] In external HDO, the pyrolysis steam is hydrodeoxygenated in a separate HDO reactor located after the pyrolysis reactor using a hydrotreating catalyst, as described, for example, in connection with FIGS. 1 and 2 below.

[0068] By using a catalyst in the pyrolysis reactor, the activation energy of the reaction is reduced, thereby having the advantage of significantly reducing the temperature required to perform pyrolysis. In addition, an increase in selectivity for the desired pyrolysis oil compound can be achieved.

[0069] It will be understood that when hydrogen is added to catalytic fast pyrolysis, it is called reactive catalytic fast pyrolysis (RCFP). Further, when catalytic fast pyrolysis is carried out at a high hydrogen pressure (> about 5 barg), it is often called catalytic hydro-pyrolysis (CHP). Hydrolysis (HP) means that hydrogen is added to the pyrolyzate, but at atmospheric pressure.

[0070] The pyrolysis step is also simple fast pyrolysis, which for the purposes of this application means that fast pyrolysis is carried out rapidly without the presence of a catalyst and hydrogen in the pyrolysis unit, i.e., fast pyrolysis does not fall into any of catalytic fast pyrolysis (CFP), hydro-pyrolysis (HP), reactive catalytic fast pyrolysis (RCFP) or catalytic hydro-pyrolysis (CHP). The pyrolysis unit can optionally not include an HDO reactor downstream. This enables a much simpler and cheaper process.

[0071] The following table summarizes the various options for fast pyrolysis, apart from auto-pyrolysis:

[0072] TIFF2025523969000003.tif82170

[0073] Thus, in an embodiment, the pyrolysis step is fast pyrolysis, the vapor residence time is 10 seconds or less, for example, 5 seconds or less, for example, about 2 seconds or 1 second, etc., or in the range of 1 to 5 seconds, and is selected from the following: simple fast pyrolysis; in-situ catalytic fast pyrolysis (CFP); ex-situ catalytic fast pyrolysis (CFP); reactive catalytic fast pyrolysis (RCFP); hydrolysis (HP); catalytic hydrolysis (CHP).

[0074] In another embodiment, the pyrolysis step is slow pyrolysis, and the vapor residence time is in the range of 10 seconds to 5 minutes, for example, 11 seconds to 3 minutes. For fast pyrolysis, the temperature is also in the range of 350 to 650 °C, for example, about 500 °C. This pyrolysis is often carried out in a pyrolysis reactor for handling different types of waste, and the vapor is combusted after the pyrolysis reactor. Typical reactors are Herschoff reactors, rotary drums, Amaron, Choren paddle pyrolysis kilns, auger reactors, and vacuum pyrolysis reactors.

[0075] In another embodiment, the pyrolysis step is slow pyrolysis, and the solid residence time is in the range of 5 minutes to 2 hours, for example, 10 minutes to 1 hour. Appropriately, the temperature is about 300 °C. This pyrolysis results in a high carbohydrate yield, and the carbon can be used as fertilizer or as carbon; the pyrolysis still produces a certain amount of gas and bio-oil, and when the carbon is used as fertilizer, the final bio-oil becomes a GHG exceeding 100%, and thus is carbon negative. Typical reactors are auger reactors - having a different residence time from intermediate pyrolysis -, fixed bed reactors, kilns, Lambiotte SIFIC / CISR retorts, Lurgi processes, wagon reactors, and Carbo Twin resorts.

[0076] In an embodiment, the pyrolysis step is a hydrothermal liquefaction step. Hydrothermal liquefaction means thermochemically converting biomass into liquid fuel by treating it in a high-temperature, pressurized water environment for a period sufficient to decompose the solid biopolymer structure mainly into liquid components. Under typical hydrothermal treatment conditions, the temperature ranges from 250 to 375 °C and the operating pressure ranges from 40 to 220 bar. This technology offers the advantages of lower temperature, higher energy efficiency, and lower tar yield operations compared to pyrolysis, e.g., fast pyrolysis. For details on the hydrothermal liquefaction of biomass, see, for example, Golakota et al., “A review of hydrothermal liquefaction of biomass”, Renewable and Sustainable Energy Reviews, vol. 81, Part 1, Jan. 2018, p. 1378-1392.

[0077] In an embodiment, the pyrolysis step is solvolysis. For the purposes of the present application, the term “solvolysis” means heating lignocellulosic biomass in methanol, ethanol, other alcohols, or recycled oil, optionally in water, at a pressure in the range of 20 to 80 bar, e.g., 40 to 60 bar, and at a temperature in the range of 150 to 450 °C, e.g., 150 to 200 °C or 325 to 425 °C, to form lignin-derived bio-crude oil (solvolysis oil) as the bio-crude feedstock.

[0078] As is well known in the art, solvolysis is a chemical reaction in which a solvent, e.g., methanol or ethanol, optionally water, is one of the reactants and is present in amounts far exceeding the amount required for the reaction. When the solvent is specifically water, solvolysis is hydrolysis. Thus, in certain embodiments, the solvolysis step is hydrolysis.

[0079] In an embodiment, pyrolysis passes a solid renewable feedstock through a solid renewable feedstock production section and further includes a preliminary stage that includes drying, for example, to remove water and / or grinding to reduce particle size. For example, any water / moisture in the solid renewable feedstock that evaporates in the pyrolysis section condenses in the pyrolysis oil stream, thereby being carried out in the process but may be undesirable. Further, the heat used for the evaporation of water removes the heat required for pyrolysis. By removing water and also providing a smaller particle size in the solid renewable feedstock, the thermal efficiency of the pyrolysis step is increased.

[0080] The preliminary step may also include performing pickling to remove metals. This is particularly relevant to the pyrolysis process where the catalyst is located within the pyrolysis reactor. Removing metals from the solid renewable feedstock extends the catalyst life.

[0081] In one embodiment, the solid renewable feedstock includes lignocellulosic biomass including wood products, forestry waste, and agricultural residues. In one embodiment, the lignocellulosic biomass includes algae. In another embodiment, the solid renewable feedstock includes nitrogen-rich renewable feedstocks such as manure or sewage sludge, particularly the organic portion thereof, such as the organic portion of sewage sludge.

[0082] The term "sewage sludge" means the residual semi-solid material produced as a by-product during the sewage treatment of industrial or municipal wastewater, for example, dehydrated sludge containing 50 - 70% by mass of organic matter and 30 - 50% by mass of inorganic components (including 1 - 4% by mass of inorganic carbon), 1 - 10% by mass of N, for example 3.4 - 4.0% by mass of nitrogen (N), and 0.5 - 2.5% by mass of phosphorus (P).

[0083] In another embodiment, the solid renewable feedstock includes municipal waste, particularly the organic portion thereof.

[0084] For the purposes of the present application, the term "municipal waste" is interchangeable with the term "municipal solid waste" and means articles discarded by the general public, such as mixed municipal waste given the waste code 20 03 01 of the European Waste Catalogue (EWC code 20 03 01).

[0085] In another embodiment, the solid renewable feedstock includes recycled solid waste, particularly its organic part, where the recycled solid waste is defined as a feedstock including materials of articles discarded by the general public, such as mixed recycled solid waste given in EU Directive 2018 / 2001 (RED II), Annex IX, Part A.

[0086] Accordingly, the renewable feedstock includes one or more of the following: - lignocellulosic biomass such as wood products, algae, forestry waste and / or agricultural residues; - nitrogen-rich renewable raw materials such as compost and sewage sludge; - municipal waste, particularly its organic part, is defined as a feedstock including articles discarded by the general public, such as mixed municipal waste given the waste code 20 03 01 of the European Waste Catalogue (EWC code 20 03 01), and / or recycled solid waste, particularly its organic part, and recycled solid waste is defined as a feedstock including articles discarded by the general public, such as mixed recycled solid waste given in EU Directive 2018 / 2001 (RED II), Annex IX, Part A.

[0087] In a particular embodiment, the lignocellulosic biomass is forestry waste and / or agricultural residues and includes biomass derived from plants including natural grass (grass derived from natural landscapes), wheat, such as wheat straw, oats, rye, reedgrass, bamboo, sugarcane, or sugarcane derivatives such as bagasse, corn and other grains.

[0088] Any of the above combinations is also envisaged.

[0089] As used herein, the term "lignocellulosic biomass" means biomass containing cellulose, hemicellulose, and optionally lignin. Lignin or a substantial portion thereof may be removed, for example, by a previous bleaching step.

[0090] In one embodiment, the method includes the following feeds to the pyrolysis unit: - At least 50 wt%, such as at least 60 wt%, or at least 70 wt% or at least 80 wt% or at least 90 wt% of a solid renewable feedstock, such as lignocellulosic biomass, municipal waste and / or recycled solid waste, to produce a pyrolysis oil stream, or an HTL oil stream, or a solvolysis oil stream as a bio-crude oil feed containing more than 10 wt% O.

[0091] In particular, hydrocarbon fuel diesel produced from a bio-crude oil feed containing more than 10 wt% O generated from the pyrolysis of lignocellulosic biomass is rich in aromatics, and thus the density and cetane index of the diesel fraction are too high to meet the EN590 diesel standard. Therefore, a major problem associated with such high-grade bio-crude oil is that it has a very large number of aromatics, so that the cyclic alkanes also do not have the best cetane index and are not necessarily sufficient for hydrodearomatization (HDA), and thus ring opening by hydrocracking is required. However, by co-processing with, for example, vegetable oils, it is now possible to minimize the hydrocracking and / or isomerization required to obtain a good cetane index, such as the cetane index (CCI according to standard ASTM D4737), which is also simply called CCI, for example higher than 40, for example 45 - 60, and at the same time increase the diesel yield.

[0092] For example, hydrotreated vegetable oil (HVO), or hydrotreated cooking oil (hydrotreated used cooking oil) has a very high cetane index and low density, but poor low-temperature flow properties. For example, the pyrolysis of lignocellulosic biomass, especially the bio-crude oil feed after said stabilization, optionally followed by HDI, and the combination with HVO or hydrotreated heating oil, results in a particularly good diesel fuel compliant with the EN590 standard, including adaptation to desirable low-temperature flow properties, for example with respect to the cloud point (CP).

[0093] Accordingly, in an embodiment, the supply of said vegetable oil and / or fatty substance is hydrotreated, for example, a supply of hydrotreated vegetable oil and / or fatty substance (for example, a supply of hydrotreated vegetable oil and / or a supply of hydrotreated fatty substance). The latter can be supplied externally or internally and can thereby be incorporated by a method further comprising subjecting the vegetable oil and / or fatty substance to a hydrogenation step, preferably a hydrodeoxygenation (HDO) step, before combining with the partially deoxygenated bio-crude oil feed.

[0094] In one embodiment, the supply of said vegetable oil and / or fatty substance is any of the following: Soybean oil, for example, soybean oil, rapeseed oil, corn oil, castor oil, cooking oil, animal fats, for example, beef, pork, milk, chicken fat; and combinations thereof.

[0095] For example, the fatty substance supply contains fatty acids and the fatty substance supply is suitably any of triglycerides, diglycerides, monoglycerides, and free fatty acids.

[0096] When combining a partially deoxygenated biocrude oil feed with a vegetable oil and / or fatty substance feed, an additional feed can be provided to produce the hydrocarbon feed. Thus, in one embodiment, the step of combining a partially deoxygenated biocrude oil feed with a vegetable oil and / or fatty substance feed is further combined with an additional feed; the additional feed is suitably the following: A feed derived from a fossil feed, i.e., a feed derived from a fossil fuel source such as diesel, kerosene, naphtha, vacuum gas oil (VGO), etc., and / or An intermediate hydrocarbon product, e.g., a recycle oil by recycling an intermediate hydrocarbon product produced in the method, i.e., a part of a hydroprocessed feed produced downstream, e.g., a first or second hydroprocessed feed.

[0097] Thus, suitably, the intermediate hydrocarbon product produced in the method is part of a first or second hydroprocessed feed.

[0098] According to one embodiment, the method further comprises feeding diesel fuel and marine (ship) fuel, or a combination thereof, as heavy components to a hydroisomerization (HDI) step in an HDI reactor and / or a hydrocracking (HCR) step in an HCR reactor to produce an intermediate hydrocarbon product, e.g., the intermediate hydrocarbon product produced during the method.

[0099] Thus, in the separation section, for example, diesel fuel and marine fuel are withdrawn therefrom and in a distillation column, and either these hydrocarbon products or a portion thereof are supplied to HDI and / or HCR. Thus, such hydrocarbon products, for example, marine fuel hydrotreated in an HCR reactor, are advantageously added after combining with a partially deoxygenated biocrude oil feed (already stabilized and subjected to HDO / DO) and appropriately hydrotreated vegetable oil and / or fatty substance feed. As already mentioned, high synergistic effects have been found by hydrotreating each of these streams separately.

[0100] In one embodiment, the method includes a pre-solvent extraction step of the biocrude oil feed, such as a toluene extraction step prior thereto, to produce the biocrude oil feed.

[0101] In a second general embodiment according to a first aspect of the present invention, a method for producing a hydrocarbon feed is also provided, including: - A hydrothermal liquefaction (HTL) step in an HTL unit of a solid feed stream or a solvolysis step in a solvolysis unit to produce a biocrude oil feed stream containing 10% by mass or less of O; - Supplying the biocrude oil feed to a hydrodeoxygenation or deoxygenation (HDO / DO) step in an HDO / DO reactor to produce a partially upgraded (partially deoxygenated) biocrude oil feed containing 2 to 8% by mass of O; - Providing a feed of vegetable oil and / or fatty substances; - Optionally in further combination with additional feeds, combining the partially deoxygenated biocrude oil feed with the vegetable oil and / or fatty substance feed to produce the hydrocarbon feed; - The method does not have a stabilization step in a stabilization reactor before supplying the biocrude oil feed to the HDO / DO step.

[0102] The HTL step or the solvolysis step has been found to supply a bio-crude oil feedstock with a low oxygen (O) content of 11% by mass or less, or 10% by mass or less, enabling the stabilization of this feedstock. Therefore, it becomes unnecessary to provide a stabilization reactor, thereby enabling a simpler process and plant layout.

[0103] In a third general embodiment according to the first aspect of the present invention, a method for producing a hydrocarbon feedstock is also provided, including the following: - Providing a bio-crude oil feedstock containing more than 10% by mass of oxygen (O); - Supplying the bio-crude oil feedstock to the stabilization step of a stabilization reactor to produce a stabilized bio-crude oil feedstock with less O than the bio-crude oil feedstock; - Supplying the stabilized bio-crude oil feedstock to the hydrodeoxygenation or deoxygenation (HDO / DO) step in an HDO / DO reactor to produce a partially deoxygenated (partially upgraded) bio-crude oil feedstock, which contains less than 10% by mass of O and at least 0.1% by mass of O, that is, the bio-crude oil feedstock contains 0.1 - 10% by mass of O, for example, 0.1 - 9% by mass of O, 2 - 7% by mass of O, 2 - 8% by mass of O, 2 - 10% by mass of O and less O than the stabilized bio-crude oil feedstock; - Providing a supply of vegetable oil and / or fatty substances; - Combining the partially deoxygenated bio-crude oil feedstock with the vegetable oil and / or fatty substances feedstock to produce the hydrocarbon feedstock, and optionally further combining with additional feedstocks.

[0104] For example, the partially deoxygenated bio-crude oil feedstock contains any one of 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0% by mass of O.

[0105] It is understood that any embodiments according to the first general aspect of the first aspect of the present invention can use the associated benefits in relation to the second and third general aspects of the first aspect of the present invention.

[0106] In a second aspect, the present invention also contemplates a plant for implementing a method according to any of the above aspects according to the first general aspect of the first aspect of the present invention.

[0107] The plant includes the following: - A stabilization reactor arranged to receive a bio-crude oil containing more than 10% by mass of oxygen (O) and supply a stabilized bio-crude oil supply having less O than the bio-crude oil supply; - A hydrodeoxygenation or deoxygenation (HDO / DO) reactor (HDO / DO reactor) arranged to receive the stabilized bio-crude oil supply, contain 2 to 10% by mass of O, and provide a partially deoxygenated bio-crude oil supply having less O than the stabilized bio-crude oil supply; - A conduit for providing a vegetable oil and / or fatty substance supply; - A mixing point for combining the partially deoxygenated bio-crude oil supply and the vegetable oil and / or fatty substance supply to provide a hydrocarbon supply.

[0108] In one embodiment, the stabilization reactor is arranged for continuous operation mode in a fixed-bed reactor under hydrogenation, and the fixed-bed reactor contains any one of Ni-Mo, Co-Mo, Ni-Cu, Mo, Pt, Pd, Ru, or Ni-based catalysts; and the stabilization reactor further operates at a temperature of 20 to 240 °C, a pressure of 100 to 200 barg, optionally, a liquid hourly space velocity (LHSV) of 0.1 to 1.1 h -1 and a hydrogen / liquid oil ratio defined as the volume ratio of hydrogen to the flow rate of the liquid oil flow of 1000 to 6000 NL / L, for example 2000 to 5000 NL / L.

[0109] In an embodiment, the plant further includes a downstream catalyst bed of the HDO / DO reactor, or a downstream HDO / reactor, and provides a first hydrogenated feed.

[0110] In one embodiment, the plant further includes a downstream hydrogenation section arranged to receive the first hydrogenated feed and supply a second hydrogenated feed.

[0111] In an embodiment, the plant further includes a separation section arranged to receive the first hydrogenated feed or the second hydrogenated feed and provide a hydrocarbon product, wherein the hydrocarbon product is any one of naphtha, diesel, jet fuel, marine (ship) fuel as a heavy fraction, or a combination thereof.

[0112] In an embodiment, the plant further includes a conduit for providing an additional feed, which is arranged to combine with either a partially deoxygenated biocrude oil feed, a vegetable oil and / or a fatty substance feed; the additional feed is any one of the following: A fossil feed, such as diesel, kerosene, naphtha, vacuum gas oil (VGO), and / or, An intermediate hydrocarbon product, such as recycled oil, that is, a recycled oil obtained by reusing a part of the intermediate hydrocarbon product produced in the plant, such as a part of the first or second hydrogenated feed.

[0113] In one embodiment, the plant further includes an HDI reactor and / or an HCR reactor, which are arranged to receive the diesel and the marine (ship) fuel as a heavy fraction or a combination thereof, and are arranged to provide the intermediate hydrocarbon product, such as the intermediate hydrocarbon product produced within the method.

[0114] The present invention also relates to a plant for implementing a method according to a second general embodiment of the first aspect of the present invention. The plant comprises the following: - A hydrothermal liquefaction (HTL) unit or a solvolysis unit arranged to receive a solid feed stream for generating a biocrude oil feed stream containing 10% by mass or less of O; - A hydrodeoxygenation or deoxygenation (HDO / DO) reactor (HDO / DO reactor) arranged to receive the biocrude oil feed stream and provide a partially deoxygenated biocrude oil feed containing 2 to 8% by mass of O; - A conduit for providing a feed of vegetable oil and / or fatty substances; - A mixing point for combining the partially deoxygenated biocrude oil feed with the vegetable oil and / or fatty substance feed to provide a hydrocarbon feed; - Further, there is no stabilization reactor upstream of the HDO / DO reactor in the plant, i.e., no stabilization reactor is arranged between the HTL unit or the solvolysis unit.

[0115] It is understood that any of the embodiments according to the first aspect of the present invention can be used in connection with the second aspect of the present invention.

Brief Description of the Drawings

[0116]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

[0117] Referring to FIG. 1, a method / plant (method and / or plant) according to an embodiment of the present invention is shown. For example, a bio-crude feed 1 containing 45% by mass of O is fed together with hydrogen 3 into a stabilization reactor 10 operated at, for example, 80 to 250° C., thereby producing a stabilized bio-crude feed 5 containing less O than the bio-crude feed 1, for example 40% by mass of O. The stabilized bio-crude feed 5 is fed into an HDO / DO reactor 12 to produce a partially deoxygenated bio-crude feed 7 containing 2 to 10% by mass of O, for example 2 to 7% by mass of O. A vegetable oil and / or fatty substance feed 9 is provided and combined with the partially deoxygenated bio-crude feed 7 to produce a hydrocarbon feed 11. The hydrocarbon feed 11 is fed into the next HDO / DO reactor 14, thereby producing a first hydroprocessed feed 13, which can be fed into a next hydroprocessing step, for example a downstream hydroprocessing step (not shown). In a further downstream separation section, here, hydrocarbon products such as naphtha 19' and heavy fraction 19' in addition to diesel 19 are produced, as schematically shown by a separator 16. A water stream 15 as well as an offgas stream 17 containing NH3, H2S and C 1-4 hydrocarbons is also withdrawn.

[0118] Referring to FIG. 6, a method / plant (method and / or plant) according to another embodiment of the present invention is shown. For example, a biocrude oil feed 101 containing 45% by mass of O is supplied together with hydrogen 103 to a stabilization reactor 110 operating at, for example, 80 to 250° C., thereby producing a stabilized biocrude oil feed 105 containing less O than the biocrude oil feed 101, for example, 40% by mass of O. The stabilized biocrude oil feed 105 is supplied to an HDO / DO reactor 112 to produce a partially deoxygenated biocrude oil feed 107 containing 2 to 10% by mass of O, for example, 2 to 7% by mass of O. A vegetable oil and / or fatty substance feed 109 is provided and hydrotreated in an HDO / DO reactor 118, thereby producing a hydrotreated vegetable oil and / or fatty substance feed 111, which is then combined with the partially deoxygenated biocrude oil feed 107. Additional feeds such as the intermediate hydrocarbon product 121 produced by this method are further combined, thereby producing a hydrocarbon feed 113, which can then be supplied to the next hydroprocessing step, for example, in a downstream hydroprocessing section (not shown). In the downstream separation section, although also schematically shown by a separator 116, hydrocarbon products such as diesel 119, as well as naphtha 119' and heavy fraction 119'' are produced. A water stream 115, as well as an offgas stream 117 containing NH3, H2S and C 1-4 is also withdrawn. The heavy fraction 119'' is hydrocracked in an HCR reactor 120 to produce an intermediate hydrocarbon product 121. In addition to the HCR reactor for producing the intermediate hydrocarbon product 121, an HDI reactor (not shown) can also be provided instead of the HCR reactor. The stabilized biocrude oil feed 105, the vegetable oil and / or fatty substance feed 109, and the heavy end stream 119'' are therefore hydrotreated separately before being combined into the hydrocarbon feed 113.

Example

[0119] Example 1 Miscibility of biocrude oil and vegetable oil (soybean oil) The composition of the used soybean oil is shown in Table 1.

[0120]

Table 1

[0121] The overview of the used bio-crude oil feedstock (bio-crude oil) is shown in the following table:

Table 2

[0122] Miscibility was first tested by using a spot test for visual detection of miscibility, which was done by mixing bio-crude oil with soybean oil and adding one droplet of the mixture to a filter. The spot test for visual detection of miscibility is the miscibility test used in P. Manara et al, “Study on phase behavior and properties of binary blends of bio-oil / fossil-based refinery intermediates: A step toward bio-oil refinery integration”; Energy Conversion and Management 165 (2018) 304-315.

[0123] As shown in Figure 2, bio-crude oils A, B, and D are immiscible with soybean oil, while bio-crude oils C and E are miscible with soybean oil and appear at the naked-eye level. Bio-crude oils C and E have the highest oxygen (O) content and seem to be the most miscible among vegetable oils.

[0124] It should be noted that when bio-crude oils A and B are mixed with soybean oil, solids precipitate. Therefore, if these feedstocks are co-processed with soybean oil in an industrial or pilot unit, the reactor and pipes will be quickly blocked.

[0125] However, when 10 wt% and 50 wt% of soybean oil in bio-crudes C and E were studied using an optical microscope, it was shown that they were immiscible in bio-crudes C and E (see Figure 3).

[0126] The miscibility of three partially deoxygenated (via HDO) catalytic pyrolysis oils was also investigated, and their compositions are shown in Table 3. The results of the spot test and optical microscope are shown in Figures 4 and 5, which indicate that these partially deoxygenated bio-crudes having an oxygen content in the range of 2 - 10 wt%, for example 2 - 8 wt%, are miscible with soybean oil when using a 1:1 mass ratio (50 wt% soybean oil). Lower mass ratios, for example 1:9 (10 wt% partially deoxygenated bio-crude and 90 wt% soybean oil), can increase the miscibility.

[0127]

Table 3

[0128] Therefore, it is possible to co-process vegetable oils and fatty acids with advanced biofuels, i.e., advanced bio-crudes, which will become miscible with vegetable oils after reducing the oxygen content in the advanced biofuels to 10 - 2 wt% by partial deoxygenation, for example at a medium severity. At this medium severity, a high concentration of aromatics is maintained and the formation of heavy ends is reduced.

[0129] Example 2 Co-processing of soybean oil with hydrotreated catalyst fast pyrolysis (CFP) oil Soybean oil with a cloud point of -7.3 and a pour point of -12.0 °C was hydrogenated in a fixed-bed once-through hydrogenation unit. The cloud point of the produced hydrogenated soybean oil was 22.7 °C and the pour point was 21.0 °C. When the hydrogenated soybean oil was mixed with catalytic fast pyrolysis oil (ratio 20 / 80 v / v), the cloud point and pour point of the feed decreased to -15.0 and -12.0 °C, respectively. Also, the cloud and pour points of the hydrogenated oil decreased to 17.3 and 18.0 °C, respectively. The cloud points and pour points of the feed and product are shown in Table 4, and the oxygen, hydrogen and specific gravity (SG) are shown in Table 5. The cloud point and pour point of the hydrogenated catalytic fast pyrolysis oil used could not be measured because it was too dark for this method. However, it was possible to measure the cloud point and pour point of another similar oil (hydrogenated in the same experiment). This oil had a cloud point and pour point of -19.9 and -21.0 °C and an oxygen content of 1.5 mass%.

[0130] This indicates that the co-treatment of soybean oil and hydrogenated catalytic fast pyrolysis reduces the cloud point and pour point compared to the independent hydrogenation of soybean oil, thus reducing the need for isomerization and the yield loss associated with isomerization.

[0131]

Table 4

[0132]

Table 5

Claims

1. A method for producing a hydrocarbon feedstock comprising the following steps: - providing a biocrude feedstock containing more than 10% by mass of oxygen (O); - feeding the biocrude feedstock to a stabilization step in a stabilization reactor to produce a stabilized biocrude feedstock having less O than the biocrude feedstock; - feeding the stabilized biocrude feedstock to a hydrodeoxygenation or deoxygenation (HDO / DO) step in an HDO / DO reactor to produce a partially deoxygenated biocrude feedstock containing 2-10% by mass of oxygen (O) and having less O than the stabilized biocrude feedstock; - providing a vegetable oil and / or fatty substance feedstock; - producing the hydrocarbon feedstock by combining the partially deoxygenated biocrude feedstock with the vegetable oil and / or fatty substance feedstock.

2. The method according to claim 1, wherein the biocrude feedstock contains at least 15% by mass of O, or at least 30% by mass of O, for example, 35-70% by mass of O, for example 40-60% by mass of O or 40-50% by mass of O.

3. The method according to any one of claims 1-2, wherein the biocrude feedstock contains 40-60% by mass of O and the stabilized biocrude feedstock contains 20-55% by mass of O.

4. The stabilization step is carried out in a fixed-bed reactor in continuous operation mode, in the presence of any of the following; in the presence of any of Ni-Mo, Co-Mo, Ni-Cu, Mo, Pt, Pd, Ru, or Ni-based catalysts, at a temperature of 20 - 240 °C, a pressure of 100 - 200 barg, optionally at a liquid hourly space velocity (LHSV) of 0.1 - 1.1 h －１ and a hydrogen-to-liquid oil ratio defined as the volume ratio of hydrogen to the flow rate of the liquid oil stream of 1000 - 6000 NL / L, for example 2000 - 5000 NL / L, comprising feeding the biocrude feed together with hydrogen, thereby forming the stabilized biocrude feed, the method according to any one of claims 1 to 3.

5. - a step of feeding the hydrocarbon feedstock to a subsequent HDO / DO step to produce a first hydroprocessed feedstock, wherein the subsequent HDO / DO step is: performed in a catalyst bed downstream of the HDO / DO reactor for producing the partially deoxygenated biocrude feedstock, or in a downstream HDO / DO reactor. The method according to any one of claims 1-4, further comprising.

6. The method according to any one of claims 1-5, further comprising feeding the first hydroprocessed feedstock to subsequent hydroprocessing steps in a downstream hydroprocessing section, for example, a hydroisomerization (HDI) step in an HDI reactor, and / or a hydrocracking (HCR) step in an HCR reactor, and / or a hydrodearomatization (HDA) step in an HDA reactor to produce a second hydroprocessed feedstock.

7. - further comprising supplying the first hydroprocessed feed or the second hydroprocessed feed to a separation step in a separation section to produce a hydrocarbon product, The method according to any one of claims 5 to 6, wherein the hydrocarbon product is any one of naphtha, diesel, jet fuel, marine (ship) fuel as a heavy fraction, or a combination thereof. **Claim 8** The mass ratio (A:B) of the partially deoxygenated biocrude oil feed (A) to the vegetable oil and / or fatty substance feed (B) is in the range of 50:50% by mass to 10:90% by mass; optionally, the subsequent HDO / DO step for producing the first hydroprocessed feed is carried out in continuous mode under the conditions of a temperature of 250 to 400 °C and a pressure of 50 to 150 bar using a fixed bed catalyst in which the catalyst is NiMoS and / or MoS. The method according to any one of claims 1 to 7. **Claim 9** The method according to any one of claims 1 to 7, wherein the mass ratio (A:B) of the partially deoxygenated biocrude oil feed (A) to the vegetable oil and / or fatty substance feed (B) is in the range of 50:50% by mass to 90:10% by mass. **Claim 10** further comprising a pyrolysis step of a solid feed stream in a pyrolysis unit selected from a pyrolysis step in a pyrolysis unit, a hydrothermal liquefaction (HTL) step in an HTL unit, or a hydrolysis step in a solvolysis unit, thereby producing a biocrude oil feed containing more than 10% by mass of O. The method according to any one of claims 1 to 9. **Claim 11** - a solid feed stream comprising at least 50% by mass, such as at least 60% by mass, or at least 70% by mass, or at least 80% by mass, or at least 90% by mass of a renewable solid feedstock, such as lignocellulosic biomass, municipal waste and / or recycled solid waste, is supplied to the pyrolysis unit to produce a pyrolysis oil stream, or an HTL oil stream, or a solvolysis oil stream as the biocrude oil feed containing more than 10% by mass of O. The method according to claim 10. **Claim 12** The method according to any one of claims 1 to 11, wherein the vegetable oil and / or fatty substance feed is a hydrogenated vegetable oil and / or fatty substance feed, such as a hydrogenated vegetable oil and / or fatty substance feed.

13. The method according to any one of claims 1 to 12, wherein the vegetable oil and / or fatty substance feed is any one of soybean oil, rapeseed oil, corn oil, castor oil, cooked oil, animal fat, and combinations thereof.

14. The method according to any one of claims 1 to 13, wherein the step of combining the partially deoxygenated bio-crude oil feed with the vegetable oil and / or fatty substance feed is further combined with an additional feed; the additional feed being: A fossil feed, such as diesel, kerosene, naphtha, vacuum gas oil (VGO), and / or An intermediate hydrocarbon product, such as recycled oil, i.e., a recycled oil obtained by reusing a part of the intermediate hydrocarbon product produced by the method, such as a part of the first or second hydrogenated feed. The method as described above.

15. The method according to any one of claims 7 to 14, further comprising supplying the diesel and the marine (ship) fuel as heavy components or combinations thereof to a hydroisomerization (HDI) step in an HDI reactor and / or a hydrocracking (HCR) step in an HCR reactor to provide the intermediate hydrocarbon product, such as the intermediate hydrocarbon product produced within the method.

16. A method for producing a hydrocarbon feed, comprising: - A hydrothermal liquefaction (HTL) step in an HTL unit of a solid feed stream or a solvolysis step in a solvolysis unit to produce a bio-crude oil feed stream containing 10% by mass or less of O; - Supplying the bio-crude oil feed to a hydrodeoxygenation or deoxygenation (HDO / DO) step in an HDO / DO reactor to produce a partially upgraded (partially deoxygenated) bio-crude oil feed containing 2 to 8% by mass of O; - Providing a vegetable oil and / or fatty substance feed; - Optionally further combining with an additional feed, combining the partially deoxygenated bio-crude oil feed with the vegetable oil and / or fatty substance feed to produce the hydrocarbon feed. comprising; - in the case where there is no stabilization step in a stabilization reactor before the bio-crude oil feed is supplied to the HDO / DO step in the method, the method.

17. A plant for implementing the method according to any one of Claims 1 to 15, - a stabilization reactor arranged to receive bio-crude oil containing more than 10% by mass of oxygen (O) and to supply a stabilized bio-crude oil feed having less O than the bio-crude oil feed; - a hydrodeoxygenation or deoxygenation (HDO / DO) reactor (HDO / DO reactor) arranged to receive the stabilized bio-crude oil feed, to contain 2 to 10% by mass of O, and to provide a partially deoxygenated bio-crude oil feed having less O than the stabilized bio-crude oil feed; - a conduit for providing a vegetable oil and / or fatty substance feed; - a mixing point for combining the partially deoxygenated bio-crude oil feed and the vegetable oil and / or fatty substance feed to provide a hydrocarbon feed; the plant comprising.

18. A plant for implementing the method according to Claim 16, - a hydrothermal liquefaction (HTL) unit, or a solvolysis unit, arranged to receive a solid feed stream for generating a bio-crude oil feed stream containing 10% by mass or less of O; - a hydrodeoxygenation or deoxygenation (HDO / DO) reactor (HDO / DO reactor) arranged to receive the bio-crude oil feed stream and to provide a partially deoxygenated bio-crude oil feed containing 2 to 8% by mass of O; - a conduit for providing a vegetable oil and / or fatty substance feed; - a mixing point for combining the partially deoxygenated bio-crude oil feed and the vegetable oil and / or fatty substance feed to provide a hydrocarbon feed; comprising, - further, there is no stabilization reactor upstream of the HDO / DO reactor; the plant.

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