Hydroprocessing of bio-crude oil with vegetable and / or fat materials

Abstract

The present application relates to a process and apparatus for producing a hydrocarbon feed comprising: providing a bio-crude oil feed comprising greater than 10 wt% oxygen (O); a stabilization step of supplying the bio-crude feed to a stabilization reactor to produce a stabilized bio-crude feed comprising less O than the bio-crude feed; supplying the bio-crude oil feed or optionally stabilized bio-crude oil feed to a hydrodeoxygenation or deoxygenation (HDO / DO) step in an HDO / DO reactor to produce a partially deoxygenated bio-crude oil feed comprising 2-10 wt% O; providing a vegetable oil and / or fat material feed; the partially deoxygenated bio-crude oil feed is combined with a vegetable oil and / or fat material feed to produce the hydrocarbon feed. The hydrocarbon feed may be further hydroprocessed into a hydrocarbon fuel.

Description

[0001] The present invention relates to a method and apparatus for hydroprocessing a biocrude feed produced by thermal decomposition of a solid feed stream together with a vegetable and / or fatty material feed.

[0002] Co-processing of hydrocarbon fuel feeds by combining fossil fuel feeds such as petroleum feeds with vegetable oil feeds in hydroprocessing is well known. However, biocrude produced by thermal decomposition (e.g., pyrolysis, hydrothermal liquefaction (HTL) or solvolysis) of solid renewable feeds (e.g., lignocellulosic biomass) is generally not miscible with vegetable oils and / or fatty materials including fatty acids, and thus, co-processing of these feeds in hydroprocessing steps (e.g., hydrodeoxygenation (HDO)) has been a significant challenge to overcome to date.

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

[0004] However, the applicant has found that vegetable oils are immiscible with most untreated catalytic pyrolysis oils and therefore it is very difficult to make them work in industrial hydrotreating reactors. Hydrotreating reactors processing co-feeds will plug after a few days of operation under industrially relevant conditions.

[0005] It has been found that while vegetable oils are immiscible with catalytic and non-catalytic pyrolysis and hydrothermal liquefaction (HTL) biocrudes, they are miscible with partially deoxygenated biocrudes, such as partially deoxygenated catalytic pyrolysis oils having an oxygen content of 2-10 wt% oxygen (O), such as 2-8 wt% O, or 2-7 wt% O.

[0006] Thus, in a first general embodiment according to the first aspect of the present invention, there is provided a method for producing a hydrocarbon feed comprising the steps of:

[0007] - providing a biocrude feed comprising greater than 10 wt% oxygen (O), such as up to 70 wt% O or up to 60 wt% O;

[0008] - supplying the biocrude feed to a stabilization step in a stabilization reactor to produce a stabilized biocrude feed comprising less O than the biocrude feed;

[0009] - supplying the stabilized biocrude feed to a hydrodeoxygenation or deoxygenation (HDO / DO) step in a HDO / DO reactor to produce a partially deoxygenated (partially upgraded) biocrude feed comprising 2-10 wt% O and comprising less O than the stabilized biocrude feed;

[0010] - providing a feed of vegetable oil and / or fatty material;

[0011] - Combining a partially deoxygenated biocrude feed with a vegetable oil and / or fatty material feed to produce said hydrocarbon feed.

[0012] For example, separate biocrude feeds comprising greater than 10 wt% oxygen (O) may be provided, or separate biocrude feeds may be combined into a single biocrude feed comprising greater than 10 wt% oxygen (O).

[0013] For example, a partially deoxygenated biocrude feed may be combined with a vegetable oil feed; or a partially deoxygenated biocrude feed may be combined with a fatty material feed, such as an animal fat feed.

[0014] For example, a partially deoxygenated biocrude feed may first be combined with a vegetable oil feed and then combined with a fatty material feed, such as an animal fat feed. Optionally, additional feeds may be provided.

[0015] In one embodiment, the vegetable oil and / or fatty material feed is a non-hydroprocessed vegetable oil and / or fatty material feed. Thus, the feed has not been subjected to a previous hydroprocessing step, such as hydrodeoxygenation (HDO).

[0016] Therefore, before the bio-crude feed is mixed with the vegetable oil and / or fatty material, the bio-crude feed is first stabilized and then partially deoxygenated. By stabilizing the bio-crude and further removing its oxygen content to the specific range of 2-10wt%, it can now be combined with the vegetable oil and / or fatty material feed without the risk of plugging the HDO / DO reactor or any related units, such as pumps and heat exchangers. In addition, the vegetable oil is used to cool the effluent from the HDO / DO reactor, i.e., the partially deoxygenated bio-crude feed, or as a cooling between catalytic beds in the HDO reactor. In addition, the formation of the heavy end fraction in the downstream separation section is reduced, thereby increasing the yield of diesel as a hydrocarbon fuel, for example. Although the oxygen (O) content below 2wt% in the bio-crude feed can help make it miscible with vegetable oil and / or fatty materials, such a low oxygen value is often accompanied by a low aromatic compound content. As will be further explained below, the presence of aromatic compounds is desirable because it enables the formation of heavy end fractions to be reduced when hydrocarbon products such as diesel and / or jet fuel are produced and / or separated downstream. The present invention provides a partial deoxygenation of a bio-crude feed with moderate severity, i.e. such that the oxygen content of the partially deoxygenated (partially upgraded) bio-crude feed is 2-10 wt% O while maintaining the aromatic compounds therein. For example, the aromatic compound content may be 20-60 wt% aromatic compounds (total), as measured according to ASTM D 6591.

[0017] For the purposes of this application, the term "first aspect of the invention" relates to the method. The term "second aspect of the invention" refers to the process equipment, ie the equipment.

[0018] The terms "present invention" and "this application" are used interchangeably.

[0019] The term "comprising" includes "comprising only", ie "consisting of.

[0020] The term "suitably" is used interchangeably with the term "optionally", ie an optional embodiment.

[0021] The term "partially deoxygenated biocrude feed" may be used interchangeably with the term "partially upgraded biocrude feed."

[0022] The term "biocrude feed" refers to the liquid oil product of the thermal decomposition step in the thermal decomposition unit. The biocrude feed may also be understood as "advanced biocrude". The thermal decomposition unit is a pyrolysis unit, a hydrothermal liquefaction (HTL) unit or a solvolysis unit. The term "unit" is understood herein as a "reactor".

[0023] The term "vegetable oil feed and / or fatty material" includes vegetable oils such as soybean oil and fatty materials such as animal fats. Fatty materials include fatty acids.

[0024] The term "section," such as "hydroprocessing section," refers to a physical section that contains a unit or combination of units used to perform one or more steps and / or sub-steps to produce a hydroprocessing feed.

[0025] The term "hydroprocessing" includes hydrotreating, and thus includes hydrodeoxygenation or deoxygenation (HDO / DO). The term "hydroprocessing" also includes hydroisomerization (HDI), or hydrocracking (HCR), or hydrodearomatization (HDA). It should be understood that the hydroprocessing step, such as the HDO / DO step, is carried out in a hydroprocessing reactor, such as an HDO / DO reactor, or in a catalytic bed of a hydroprocessing reactor, such as a catalytic bed of an HDO / DO reactor. Other definitions will be explained below in association with one or more embodiments of the present invention.

[0026] In one embodiment, the biocrude feed comprises at least 15 wt% O, or at least 30 wt% O, such as 35-70 wt% O, such as 40-60 wt% O or 40-50 wt% O.

[0027] In principle, the higher the oxygen (O) content, the more reactive the biocrude feed is, and therefore the higher the tendency to form solid particles or aggregates and thus plug the HDO / DO reactor and related units. For example, the composition of the biocrude feed is 45 wt% C, 9 wt% H and 46 wt% O, which is a typical pyrolysis oil, while a typical vegetable oil (such as soybean oil) may have 79 wt% C, 12 wt% H and 12 wt% O.

[0028] In one embodiment, the biocrude feed comprises 40-60 wt% O and the stabilized biocrude feed comprises 20-55 wt% O.

[0029] Therefore, the oxygen content in the stabilized bio-crude feed is suitably ~5% or ~10% or ~20% relative to, i.e. based on, the oxygen content of the bio-crude feed. For example, the bio-crude feed may have 45wt% O, and the stabilized bio-crude feed may have 40wt% O or 35wt% or 25w% O.

[0030] Suitably, in the combining step, the weight ratio (A:B) of the partially upgraded (partially deoxygenated) biocrude feed (A) to the vegetable oil and / or fatty material feed (B) is in the following range: 9:1 (i.e., wt% ratio of 90:10) to 1:9 (i.e., wt% ratio of 10:90); for example, 4:1 (i.e., wt% ratio of 80:20), 3:1 (i.e., wt% ratio of 75:25), 2:1 (i.e., wt% ratio of 66.6:33.3); 1:1 (i.e., wt% ratio of 50:50); 1:2 (i.e., wt% ratio of 33.3:66.6). For example, 1:3 (i.e., wt% ratio of 25:75), 1:4 (i.e., wt% ratio of 20:80), 1:5 (i.e., wt% ratio of 17:83), 1:6, for example, 1:5.7 (i.e., wt% ratio of 15:85).

[0031] In one embodiment, the stabilization step is carried out in a fixed bed reactor in a continuous operation mode, comprising supplying hydrogen to the bio-crude feed in the presence of any one 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, and optionally a liquid hourly space velocity (LHSV) of 0.1-1.1 h -1 , and the ratio of hydrogen to liquid oil (bio-crude feed) is 1000-6000NL / L, for example 2000-5000NL / L, thereby forming the stabilized bio-crude feed, and the ratio of hydrogen to liquid oil is defined as the volume ratio of hydrogen to liquid oil flow.

[0032] 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 titanium dioxide), or a Pt / TiO2 based catalyst.

[0033] The terms "Ni-Mo based catalyst", "Co-Mo based catalyst" and the like mean that Ni-Mo are active elements of the catalyst.

[0034] Suitably, Ni—Mo, Co—Mo or Mo is in a sulphided form, such as NiMoS. Also suitably, Ni is in a sulphided or reduced form.

[0035] The term "stabilization" refers to the conversion of carbonyl groups present in liquid oil compounds such as (e.g., aldehydes, ketones, and acids) into alcohols. Other molecules (e.g., sugars and furans) may also be converted in the stabilization step. For example, the stabilization step may be carried out by a NiMo-based catalyst, as disclosed in Shumeico et al. in "Efficient one-stage bio-oil upgrading oversulfide catalysts", ACS Sustainable Chem. Eng. 2020, 8, 15149-15167. Suitably, stabilization is carried out according to the method disclosed in the applicant's co-pending European patent application 21152117.4 (corresponding to international application PCT / EP 2022 / 050877).

[0036] As used herein, the term "stabilization" or "stabilization step" is also well known in the art and refers to a step carried out in a stabilization reactor, wherein, for example, the oxygen content in the bio-crude feed is reduced to avoid the formation of solid particles or aggregates, which may plug the HDO / DO unit and related equipment arranged downstream. As already stated, the oxygen content (O content, in wt%) in the stabilized bio-crude feed is, for example, 5% or 10% or 20% relative to the bio-crude feed.

[0037] Applicants have found that even when a biocrude feed having a low oxygen content (e.g., produced by catalytic fast pyrolysis (CFP) having about 14 wt% O) is combined (i.e., co-processed) with a typical vegetable oil having an inherently lower oxygen content (e.g., about 11 wt% O) in a small hydroprocessing unit (HDO unit), the unit becomes clogged after a few days, and therefore some stabilization treatment is required before the catalytic pyrolysis oil is sufficiently stable for further hydrodeoxygenation.

[0038] Furthermore, making bio-crude oils properly miscible with vegetable oils etc. is extremely challenging because the miscibility of bio-crude oils is not directly linked to oxygen content. As shown in the further examples below (Example 1), the bio-crude oil samples that initially appeared more miscible in vegetable oils were the samples with the highest oxygen content (Samples C and E).

[0039] In one embodiment, the method further comprises:

[0040] - supplying the hydrocarbon feed to a subsequent HDO / DO step to produce a first hydroprocessed feed, e.g., a hydrotreated feed; wherein the subsequent HDO / DO step is carried out in:

[0041] a downstream catalytic bed of said HDO / DO reactor producing said partially deoxygenated biocrude feed; or

[0042] Downstream HDO / DO reactor.

[0043] The term "first hydroprocessed feed" may be used interchangeably with the term "hydrotreated feed" to refer to the effluent stream from the HDO / DO reactor that processes the combined feed (co-feed). It will be appreciated that while deoxygenation (DO) is strictly speaking absent (e.g., by added) hydrogen, it is still considered a hydroprocessing step for purposes of this application.

[0044] Therefore, several layouts have been proposed; for example:

[0045] - providing at least two HDO / DO reactors, wherein the oxygen content is reduced to 2-10 wt% for pyrolysis oil and 2-8 wt% for HTL oil or solvolysis oil; then mixing vegetable oil with the product from the first HDO / DO reactor and sending the mixture to the subsequent (second) HDO / DO reactor.

[0046] - Only one HDO / DO reactor is provided and the vegetable oil is co-processed by feeding the vegetable oil into the lower bed in the HDO / DO reactor.

[0047] The present application enables co-processing of vegetable oils and / or fatty materials, such as fatty acids, with HTL oils or pyrolysis oils or solvolysis oils, which would not otherwise be feasible. In addition, the vegetable oils, for example, are used to cool the products from the first HDO / DO reactor, or as cooling between beds in the first HDO reactor. In addition, the effluent from the HDO / DO of, for example, the HTL, i.e., the partially deoxygenated biocrude feed containing 2-10 wt% O, can be highly aromatic, while the product from the HDO of the vegetable oil is highly paraffinic, thus co-processing results in better quality diesel compared to the HDO of the HTL oil alone, or the pyrolysis oil alone, or the solvolysis oil alone.

[0048] In one embodiment, the method further comprises:

[0049] - supplying the first hydroprocessed feed (e.g., hydrotreated feed) to a subsequent hydroprocessing step in a downstream hydroprocessing section, such as 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 feed.

[0050] Thus, the subsequent hydroprocessing step comprises treating the hydrotreated feed in one or more additional catalytic hydroprocessing units (e.g., a third catalytic hydroprocessing unit or a cracking section) with the addition of hydrogen. For example, it will be appreciated that when a hydrocarbon product boiling in the jet fuel range is desired, such as before sending the thus hydroprocessed stream to HDI, a hydrocracking (HCR) unit is suitably used.

[0051] Typically, pyrolysis oil contains a large amount of oxygenates and unsaturated hydrocarbons. During hydrotreatment of this feed, oxygen is removed primarily in the form of H2O, which results in a fuel composed primarily of naphthenes and aromatics. This is known as the hydrodeoxygenation (HDO) pathway. Oxygen can also be removed via the decarboxylation pathway, which produces CO2 instead of H2O:

[0052] HDO pathway:

[0053] Decarboxylation pathway:

[0054] Furthermore, while decarbonylation is generally not dominant in the HDO of triglycerides in typical renewable feeds, it can be more dominant during the HDO of pyrolysis oils:

[0055] Decarbonylation pathway: RCH2COH+H2<->RCH3+CO

[0056] Materials catalytically active in HDO (as used herein interchangeably with the term hydroprocessing) typically comprise an active metal (a sulfided base metal such as nickel, cobalt, tungsten and / or molybdenum, but also possibly an elemental noble metal such as platinum and / or palladium) and a refractory support such as alumina, silica or titania, or a combination thereof.

[0057] HDO conditions involve temperatures in the range of 250-400°C, pressures in the range of 30-150 bar, and liquid hourly space velocities (LHSV) in the range of 0.1-2, optionally together with intermediate cooling by quenching with cold hydrogen, feed or product.

[0058] Materials having catalytic activity in the hydroisomerization of HDI generally 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 (generally a molecular sieve showing high shape selectivity and having a topology such as MOR, FER, MRE, MWW, AEL, TON and MTT) and a refractory support (e.g., alumina, silica or titania, or a combination thereof).

[0059] The HDI conditions involve a temperature in the range of 250-400°C, a pressure in the range of 20-100 bar and a liquid hourly space velocity (LHSV) in the range of 0.5-8.

[0060] The materials catalytically active in hydrocracking (HCR) have similar properties to those catalytically active in isomerization and generally comprise active metals (elemental noble metals such as platinum and / or palladium or sulfided base metals such as nickel, cobalt, tungsten and / or molybdenum), an acidic support (generally a molecular sieve showing high cracking activity and having a topology such as MFI, BEA and FAU) and a refractory support (such as alumina, silica or titania or a combination thereof). The difference to the materials catalytically active in isomerization is generally the nature of the acidic support, which may have a different structure (even amorphous silica-alumina) or have a different acidity, for example due to the silica / alumina ratio.

[0061] HCR conditions include temperatures in the range of 250-400°C, pressures in the range of 30-150 bar, and liquid hourly space velocities (LHSV) in the range of 0.5-8, optionally together with intermediate cooling by quenching with cold hydrogen, feed or product.

[0062] The materials that are catalytically active in HDA typically comprise an active metal (usually an elemental noble metal such as platinum and / or palladium, but may also be a sulfided base metal such as nickel, cobalt, tungsten and / or molybdenum) and a refractory support (e.g., amorphous silica-alumina, alumina, silica or titania, or a combination thereof).

[0063] HDA conditions involve a temperature in the range of 200-350°C, a pressure in the range of 20-100 bar or 20-200 bar, and a liquid hourly space velocity (LHSV) in the range of 0.5-8.

[0064] In one embodiment, the method comprises:

[0065] - supplying the first hydroprocessed feed or the second hydroprocessed feed to a separation step in a separation section to produce a hydrocarbon product, the hydrocarbon product being any one of: naphtha, diesel, jet fuel, marine (ship) fuel as a heavy end fraction, or a combination thereof.

[0066] Therefore, marine (bunker) fuel is suitably taken as the heavy ends fraction.

[0067] In one embodiment, the weight ratio (A:B) of the partially upgraded (partially deoxygenated) biocrude feed (A) to the vegetable oil and / or fatty material feed (B) is in the range of 1:1, i.e. 50:50 wt% (i.e. 1:1) to 10:90 wt% (i.e. 1:9), for example 20:80 wt% (i.e. 1:4) or 15:85 wt% (1:5.7); and optionally, the subsequent HDO / DO step is carried out in a continuous mode under the following conditions: 250-400°C, for example 350-380°C, at a pressure of 50-150 bar, for example 100 bar, and using a fixed bed catalyst whose catalyst is NiMoS and / or MoS.

[0068] At the above weight ratio (A:B), the best results in terms of cetane index and compliance with specification (EN 590 specification) were achieved. Furthermore, providing a MoS catalyst, for example by loading it on top of the HDO / DO reactor, further reduces the formation of heavy ends.

[0069] It is to 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.

[0070] Suitably, the stabilization reactor and any hydroprocessing reactors such as the HDO / DO reactor or the HDI or HCR reactor or the HDA reactor are adiabatic fixed bed reactors.

[0071] As described above, co-treatment at these weight ratios and providing a specific combination of NiMoS and / or MoS catalysts in the subsequent HDO / DO step can reduce the heavy end fraction (C18+ formation). Thus, the production of diesel in the C15-C18 range is increased.

[0072] In one embodiment, the desired downstream hydrocarbon product is diesel, which is suitably represented by C15-C18 hydrocarbons as a hydrocarbon product boiling in the range of transportation fuels. Hydrocarbons with carbon numbers higher than 18 (C18+) can be taken out downstream of the separation section as a heavy end fraction (also referred to herein as a heavy end fraction), however it is desirable to reduce the heavy end fraction portion, thereby increasing the yield of the C15-C18 portion, and thus increasing the yield of diesel fuel. It has been found that when a partially deoxygenated biocrude is provided in a co-feed, for example, when provided in a weight range as described above (50:50wt% to 10:90wt%), there is a lower heavy end fraction yield while still maintaining the appropriate miscibility of the feed. Without being bound by any theory, it is believed that the aromatic compounds in the partially deoxygenated biocrude feed act as hydrogen donors, thereby reducing the formation of heavy end fractions. When processing the heavy end fraction, the conventional method is to hydrocracking the heavy portion of the product to remove the heavy end fraction. However, hydrocracking results in yield losses; therefore, minimizing the formation of heavy ends can increase the overall yield of the process, here particularly diesel yield.

[0073] In another embodiment, the weight ratio (A:B) of partially upgraded (partially deoxygenated) biocrude feed (A) to vegetable oil and / or fatty material feed (B) is 50:50 wt% to 90:10 wt%; and optionally, any HDO / DO step is carried out in a continuous mode under the following conditions: 250-400°C, for example 340-400°C, at a pressure of 50-150 bar, using a fixed bed catalyst, wherein the catalyst is NiMoS and / or MoS.

[0074] Therefore, the weight ratio (A:B) of the partially deoxygenated biocrude feed (A) to the vegetable oil and / or fatty material feed (B) is in the range of 50:50 wt% to 90:10 wt%, such as 80:20 wt% or 75:25 wt%. For example, 80 vol.% of hydrotreated catalytic fast pyrolysis oil can be used as partially deoxygenated biocrude (A) and has an oxygen (O) content of about 2 wt%, with 20 vol.% of soybean oil as vegetable oil (B), which reduces the cloud point and pour point of the mixture compared to the separate hydrotreatment of soybean oil. This brings a benefit that the need for hydroisomerization (HDI) is reduced, and therefore, the associated yield loss during the hydroisomerization process is also reduced. As a result, the capital expenditure (CAPEX) and operating expenditure (OPEX) of the isomerization process are also reduced.

[0075] As is well known in the art, the cloud point of any petroleum product is an indicator of how the hydrocarbon product (e.g., diesel) will behave under cold weather conditions. The pour point is the opposite of the cloud point and refers to the lowest temperature at which oil movement is observed so that diesel can be pumped.

[0076] Suitably, the subsequent HDO / DO step is carried out in continuous mode at 250-400°C, such as 350-380°C, at a pressure of 50-150 bar, such as 100 bar, and using a fixed bed catalyst, wherein the catalyst is NiMoS and / or MoS.

[0077] At the above weight ratio (A:B), for example by combining hydroprocessed (e.g., hydrotreated) waste tire pyrolysis oil and hydrotreated vegetable oil (e.g., HVO), the resulting diesel shows desirable results in terms of cetane index and compliance with specifications (EN 590 specifications), including improved low temperature flow properties (in terms of cloud point). In addition, a MoS catalyst is provided, for example by loading it on top of the HDO / DO reactor, which further reduces the formation of heavy end fractions.

[0078] In one embodiment, the method further comprises a thermal decomposition step of the solid feed stream in a thermal decomposition unit, wherein the thermal decomposition unit is selected from a thermal decomposition step in a thermal decomposition unit (pyrolysis reactor) and a hydrothermal liquefaction (HTL) step in a HTL unit or a solvent decomposition step in a solvent decomposition unit, thereby producing the biocrude feed stream containing greater than 10 wt% O.

[0079] In one embodiment, the thermal decomposition step is a pyrolysis step, such as a flash pyrolysis step.

[0080] The pyrolysis step may include the use of a pyrolysis unit, such as a fluidized bed, a conveyed bed, or a circulating fluidized bed, as is known in the art. For example, the pyrolysis step may include the use of a pyrolysis unit (also referred to herein as a pyrolysis reactor), a cyclone separator (for removing particulate solids, such as char), and a cooling unit to produce the first waste gas stream (i.e., pyrolysis waste gas) and the first liquid oil stream, i.e., condensed pyrolysis oil. The first waste gas stream contains light hydrocarbons, such as C1-C4 hydrocarbons, CO, and CO2. The first liquid oil stream is also called pyrolysis oil or bio-oil, and is a liquid substance rich in a molecular blend typically consisting of more than two hundred different compounds, including aldehydes, ketones, and / or other compounds, such as furfural having a carbonyl group, which is formed by the depolymerization of the products of the pyrolysis treatment.

[0081] For the purposes of the present invention, the pyrolysis step is preferably fast pyrolysis, also known in the art as flash pyrolysis. Fast pyrolysis refers to the thermal decomposition of solid renewable raw materials at a temperature of 350-650°C (e.g., about 500°C) and a reaction time of 10 seconds or less (e.g., less than 10 seconds, e.g., 5 seconds or less, e.g., about 2 seconds) in the absence of oxygen; i.e., the vapor residence time is 10 seconds or less (e.g., 2 seconds or less, e.g., about 2 seconds). Traditionally, fast pyrolysis can also be carried out, for example, by autothermal operation, such as in a fluidized bed reactor. The latter is also called autothermal pyrolysis, which is characterized in that air (optionally with an inert gas or a recycled gas) is used as a fluidizing gas, or a mixture of air and an inert gas or a recycled gas is used. Therefore, partial oxidation of the pyrolysis compounds produced in the pyrolysis reactor (autothermal reactor) provides energy for pyrolysis while improving heat transfer. For details on autothermal pyrolysis, reference is made, for example, to "Heterodoxy in Fast Pyrolysis of Biomass" by Robert Brown:

[0082] https: / / dx.doi.org / 10.1021 / acs.energyfuels.0c03512

[0083] Therefore, in one embodiment of the present application, autothermal pyrolysis is used. That is, autothermal operation is provided as a specific embodiment for performing fast pyrolysis, that is, the pyrolysis step is performed by autothermal pyrolysis.

[0084] There are several types of fast pyrolysis in which catalysts are used. Sometimes an acid catalyst (e.g., a zeolite catalyst) is used in a pyrolysis unit (pyrolysis reactor) to upgrade the pyrolysis vapor; this technology is referred to as catalytic fast pyrolysis (CFP), which can be operated either in situ mode (the catalyst is located in the pyrolysis unit) or in ex situ mode (the catalyst is placed in a separate reactor; the pyrolysis gas is sent to a deoxygenation (DO) reactor to catalytically deoxygenate the pyrolysis oil before it condenses, as described above). More specifically, in in situ catalytic fast pyrolysis, the catalyst is located in the pyrolysis unit, and deoxygenation (by, for example, decarbonylation, decarboxylation by an acid-based catalyst such as a zeolite catalyst) occurs in the pyrolysis reactor immediately after the pyrolysis vapor is formed. Catalysts suitable for CFP include alumina and all types of zeolite catalysts commonly used for cracking in hydrocracking (HCR) and refining processes, such as HZSM-5. A more extensive list of catalytic materials for HCR is further provided below in this application.

[0085] Similarly, in in-situ HDO (also known as reactive catalytic fast pyrolysis, RCFP), the hydroprocessing (HDO) catalyst is located in the pyrolysis unit, and the pyrolysis vapors are thereby hydrodeoxygenated in the pyrolysis reactor immediately after their formation. Suitably, the catalyst used for HDO is a metal-based catalyst, including Ni, Mo, Co, Pt, Pd, Re, Ru, Fe in reduced form, such as CoMo or NiMo catalysts, also suitably in sulfide form: CoMoS, NiS, NiMoS, NiWS, RuS. The catalyst support may be the same as conventional HDO in refining processes, typically a refractory support, such as alumina, silica or titania or a combination thereof. In the following of this application, HDO conditions are also described.

[0086] In ex situ deoxygenation (DO), the steam is deoxygenated in a separate DO reactor located after the pyrolysis unit. Thus, in ex situ catalytic fast pyrolysis, the steam is deoxygenated using an acid catalyst such as a zeolite catalyst.

[0087] In ex-situ HDO, the pyrolysis vapors are hydrodeoxygenated in a separate HDO reactor located after the pyrolysis reactor using a hydrotreating catalyst, such as, for example, the following in combination Figure 1 and 2 Further described.

[0088] The use of a catalyst in the pyrolysis reactor has the advantage of lowering the activation energy of the reaction, thereby significantly reducing the temperature required to carry out pyrolysis. In addition, it can also increase the selectivity to the desired pyrolysis oil compounds.

[0089] It will be appreciated that where hydrogen is added to the catalytic fast pyrolysis, it is referred to as reactive catalytic fast pyrolysis (RCFP). In addition, if the catalytic fast pyrolysis is carried out at high hydrogen pressure (~>5 barg), it is often referred to as catalytic hydropyrolysis (CHP). Hydropyrolysis (HP) refers to the addition of hydrogen to the pyrolysis at atmospheric pressure.

[0090] The pyrolysis step is also suitably a simple fast pyrolysis, which for the purposes of the present application means that the fast pyrolysis is carried out in the absence of a catalyst and hydrogen in the pyrolysis unit, i.e. the fast pyrolysis is not any of the following: catalytic fast pyrolysis (CFP), hydropyrolysis (HP), reactive catalytic fast pyrolysis (RCFP) or catalytic fast hydropyrolysis (CHP). The HDO reactor may not be included downstream of the pyrolysis unit. This makes the process simpler and cheaper.

[0091] The following table summarizes the different options for fast pyrolysis in addition to autothermal pyrolysis:

[0092]

[0093] Thus, in one embodiment, the pyrolysis step is fast pyrolysis, wherein the vapor residence time is 10 seconds or less, such as less than 10 seconds, such as 5 seconds or less, such as about 2 seconds, or 1 second, or in the range of 1-5 seconds, and is selected from: simple fast pyrolysis; in situ catalytic fast pyrolysis (in situ CFP); ex situ catalytic fast pyrolysis (ex situ CFP); reactive catalytic fast pyrolysis (RCFP); hydropyrolysis (HP); catalytic fast hydropyrolysis (CHP).

[0094] In another embodiment, the pyrolysis step is an intermediate pyrolysis, wherein the steam residence time is 10 seconds to 5 minutes, for example 11 seconds to 3 minutes. For fast pyrolysis, the temperature is also in the range of 350-650° C., for example about 500° C. This pyrolysis is usually carried out in a pyrolysis reactor for treating different types of waste, wherein the steam is burned after the pyrolysis reactor. Typical reactors include: Herreshoff furnace, rotary drum, amaron, CHOREN paddle pyrolysis kiln, auger reactor and vacuum pyrolysis reactor.

[0095] In another embodiment, the pyrolysis step is a slow pyrolysis, wherein the solid residence time is 5 minutes to 2 hours, for example 10 minutes to 1 hour. The temperature is suitably about 300°C. This pyrolysis produces a high charcoal yield, and the char can be used as a fertilizer or as charcoal; pyrolysis still produces some gas and bio-crude oil, and if the carbon is used as a fertilizer, the final bio-oil can have more than 100% GHG, so it is carbon negative. Typical reactors are spiral reactors (but their residence time is different from that of intermediate pyrolysis), fixed bed reactors, kilns, lambiotte SIFIC / CISR rotary kilns, Lurgi process, cart reactors, and carbo twin reactors.

[0096] In one embodiment, the thermal decomposition step is a hydrothermal liquefaction step. Hydrothermal liquefaction refers to the thermochemical conversion of biomass into liquid fuels by treating enough time in a hot pressurized water environment to decompose the solid biopolymer structure into the main liquid components. Typical hydrothermal treatment conditions are a temperature of 250-375 ° C and an operating pressure of 40-220 bar. Compared with pyrolysis (such as fast pyrolysis), this technology provides the advantages of lower temperature, higher energy efficiency and lower tar yield. For details on the hydrothermal liquefaction of biomass, refer to "A review ofhydrothermal liquefaction of biomass" by, for example, Golakota et al., Renewable and Sustainable Energy Reviews, Vol. 81, Part 1, January 2018, pp. 1378-1392.

[0097] In one embodiment, the thermal decomposition step is solvolysis. For the purposes of this application, the term "solvolysis" refers to heating the lignocellulosic biomass in methanol or ethanol or other alcohols or recycled oil, optionally also in water, at a pressure of 20-80 bar, for example 40-60 bar and a temperature of 150-450° C., for example 150-200° C. or 325-425° C., to form a lignin-derived biocrude (solvolysis oil) as the biocrude feed.

[0098] As is well known in the art, solvolysis is a chemical reaction in which a solvent (e.g., methanol or ethanol, optionally with water) is one of the reactants and is present in an amount far in excess of that required for the reaction. When the solvent is specifically water, solvolysis is hydrolysis. Thus, in a specific embodiment, the solvolysis step is hydrolysis.

[0099] In one embodiment, the pyrolysis further comprises a preliminary step of passing the solid renewable feedstock through a solid renewable feedstock preparation section, the preliminary step comprising, for example, drying to remove water and / or comminution to reduce particle size. Any water / moisture in the solid renewable feedstock, after evaporation in, for example, the pyrolysis section, will condense in the pyrolysis oil stream and thus be entrained in the process, which may be undesirable. In addition, the heat used for water evaporation will take away the heat that would otherwise be necessary for pyrolysis. By removing water and providing a smaller particle size in the solid renewable feedstock, the thermal efficiency of the pyrolysis step can be improved.

[0100] The preparatory step may also include an acid wash to remove metals. This is particularly important for pyrolysis processes where the catalyst is located in the pyrolysis reactor. Removing metals from solid renewable feedstocks can extend the life of the catalyst.

[0101] In one embodiment, the solid renewable feedstock comprises lignocellulosic biomass, including wood products, forestry wastes, and agricultural residues. In one embodiment, the lignocellulosic biomass comprises algae. In another embodiment, the solid renewable feedstock comprises a nitrogen-rich renewable feedstock, such as feces or sewage sludge, in particular the organic fraction thereof, such as the organic fraction of sewage sludge.

[0102] The term "sewage sludge" refers to residual semi-solid material produced as a by-product during the sewage treatment process of industrial or municipal wastewater; for example, dewatered sludge contains: 50-70wt% organic matter and 30-50wt% mineral components (including 1-4wt% inorganic carbon), 1-10wt% N, such as 3.4-4.0wt% nitrogen (N), 0.5-2.5wt% phosphorus (P).

[0103] In another embodiment, the solid renewable raw material comprises municipal waste, in particular the organic fraction thereof.

[0104] For the purposes of this application, the term "municipal waste" is interchangeable with the term "municipal solid waste" and refers to raw materials containing material discarded by the public, such as mixed municipal waste of waste code 200301 in the European Waste Catalogue (EWC code 20 0301).

[0105] In another embodiment, the solid renewable raw material comprises recycled solid waste, in particular its organic fraction, wherein recycled solid waste is defined as raw material containing material discarded by the public, such as mixed recycled solid waste as given in EU Directive 2018 / 2001 (RED II), Annex IX, Part A.

[0106] Therefore, renewable raw materials include one or more of the following:

[0107] - lignocellulosic biomass, such as wood products, algae, forestry waste and / or agricultural residues;

[0108] - Nitrogen-rich renewable raw materials, such as manure or sewage sludge;

[0109] - municipal waste, in particular its organic fraction, wherein municipal solid waste is defined as raw material containing material discarded by the public, for example mixed municipal waste given waste code 200301 in the European Waste Catalogue (EWC code 200301); and / or recycled solid waste, in particular its organic fraction, wherein recycled solid waste is defined as raw material containing material discarded by the public, for example mixed recycled solid waste given in EU Directive 2018 / 2001 (RED II), Annex IX, part A.

[0110] In a specific embodiment, the lignocellulosic biomass is forestry waste and / or agricultural residues and comprises biomass derived from plants, including grasses, such as native grasses (grasses derived from the natural landscape), wheat (e.g., wheat straw), oats, rye, reed grass, bamboo, sugarcane or sugarcane derivatives (e.g., bagasse), corn, and other cereals.

[0111] Any combination of the above is also contemplated.

[0112] As used herein, the term "lignocellulosic biomass" refers to biomass containing cellulose, hemicellulose and optionally also lignin. The lignin or a large part thereof may have been removed, for example by a previous bleaching step.

[0113] In one embodiment, the method comprises feeding the following to a thermal decomposition unit:

[0114] - a solid feed stream comprising 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 solid renewable feedstocks, such as lignocellulosic biomass, municipal waste and / or recycled solid waste, to produce a pyrolysis oil stream, or a HTL oil stream, or a solvolysis oil stream as the biocrude feed comprising greater than 10 wt% O.

[0115] In particular, it has been found that hydrocarbon fuel diesel produced from biocrude feeds containing more than 10 wt% of O, produced by thermal decomposition of lignocellulosic biomass, is rich in aromatic compounds, so that the density and cetane index of the diesel fraction are too high to meet the EN 590 diesel specification. Therefore, a significant problem associated with such advanced biocrudes is that they contain too many aromatic compounds, so that they are not necessarily sufficient for hydrodearomatization (HDA), because the cetane number of the cycloalkanes is also not optimal, so ring opening by hydrocracking is required. However, by co-processing them with, for example, vegetable oils, it is now possible to minimize the hydrocracking and / or isomerization required to obtain a good cetane index, for example a cetane index (CCI according to standard ASTM D4737), hereinafter also referred to as CCI, above 40, for example 45-60, while increasing the diesel yield.

[0116] For example, hydrotreated vegetable oils (HVO) or hydrotreated cooked oils (hydrotreated waste cooking oils) have very high cetane index and low density, but poor cold flow properties. Combining, for example, a biocrude feed obtained by thermal decomposition of lignocellulosic biomass (particularly after said stabilization) with HVO or hydrotreated cooked oils (optionally with subsequent HDI) can produce particularly good diesel fuels that meet the EN 590 specification, including meeting the desired cold flow properties, for example in terms of cloud point (CP).

[0117] Thus, in one embodiment, the vegetable oil and / or fatty material feed is hydroprocessed, such as a hydrotreated vegetable oil and / or fatty material feed (e.g., a hydrotreated vegetable oil feed and / or a hydrotreated fatty material feed). The latter may be of external origin, or of internal origin and integrated into the process by the process further comprising subjecting the vegetable oil and / or fatty material to a hydroprocessing step, preferably a hydrotreating (HDO) step, prior to mixing with the partially deoxygenated biocrude feed.

[0118] In one embodiment, the vegetable oil and / or fat material feed is any of the following:

[0119] Soybean oils, such as soybean oil, rapeseed oil, corn oil, castor oil, cooked oil, animal fats, such as beef, pork, milk and chicken fat; or combinations thereof.

[0120] For example, the fatty material feed comprises fatty acids; the fatty material feed is suitably any one of: triglycerides, diglycerides, monoglycerides, and free fatty acids.

[0121] When the partially deoxygenated bio-crude feed is combined with a vegetable oil and / or fatty material feed to produce the hydrocarbon feed, an additional feed may be provided. Thus, in one embodiment, the step of combining the partially deoxygenated bio-crude feed with a vegetable oil and / or fatty material feed is further combined with an additional feed; the additional feed is suitably:

[0122] Fossil feedstocks, i.e. feedstocks derived from fossil fuel sources, such as diesel, kerosene, naphtha and vacuum gas oil (VGO), and / or

[0123] The intermediate hydrocarbon product, such as recycle oil, is obtained by recycling an intermediate hydrocarbon product produced in the process, such as a portion of the hydroprocessing feed produced downstream, ie, the first or second hydroprocessing feed.

[0124] Thus, suitably, said intermediate hydrocarbon product produced in the process is part of the feed to the first or second hydroprocessing.

[0125] In one embodiment, the process further comprises supplying the diesel and the marine fuel as a heavy end fraction or a combination thereof to a hydroisomerization (HDI) step in a HDI reactor, and / or a hydrocracking (HCR) step in a HCR reactor, to provide the intermediate hydrocarbon products, such as the intermediate hydrocarbon products produced in the process.

[0126] Thus, in a separation section, e.g. in a distillation column from which diesel and marine fuel are taken, any of these hydrocarbon products or a portion thereof is supplied to the HDI and / or HCR. Thus, such hydrocarbon products, e.g. marine fuels hydrotreated in the HCR reactor, are advantageously added after the partially deoxygenated biocrude feed (which has been subjected to stabilization and HDO / DO) has been combined with the suitably hydrotreated vegetable oil and / or fatty material feed. By hydrotreating these streams separately as described above, high synergistic effects have been found.

[0127] In one embodiment, the method comprises a prior solvent extraction step of a biocrude feedstock, such as a prior toluene extraction step, to produce the biocrude feedstock.

[0128] In a second general embodiment according to the first aspect of the present invention, there is also provided a method for producing a hydrocarbon feed, comprising:

[0129] - a hydrothermal liquefaction (HTL) step of a solid feed stream in a HTL unit or a solvolysis step in a solvolysis unit for producing a biocrude feed stream comprising not more than 10 wt% O;

[0130] - supplying the biocrude feed to a hydrodeoxygenation or deoxygenation (HDO / DO) step in a HDO / DO reactor to produce a partially deoxygenated biocrude feed comprising 2-8 wt% O;

[0131] - providing a feed of vegetable oil and / or fatty material;

[0132] - combining a partially deoxygenated biocrude feed with a vegetable oil and / or fatty material feed, optionally further with another feed, to produce said hydrocarbon feed;

[0133] - The process is devoid of a stabilization step in a stabilization reactor before supplying the biocrude feed to said HDO / DO step.

[0134] It has been found that the HTL step or the solvolysis step provides a biocrude feed with an oxygen (O) content as low as 11 wt% or as low as 10 wt% or even lower, thus enabling stabilization of the feed. Thus, the setup of a stabilization reactor can be eliminated, thereby also enabling a simpler process and equipment layout.

[0135] In a third general embodiment according to the first aspect of the present invention, there is also provided a method for producing a hydrocarbon feed, comprising:

[0136] - providing a biocrude feed comprising greater than 10 wt% oxygen (O);

[0137] - supplying the biocrude feed to a stabilization step in a stabilization reactor to produce a stabilized biocrude feed comprising less O than the biocrude feed;

[0138] - supplying the stabilized biocrude feed to a hydrodeoxygenation or deoxygenation (HDO / DO) step in a HDO / DO reactor to produce a partially deoxygenated (partially upgraded) biocrude feed comprising less than 10 wt% O and at least 0.1 wt% O, i.e. the biocrude feed comprising 0.1 to 10 wt% O, e.g. 0.1-9 wt% O, 2-7 wt% O, 2-8 wt% O, 2-10 wt% O, and less O than the stabilized biocrude feed;

[0139] - providing a feed of vegetable oil and / or fatty material;

[0140] - combining a partially deoxygenated biocrude feed with a vegetable oil and / or fatty material feed, optionally further with an additional feed, to produce said hydrocarbon feed.

[0141] For example, the partially deoxygenated biocrude feed contains any of the following: 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 wt % O.

[0142] It should be understood that any of the embodiments and associated benefits of the first general embodiment according to the first aspect of the present invention may be used in conjunction with the second and third general embodiments of the first aspect of the present invention.

[0143] In a second aspect, the present invention also contemplates an apparatus for carrying out the method according to any of the above-described embodiments of the first general embodiment of the first aspect of the present invention.

[0144] The equipment includes:

[0145] - a stabilization reactor arranged to receive a biocrude comprising greater than 10 wt% oxygen (O) and to provide a stabilized biocrude feed comprising less O than the biocrude feed;

[0146] - a hydrodeoxygenation or deoxygenation (HDO / DO) reactor (HDO / DO reactor) arranged to receive the stabilized biocrude feed and to provide a partially deoxygenated biocrude feed comprising 2-10 wt% O and less O than the stabilized biocrude feed;

[0147] - a conduit for providing a feed of vegetable oil and / or fatty material;

[0148] - A mixing point, such as a mixing unit or a junction, for combining the partially deoxygenated biocrude feed with the vegetable oil and / or fatty material feed and providing a hydrocarbon feed.

[0149] In one embodiment, the stabilization reactor is arranged to work in a continuous operation mode in a fixed bed reactor with the addition of hydrogen, the fixed bed reactor comprising any of Ni-Mo, Co-Mo, Ni-Cu, Mo, Pt, Pd, Ru or Ni based catalysts, and the stabilization reactor is further arranged to operate at a temperature of 20-240°C, a pressure of 100-200 barg, optionally 0.1-1.1 h -1 The reactor is operated at a liquid hourly space velocity (LHSV) of 1000-6000 NL / L, for example 2000-5000 NL / L.

[0150] In one embodiment, the apparatus further comprises a downstream catalytic bed of the HDO / DO reactor or a downstream HDO / reactor and provides a feed to the first hydroprocessing.

[0151] In one embodiment, the apparatus further comprises a downstream hydroprocessing section arranged to receive the first hydroprocessed feed and to provide a second hydroprocessed feed.

[0152] In one embodiment, the apparatus further comprises a separation section arranged to receive the first hydroprocessed feed or the second hydroprocessed feed and provide a hydrocarbon product, the hydrocarbon product being any one of: naphtha, diesel, jet fuel, marine (ship) fuel as a heavy end fraction, or a combination thereof.

[0153] In one embodiment, the apparatus further comprises a conduit for providing an additional feed, and the conduit is arranged for combination with any one of: a partially deoxygenated biocrude feed, a vegetable oil and / or a fatty material feed; the additional feed being:

[0154] Fossil feedstocks such as diesel, kerosene, naphtha and vacuum gas oil (VGO), and / or

[0155] The intermediate hydrocarbon product, such as recycle oil, is obtained by recycling a portion of the intermediate hydrocarbon product produced in the plant, such as the feed to the first or second hydroprocessing.

[0156] In one embodiment, the apparatus further comprises: an HDI reactor and / or an HCR reactor arranged to receive the diesel, the marine fuel as a heavy end fraction or a combination thereof and to provide the intermediate hydrocarbon product, such as the intermediate hydrocarbon product produced in the apparatus.

[0157] The present invention also envisages an apparatus for carrying out the method according to the second general embodiment of the first aspect of the invention.

[0158] The equipment includes:

[0159] a hydrothermal liquefaction (HTL) unit, or a solvolysis unit, arranged to receive a solid feed stream and to produce a biocrude feed stream comprising no more than 10 wt% O;

[0160] - a hydrodeoxygenation or deoxygenation (HDO / DO) reactor (HDO / DO reactor) arranged to receive said biocrude feed stream and to provide a partially deoxygenated biocrude feed comprising 2-8 wt% O;

[0161] - a conduit for providing a feed of vegetable oil and / or fatty material;

[0162] - A mixing point for combining the partially deoxygenated biocrude feed with the vegetable oil and / or fatty material feed and providing a hydrocarbon feed.

[0163] The plant also lacks the presence of a stabilization reactor upstream of the HDO / DO reactor, ie no stabilization reactor is arranged between the HT unit or solvolysis unit and the HDO / DO reactor.

[0164] It will also be appreciated that any embodiments and associated benefits according to the first aspect of the present invention may be used in conjunction with the second aspect of the present invention.

[0165] Figure 1 A schematic layout of a method and apparatus according to one embodiment of the present invention is shown.

[0166] Figure 2 , according to Example 1, a spot test of different concentrations of soybean oil with different bio-crude oils (AE) is shown.

[0167] Figure 3 , according to Example 1, microscope pictures of different soybean oil mixtures mixed with bio-crude oils C and E are shown.

[0168] Figure 4 , according to Example 1, spot tests of 50 wt% soybean oil in biocrudes F, G and H are shown.

[0169] Figure 5 , according to Example 1, microscope pictures of 50 wt% soybean oil with bio-crude oil F, G and H are shown.

[0170] Figure 6Another schematic layout of a method and apparatus according to an embodiment of the present invention is shown.

[0171] Reference Figure 1 , shows a method / apparatus (method and / or apparatus) according to an embodiment of the present invention. A biocrude feed 1, for example containing 45 wt% O, is fed together with hydrogen 3 to a stabilization reactor 10 operating at, for example, 80-250° C., thereby producing a stabilized biocrude feed 5 containing less O (e.g., 40 wt% O) than the biocrude feed 1. The stabilized biocrude feed 5 is supplied to a HDO / DO reactor 12 to produce a partially deoxygenated biocrude feed 7 containing 2-10 wt% O, for example, 2-7 wt% O. A vegetable oil and / or fatty material feed 9 is provided and combined with the partially deoxygenated biocrude feed 7 to produce a hydrocarbon feed 11. The hydrocarbon feed 11 is supplied to a subsequent HDO / DO reactor 14, thereby producing a first hydroprocessed feed 13, which can then be supplied to a subsequent hydroprocessing step, for example in a downstream hydroprocessing section (not shown). In a further downstream separation section (schematically illustrated here by separator 16), hydrocarbon products such as diesel 19 as well as naphtha 19' and heavy ends 19" are produced. A water stream 15 and a fraction containing NH3, H2S and C 1-4 A hydrocarbon waste gas stream 17 is provided.

[0172] Reference Figure 6 , shows a method / apparatus (method and / or apparatus) according to another embodiment of the present invention. A biocrude feed 101, for example containing 45 wt% O, is fed together with hydrogen 103 to a stabilization reactor 110 operated at, for example, 80-250° C., thereby producing a stabilized biocrude feed 105 containing less O (e.g., 40 wt% O) than the biocrude feed 101. The stabilized biocrude feed 105 is supplied to an HDO / DO reactor 112 to produce a partially deoxygenated biocrude feed 107 containing 2-10 wt% O, for example, 2-7 wt% O. A vegetable oil and / or fatty material feed 109 is provided and hydrotreated in an HDO / DO reactor 118 to produce a hydrotreated vegetable oil and / or fatty material feed 111, which is then combined with the partially deoxygenated biocrude feed 107. The hydrocarbon feed 113 is further combined with another feed, such as an intermediate hydrocarbon product 121 produced in the process, to produce a hydrocarbon feed 113, which can then be supplied to a subsequent hydroprocessing step, such as in a downstream hydroprocessing section (not shown). In a downstream separation section (also schematically illustrated here by separator 116), hydrocarbon products such as diesel 119 and naphtha 119' and heavy end fraction 119" are produced. A water stream 115 and a stream containing NH3, H2S and C 1-4A waste gas stream 117 of hydrocarbons. The heavy end fraction 119" is hydrocracked in the HCR reactor 120 to produce intermediate hydrocarbon products 121. An HDI reactor (not shown) may also be provided instead of the HCR reactor, or in addition to the HCR reactor, for producing the intermediate hydrocarbon products 121. Therefore, before being combined into the hydrocarbon feed 113, the stabilized biocrude feed 105, the vegetable oil and / or fatty material feed 109 and the heavy end fraction stream 119" are separately hydrotreated.

[0173] Example 1

[0174] Miscibility of biocrude oil and vegetable oil (soybean oil)

[0175] The composition of the soybean oil used is shown in Table 1.

[0176] Table 1. Composition of soybean oil used (measured by elemental analyzer)

[0177] C (wt%) H (wt%) O(wt%) 78 12 12

[0178] The following table shows an overview of the biocrude feed (biocrude) used:

[0179] Table 2: Biocrude feedstock

[0180]

[0181] *EA: Elemental Analysis

[0182] Miscibility is first tested by using a point test for visual miscibility, which is performed by mixing the biocrude oil with soybean oil and adding a drop of the mixture to the filter. The point test for visual miscibility is a compatibility test, such as that 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.

[0183] like Figure 2 As shown, biocrudes A, B, and D are immiscible in soybean oil, while biocrudes C and E appear to be miscible with soybean oil on a macroscopic level. Biocrudes C and E have the highest oxygen (O) content but appear to be most miscible with vegetable oil.

[0184] It should be noted that mixing Biocrude A and B with soybean oil resulted in precipitation of solids, therefore co-processing these feeds with soybean oil in an industrial or pilot unit would result in rapid plugging of reactors and pipes.

[0185] However, studies of 10 wt% and 50 wt% soybean oil in bio-crudes C and E by optical microscopy showed that it was immiscible in bio-crudes C and E; see Figure 3 .

[0186] The miscibility of three (3) partially deoxygenated (via HDO) catalytic pyrolysis oils was also investigated and their compositions are shown in Table 3. The results from spot testing and optical microscopy are shown in Figure 4 and Figure 5 , it is shown that these partially deoxygenated bio-crudes with oxygen contents of 2-10 wt%, such as 2-8 wt%, are miscible with soybean oil when a 1:1 weight ratio is used (50 wt% soybean oil). Lower weight ratios, such as 1:9 (10 wt% partially deoxygenated bio-crude and 90 wt% soybean oil) can increase miscibility.

[0187] Table 3. Hydrotreated catalytic pyrolysis oil

[0188] F G H C (wt%) EA* 81 81 83 H (wt%) EA* 11 10 11 O(wt%) EA* 5.9 7.3 5.2

[0189] *EA: Elemental Analysis

[0190] Thus, co-processing of vegetable oils and fatty acids with advanced biofuels (i.e., bio-crude oils) is achieved by first reducing the oxygen content in the advanced biofuels to 2-10 wt% by partial deoxygenation (e.g., at moderate severity) before they become miscible with the vegetable oils. At this moderate severity, a high concentration of aromatic compounds is maintained, thereby reducing the production of heavy end fractions.

[0191] Example 2

[0192] Co-processing of soybean oil with hydrotreated catalytic fast pyrolysis (CFP) oil

[0193] Soybean oil with a cloud point and pour point of -7.3 and -12.0°C was hydrotreated in a fixed bed single pass hydroprocessing unit. The produced hydrotreated soybean oil had a cloud point of 22.7°C and a pour point of 21.0°C. The soybean oil was blended with a hydrotreated catalytic fast pyrolysis oil (ratio 20 / 80 v / v) to reduce the cloud point and pour point of the feed to -15.0°C and -12.0°C, respectively. The cloud point and pour point of the hydrotreated oil were also reduced to 17.3 and 18.0°C, respectively. The cloud point and pour point of the feed and product are shown in Table 4, and the oxygen, hydrogen and specific gravity (SG) are shown in Table 5. Since the hydrotreated catalytic fast pyrolysis oil used was too dark in color, its cloud point and pour point could not be measured using this method. However, the cloud point and pour point of another similar oil (hydrotreated oil in the same experiment) can be measured. The cloud point and pour point of this oil were -19.9°C and -21.0°C respectively and the oxygen content was 1.5 wt%.

[0194] This suggests that co-treatment of soybean oil and hydrotreated catalytic fast pyrolysis oil reduces the cloud point and pour point compared to hydrotreating soybean oil alone, and therefore co-treatment reduces the need for isomerization and thus also reduces the yield loss associated with isomerization.

[0195] Table 4

[0196]

[0197] Table 5

[0198]

Claims

1. A method for producing a hydrocarbon feed comprising the following steps: - providing a biocrude feed comprising greater than 10 wt% oxygen (O); - supplying the biocrude feed to a stabilization step in a stabilization reactor to produce a stabilized biocrude feed comprising less O than the biocrude feed; - supplying the stabilized biocrude feed to a hydrodeoxygenation or deoxygenation (HDO / DO) step in a HDO / DO reactor to produce a partially deoxygenated biocrude feed comprising 2-10 wt% O and comprising less O than the stabilized biocrude feed; - providing a feed of vegetable oil and / or fatty material; - Combining a partially deoxygenated biocrude feed with a vegetable oil and / or fatty material feed to produce said hydrocarbon feed.

2. The method of claim 1, wherein the biocrude feed comprises at least 15 wt% O, or at least 30 wt% O, such as 35-70 wt% O, such as 40-60 wt% O or 40-50 wt% O.

3. The method according to any one of claims 1-2, wherein the biocrude feed comprises 40-60 wt% O and the stabilized biocrude feed comprises 20-55 wt% O.

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

5. The method according to any one of claims 1 to 4, further comprising: - supplying the hydrocarbon feed to a subsequent HDO / DO step to produce a first hydroprocessed feed; Wherein the subsequent HDO / DO step is carried out as follows: a downstream catalytic bed of the HDO / DO reactor to produce the partially deoxygenated bio-crude feed; or Downstream HDO / DO reactor.

6. The method according to any one of claims 1 to 5, further comprising: - supplying the first hydroprocessed feed to a subsequent hydroprocessing step in a downstream hydroprocessing section, such as a hydroisomerization (HDI) step in a HDI reactor, and / or a hydrocracking (HCR) step in a HCR reactor, and / or a hydrodearomatization (HDA) step in a HDA reactor, to produce a second hydroprocessed feed.

7. The method according to any one of claims 5 to 6, 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 hydrocarbon product being any one of: naphtha, diesel, jet fuel, marine (ship) fuel as a heavy end fraction, or a combination thereof.

8. A process according to any one of claims 1 to 7, wherein the weight ratio (A:B) of the partially deoxygenated biocrude feed (A) to the vegetable oil and / or fatty material feed (B) is in the range of 50:50 wt% to 10:90 wt%; and optionally, a subsequent HDO / DO step for producing a feed for the first hydroprocessing is carried out in a continuous mode under the following conditions: 250-400°C, at a pressure of 50-150 bar, using a fixed bed catalyst, wherein the catalyst is NiMoS and / or MoS.

9. The method according to any one of claims 1-7, wherein the weight ratio (A:B) of the partially deoxygenated biocrude feed (A) to the vegetable oil and / or fatty material feed (B) is in the range of 50:50wt% to 90:10wt%.

10. The method according to any one of claims 1-9, further comprising a thermal decomposition step of a solid feed stream in a thermal decomposition unit, wherein the thermal decomposition step is selected from a pyrolysis step in a pyrolysis unit, a hydrothermal liquefaction (HTL) step in a HTL unit, or a solvolysis step in a solvolysis unit, thereby producing the biocrude feed containing greater than 10 wt% O.

11. The method of claim 10, wherein the method comprises feeding the thermal decomposition unit with: - a solid feed stream comprising 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 solid renewable feedstocks, such as lignocellulosic biomass, municipal waste and / or recycled solid waste, to produce a pyrolysis oil stream, or a HTL oil stream, or a solvolysis oil stream, which is used as the bio-crude feed comprising greater than 10 wt% O.

12. The method according to any one of claims 1 to 11, wherein the vegetable oil and / or fatty material feed is a hydroprocessed vegetable oil and / or fatty material feed, such as a hydrotreated vegetable oil and / or fatty material feed.

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

14. The process of any one of claims 1 to 13, wherein the step of combining the partially deoxygenated biocrude feed with the vegetable oil and / or fatty material feed is also combined with an additional feed; the additional feed being: Fossil feedstocks such as diesel, kerosene, naphtha and vacuum gas oil (VGO), and / or An intermediate hydrocarbon product, such as recycle oil, ie a portion of the intermediate hydrocarbon product produced in the process, such as the feed to the first or second hydroprocessing, is recycled.

15. The method according to any one of claims 7 to 14, wherein the method further comprises supplying the diesel and the marine fuel as a heavy end fraction or a combination thereof to a hydroisomerization (HDI) step in a HDI reactor and / or a hydrocracking (HCR) step in a HCR reactor to provide the intermediate hydrocarbon products, such as the intermediate hydrocarbon products produced in the method.

16. A method for producing a hydrocarbon feed, comprising: - a hydrothermal liquefaction (HTL) step of a solid feed stream in a HTL unit or a solvolysis step in a solvolysis unit for producing a biocrude feed stream comprising not more than 10 wt% O; - supplying the biocrude feed to a hydrodeoxygenation or deoxygenation (HDO / DO) step in a HDO / DO reactor to produce a partially upgraded (partially deoxygenated) biocrude feed comprising 2-8 wt% O; - providing a feed of vegetable oil and / or fatty material; - combining a partially deoxygenated biocrude feed with a vegetable oil and / or fatty material feed, optionally further with another feed, to produce said hydrocarbon feed; - The process is devoid of a stabilization step in a stabilization reactor before supplying the biocrude feed to said HDO / DO step.

17. Apparatus for carrying out the method according to any one of claims 1 to 15, comprising: - a stabilization reactor arranged to receive a biocrude comprising greater than 10 wt% oxygen (O) and to provide a stabilized biocrude feed comprising less O than the biocrude feed; a hydrodeoxygenation or deoxygenation (HDO / DO) reactor (HDO / DO reactor) arranged to receive the stabilized biocrude feed and to provide a partially deoxygenated biocrude feed comprising 2-10 wt% O and comprising less O than the stabilized biocrude feed; - a conduit which provides a feed of vegetable oil and / or fatty material; - A mixing point for combining the partially deoxygenated biocrude feed with the vegetable oil and / or fatty material feed and providing a hydrocarbon feed.

18. Apparatus for carrying out the method according to claim 16, comprising: a hydrothermal liquefaction (HTL) unit or a solvolysis unit arranged to receive a solid feed stream to produce a biocrude feed stream comprising no more than 10 wt% O; - a hydrodeoxygenation or deoxygenation (HDO / DO) reactor (HDO / DO reactor) arranged to receive said biocrude feed stream and to provide a partially deoxygenated biocrude feed comprising 2-8 wt% O; - a conduit for providing a feed of vegetable oil and / or fatty material; - a mixing point for combining the partially deoxygenated biocrude feed with the vegetable oil and / or fatty material feed and providing a hydrocarbon feed; - The plant also does not present a stabilization reactor upstream of the HDO / DO reactor.

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