Method for stabilizing nitrogen-enriched oils

Abstract

The present invention is a method for producing a catalyst-free olefin by continuous operation in a fixed-bed reactor at a temperature of 80 to 250°C, a total pressure of 10 to 200 barg, and a liquid hourly space velocity (LHSV) of 0.1 to 6 h -1 and a method for hydrotreating a nitrogen-enriched liquid oil stream by reacting said nitrogen-enriched liquid oil stream with hydrogen, thereby producing a stabilized liquid oil stream.

Description

[Technical Field]

[0001] Technical Field The present invention relates to a method for hydrotreating a nitrogen-enriched liquid oil stream by reacting the nitrogen-enriched liquid oil stream with hydrogen in the presence of a catalyst in a fixed bed reactor operated continuously at a temperature of 80 to 250°C, a pressure of 10 to 200 barg, and a liquid hourly space velocity (LHSV) of 0.1 to 6 h, thereby producing a stabilized liquid oil stream. [Background technology]

[0002] background The field of renewable feedstocks is receiving a lot of attention not only in Europe but also in the USA and China. The use of renewable feedstocks offers a sustainable approach to hydrocarbon products used as transportation fuels, especially marine fuels, diesel fuel, jet fuel, naphtha, as well as petrochemical feedstocks, e.g. steam cracker feedstocks.

[0003] Oils derived from nitrogen-rich feedstocks, such as sewage sludge, algae, or other nitrogen-rich renewable sources, have a higher tendency to polymerize than oils derived from wood or straw.

[0004] If oil from nitrogen-enriched feedstocks is not stabilized, it can quickly coke and clog the catalyst bed. Stabilizing it in the same way as pyrolysis oil from wood biomass would result in unnecessary high pressures, low LHSV, and very expensive catalysts, resulting in very high CAPEX.

[0005] WO2022 / 152900 describes a method for low-temperature stabilization of liquid oils.

[0006] Zacher et al., “Technology advancements in hydroprocessing of bio-oils”, Biomass and Bioenergy, 125 (2019) 151-168, suggests that oils with a carbonyl content of 1.3 mmol / g are stable enough to undergo hydroprocessing at 400°C. This teaching suggests avoiding low-temperature stabilization steps, as these add cost and complexity to the process. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] WO2022 / 152900 [Non-patent literature]

[0008] [Non-Patent Document 1] Zacher et al “Technology advancements in hydroprocessing of bio-oils”, Biomass and Bioenergy, 125 (2019) 151-168

[0009] However, this has been found to be the case when the nitrogen content of the feed oil is high. Feeds with high nitrogen content and carbonyl contents in the range of <0.5-1.13 mmol / g can cause reactor plugging at operating temperatures of 300 °C. Summary of the Invention [Problem to be solved by the invention]

[0010] This technology provides a new solution to the problem of reactor clogging being a risk when the feed has a carbonyl number above the detection limit but less than 1.13 mmol / g and the nitrogen concentration is high. Another objective of this technology is to provide a stable renewable crude oil that can be hydrotreated under known hydrotreating conditions and a method for producing the same. [Means for solving the problem]

[0011] summary The present inventors have discovered that plugging of hydroprocessing reactors with high nitrogen, low carbonyl feedstocks can be reduced or avoided by first stabilizing the feedstock.

[0012] Accordingly, a first embodiment of the present invention relates to a process for the hydrotreatment of a nitrogen-enriched liquid oil stream, in continuous operation in a fixed bed reactor, in the presence of a catalyst, at a temperature of 80-250°C, a pressure of 10-200 barg, a liquid hourly space velocity (LHSV) of 0.1-6 h -1 by reacting a nitrogen-enriched liquid oil stream with hydrogen to form a stabilized liquid oil stream.

[0013] Detailed Disclosure The unit "barg" indicates pressure above atmospheric pressure (atmospheric pressure: approximately 1 bar).

[0014] A method for hydrotreating a nitrogen-enriched liquid oil stream having a nitrogen content of at least 0.5% by mass and a carbonyl content of between 0.5 mmol / g and 1.13 mmol / g is provided, the method comprising hydrotreating the nitrogen-enriched liquid oil stream in a continuous fixed-bed reactor at a temperature of between 80 and 250°C, a pressure of between 10 and 200 barg, and a liquid hourly space velocity (LHSV) of between 0.1 and 6 h. -1 The present invention provides a method for stabilizing a nitrogen-enriched liquid oil stream by reacting the nitrogen-enriched liquid oil stream with hydrogen in the presence of a catalyst under conditions of

[0015] In a preferred embodiment, the temperature is in the range of 180 to 220° C., for example, 190 to 200° C. In another embodiment, the pressure is in the range of 80 to 175 barg, for example, 150 barg. 、 LHSV is 0.2 to 4.0 hours -1 For example, 0.2 to 0.2h -1 or 0.8 to 1.0 hours -1 , e.g. 0.9h -1 is.

[0016] In yet another embodiment, the temperature is in the range of 180 to 220°C, for example, 190 to 200°C. In another embodiment, the pressure is in the range of 15 to 80 barg, for example, 50 barg. In another embodiment, the LHSV is 0.2 to 4.0 h -1 For example, the range is 0.2 to 0.2h. -1 or 0.8 to 1.0 hours -1 For example, 0.9h -1 is.

[0017] The temperature range of 80-250°C includes the inlet temperature of the liquid oil stream and the outlet temperature of the stabilized liquid oil stream. Preferred temperature ranges include 100-250°C, 120-250°C, and 150-250°C. Because the process is exothermic, the temperature may rise by about 100°C or more. Higher inlet temperatures, e.g., 80°C, facilitate ignition of the process and the initiation of the exothermic reaction. Outlet temperatures can be, for example, 150°C, 200°C, or 240°C. More generally, the temperature of a particular step or reactor (unit) refers to the inlet temperature in an adiabatic step or the reaction temperature in an isothermal step.

[0018] In the present invention, a continuous operation process is used because, unlike a batch operation, the discharged product (stabilized liquid oil) does not need to be constantly fluid. In the known art, continuous operation means that the flow of liquid oil is continuous during a specific production cycle, and the flow of stabilized liquid oil is also continuous. This is in contrast to a batch operation, i.e., an intermittent operation, in which the total amount of liquid oil and catalyst is introduced at the start of the process, and the product is recovered after a certain period of time, as is also well known in the art.

[0019] In this method, the volume ratio of hydrogen to liquid oil (volume ratio of hydrogen to liquid oil flow) is preferably 100 to 8000 NL / L, for example, 2000 to 5000 NL / L.

[0020] In the present invention, the method is also carried out under conditions where the hydrogen to liquid oil ratio is 1000 to 6000 NL / L, for example, 2000 to 5000 NL / L, for example, 2500, 3000, 3500, 4000, or 4500 NL / L. As used herein, "hydrogen to liquid oil ratio" or "H2 / oil ratio" refers to the volumetric ratio of hydrogen to liquid oil streams. The unit NL means "standard" liter, i.e., the amount of gas that occupies this volume at 0°C and 1 atmosphere. The volume of liquid oil is measured according to the art at 15°C and 1 atmosphere.

[0021] In one embodiment, the liquid oil stream comprises at least 2% by weight nitrogen (N), or at least 5% by weight nitrogen. The liquid oil stream may comprise 10% by weight nitrogen (N), such as at least 2% by weight nitrogen, or at least 5% by weight nitrogen. Nitrogen content is suitably determined by standard elemental analysis.

[0022] In an example embodiment, the liquid oil stream comprises at least 0.5 wt.% oxygen (O), such as at least 2 wt.% O, or at least 4 wt.% O. Oxygen content is suitably determined by standard elemental analysis.

[0023] In one embodiment, the microcarbon residue (MCR) of the liquid oil stream prior to hydrotreating is in the range of 5 to 20 mass %, for example, 5 to 15 mass %, as measured by ASTM D 4530. Such high MCR values ​​indicate a tendency for coke deposition. After hydrotreating, the stabilized liquid oil stream has a microcarbon residue (MCR) of less than 5 mass %, preferably less than 4.5 mass %, as measured by ASTM D 4530, indicating a low tendency for coke deposition.

[0024] In one example embodiment, the liquid oil stream is a pyrolysis oil stream or a hydrothermal liquefaction (HTL) oil stream. In one example embodiment, the liquid oil stream is an oil stream derived from a thermochemical cracking process, such as pyrolysis or hydrothermal liquefaction, which may be part of the same process plant or a separate process plant. In one example embodiment, the liquid oil stream is a pyrolysis oil stream containing at least 0.5 mol / kg of at least one of: aldehyde compounds, ketones, alcohols, furfural, as measured by ASTM E3146-20. In one example embodiment, the liquid oil stream has an elemental composition ranging from 50% to 70%, 50% to 80%, or 50% to 85% by weight carbon (C) and 2% to 50%, 3% to 50%, or 10% to 50% by weight oxygen (O), which is a typical elemental composition range of liquid non-aqueous pyrolysis products such as pyrolysis oil streams or hydrothermal liquefaction (HTL) oil streams. 14 C / 12 If the C isotope ratio is between 0.5 and 2 ppt, this is the isotopic composition that defines a biologically derived sample.

[0025] In one embodiment, the catalyst is Ni-based, Mo-based, CoMo-based, NiMo-based, W-based, NiW-based, or Ru-based, optionally in sulfided or reduced form.

[0026] When a catalyst is "based" on a particular metal (e.g., Ni-based), this means that the specified metal (Ni, Mo, etc.) accounts for 90%, 99%, or 100% or more by weight of the materials in Groups 1-12 contained in the catalyst. Ranges for each category are as follows: Ni-based (2-30% by weight Ni sulfide or reduced form), Mo-based (2-30% by weight Mo, preferably sulfide), CoMo-based (1-10% by weight Co, 2-30% by weight Mo, preferably sulfide), NiMo-based (1-10% by weight Ni, 2-30% by weight Mo, preferably sulfide), W-based (2-30% by weight W, preferably sulfide), NiW-based (1-10% by weight Ni, 2-30% by weight W, preferably sulfide), or Ru-based (0.1-10% by weight, preferably reduced form), optionally including sulfide or reduced forms.

[0027] In one embodiment of the present method, the catalyst is a supported catalyst having a Mo content of 2-30 wt. % and, optionally, a P content of 0-3 wt. % based on the total weight of the catalyst. The support is selected from alumina, silica, titania, or a combination thereof; optionally, combined with a solid acid, e.g., silica-alumina, or a molecular sieve having the MFI, BEA, or FAU topology. As used herein, the term "topology MFI, BEA, or FAU" refers to the structures assigned and maintained by the International Zeolite Association Structure Committee in the "Zeolite Framework Types Atlas," including those listed at http: / / www.iza-structure.org / databases / or, for example, those defined in the "Zeolite Framework Types Atlas" by Ch. Baerlocher, L.B. McCusker, and D.H. Olson, Sixth Revised Edition 2007.

[0028] The method can further include a prior step of pyrolysis of the solid renewable feedstock. For convenience, the term "pyrolysis" is used herein to broadly refer to any decomposition process in which a material is partially decomposed at elevated temperatures (typically 250°C to 800°C or 1000°C) in the presence of submolar amounts of oxygen (including the absence of oxygen). The products are typically a combined liquid and gas stream and a quantity of solid char. The term is intended to include processes involving pyrolysis and hydrothermal liquefaction, with or without a catalyst.

[0029] Thus, in certain embodiments, the thermal cracking is pyrolysis (e.g., fast pyrolysis), thereby producing a pyrolysis oil stream. It should be understood that the thermal cracking is carried out in a thermal cracking section. Thus, pyrolysis is carried out in the pyrolysis section, and hydrothermal liquefaction is carried out in the hydrothermal liquefaction section. As used herein, "section" refers to a physical section that includes a unit or combination of units for carrying out one or more steps and / or substeps.

[0030] One type of pyrolysis is fast pyrolysis, also known in the art as flash pyrolysis. Fast pyrolysis refers to the thermal decomposition of solid renewable feedstocks in the absence of oxygen at temperatures ranging from 350 to 650°C (e.g., about 500°C) and with reaction times of 10 seconds or less (e.g., 5 seconds or less, e.g., about 2 seconds). Fast pyrolysis may be carried out, for example, by autothermal operation in a fluidized-bed reactor. The latter, also known as autothermal pyrolysis, is characterized by the use of air, optionally with an inert or recycled gas, or a mixture of air and an inert or recycled gas as the fluidizing gas. This allows the partial oxidation of pyrolysis compounds produced in the pyrolysis reactor (autothermal reactor) to provide the energy source for pyrolysis, while also improving heat transfer. For more information on autothermal pyrolysis, see, for example, Robert Brown, "Heterodoxy in Fast Pyrolysis of Biomass."https: / / dx.doi.Org / 10.1021 / acs.energyfuels.0c03512。 In one embodiment, the pyrolysis is fast pyrolysis, which is suitably carried out in the absence of a catalyst and hydrogen.

[0031] "Intermediate" or "delayed" pyrolysis is also suitable for high-N feedstocks and may be preferable to fast pyrolysis in some cases, in part because high-N feedstocks tend to be rich in alkali metals, which increases the risk of agglomeration and fluidization problems.

[0032] In another embodiment, the pyrolysis step is an intermediate pyrolysis, with a vapor residence time ranging from 10 seconds to 5 minutes (e.g., 11 seconds to 3 minutes). Similar to the fast pyrolysis, the temperature ranges from 350 to 650°C (e.g., about 500°C). This pyrolysis is often carried out in a pyrolysis reactor for processing different types of waste, with post-pyrolysis vapor combustion. Typical reactors include Herreshoff furnaces, rotary drums, Amaron and CHOREN paddle pyrolysis furnaces, auger reactors, and vacuum pyrolysis reactors.

[0033] In another embodiment, the pyrolysis step is delayed pyrolysis, with solids residence time ranging from 5 minutes to 2 hours (e.g., 10 minutes to 1 hour). The temperature is suitably about 300°C. This pyrolysis produces high char yields, and the char can be used as fertilizer or charcoal; pyrolysis produces some gas and renewable crude oil, and if the carbon is used as fertilizer, the final bio-oil is more than 100% GHG-negative and carbon-negative. Typical reactors include auger reactors (which have different residence times than intermediate pyrolysis), fixed-bed reactors, kilns, Lambiot SIFIC / CISR furnaces, Lurgi process, wagon reactors, and CarboTwin furnaces.

[0034] Hydrothermal liquefaction (HTL) effectively involves reacting biomass or organic materials in the presence of water or other solvents under hydrothermal conditions at temperatures ranging from 250°C to 450°C and pressures ranging from approximately 100 to 350 bar. Under these conditions, water maintains a liquid or relatively dense supercritical state. Because of the need for a wet reaction environment, HTL is particularly suited to wet feedstocks, which do not require a drying step. During HTL processing, organic materials undergo polymerization reactions, including hydrolysis, dehydration, and decarboxylation, to produce water-soluble intermediates, followed by polymerization reactions involving various condensation mechanisms to produce water-insoluble products, including renewable crude oil and chars. Other products include gases, typically dominated by CO2, but with varying amounts of H2, CH4, and CO depending on the biomass and reaction conditions. An aqueous phase containing water-soluble organic matter, primarily alcohols, acids, and phenols, is also present (in the case of lignocellulose).

[0035] Thus, suitably, said pyrolysis step comprises: - pyrolysis, for example, fast pyrolysis, intermediate pyrolysis or delayed pyrolysis, to produce a pyrolysis oil stream; or - hydrothermal liquefaction (HTL), producing an HTL oil stream; is.

[0036] In one aspect of the method of the present invention, the solid renewable feedstock comprises: - Lignocellulosic-based biomass, including wood products, forestry waste, and agricultural residues; and / or - Municipal waste, in particular its organic components, defined as a feedstock containing materials from items discarded by society, such as mixed municipal waste as defined in EU Directive 2018 / 2001 (RED II), Annex IX, Part A.

[0037] The term "renewable" excludes fossil crude oil but includes recycled waste products of fossil origin, including, for example, plastic waste. Combinations of any of the above are also contemplated.

[0038] In this article, "lignocellulose-based biomass" means biomass containing cellulose, hemicellulose, and optionally lignin. The lignin, or a substantial portion thereof, may have been removed, for example, by a prior bleaching step. Lignocellulose-based biomass is suitably forestry waste and / or agricultural residues, and includes biomass of plant origin, such as natural grasses (grasses from natural landscapes), wheat, e.g., wheat straw, oats, rye, reedgrass (reeds), bamboo, sugarcane or sugarcane derivatives, e.g., bagasse, corn, and other cereals.

[0039] In one embodiment, the method further comprises passing the stabilized liquid oil stream through a hydrodeoxygenation (HDO), hydrodenitration (HDN) or hydrodesulfurization (HDS) step, suitably wherein the HDO is preferably carried out at a higher temperature than the preceding step to form the stabilized liquid oil stream.

[0040] This removes the organic nitrogen present in the stabilized pyrolysis oil stream and produces a hydrotreated stream, which can be further processed to produce hydrocarbon products boiling in the transportation fuel range, such as diesel fuel, jet fuel, and naphtha. During hydroprocessing of renewable feedstocks or liquid oils, oxygen is removed primarily as HO, producing paraffinic fuels consisting of paraffins with the same number of carbon atoms as in the triglyceride backbone. This is called the hydrodeoxygenation (HDO) pathway. Oxygen can also be removed via the dicarboxylic acid (DCO) pathway, in which CO is produced instead of HO: HDO Pathway: C 17 H 34 COOH+3.5H2<->C 18 H 38 +2H2O, decarboxylation pathway: C 17 H 34 COOH+0.5H2<->C 17 H 36 +CO2.

[0041] Materials that are catalytically active in hydroprocessing, e.g., HDO, typically include an active metal (which can be a sulfide-containing metal such as nickel, cobalt, tantalum, molybdenum, or an elemental noble metal such as platinum or palladium) and a refractory support (alumina, silica, titania, or a combination thereof).

[0042] In one example embodiment, the method further comprises passing the stabilized liquid oil stream through one or more metal guards active in hydrometallation (HDM) and / or hydrodeoxygenation (HDO) prior to the HDO step. A suitable guard layer (protective layer) for removing at least P and Fe is a porous material comprising alumina containing alpha-aluminum, the porous material comprising one or more metals selected from Co, Mo, Ni, W, and combinations thereof, the porous material having a BET specific surface area of ​​1 to 110 m as measured by mercury intrusion porosimetry. 2 The guard layer has a pore size distribution (PSD) of 0.50-0.80 ml / g, preferably a total pore volume of 0.50-0.80 ml / g, with at least 30% by volume of the total pore volume being pores with a radius of >400 Å, preferably >500 Å, for example, up to 5000 Å; see, for example, co-filed patent application PCT / EP2021 / 068656. Another suitable guard layer is a catalyst containing molybdenum supported on alumina, i.e., Mo / Al2O3 catalyst. Yet another suitable catalyst is one with demetallization activity and moderate hydrodesulfurization activity, such as a nickel-molybdenum catalyst (NiMo catalyst), with a metal content of, for example, 6.0% by mass of Mo and 1.8% by mass of Ni.

[0043] Hydrometallation (HDM), as is well known in the art, refers to a pretreatment process in which organically bound metals are precipitated as sulfides or oxides. The reaction is similar to hydrodesulfurization (HDS), except that heteroatoms (S) are removed as gaseous HS. [Example]

[0044] example overview Oils derived from sewage sludge and other nitrogen-rich feedstocks are characterized by high nitrogen content (>1 wt%). Although these oils are more thermally stable than fast pyrolysis oils, a stabilization step is still required before heating to 300 °C. In this study, NiMoS / Al2O3 (Mo: 6.0 wt%, Ni: 1.8 wt%) catalyst was used at LHSVs of 0.25–0.5 h. -1 , 20-120 barg, 190-220°C to stabilize an oil with a nitrogen content of 9% by mass. The oil was successfully stabilized and further hydrotreated to reduce the nitrogen content to 0.17% by mass.

[0045] Catalyst, Feedstock and Test Conditions The composition of the oil is shown in Table 1. This oil was produced from sewage sludge and therefore had a high nitrogen content (9.0% by mass).

[0046] [Table 1]

[0047] Three tests were carried out in two once-through trickle-bed reactors (reactors connected in series and operating as R1 and R2) using 100% hydrogen as the process gas. The catalyst was diluted with carborundum and packed into an isothermal stainless steel tube reactor. A total volume of 230 ml was used for each test. The catalyst was activated before the test. Under each condition, gas and liquid product samples were taken and analyzed after lineout was reached. The test conditions are outlined in Table 2.

[0048] [Table 2]

[0049] Catalyst A is a guard catalyst with moderate HDS / HDO / HDN activity. Mo: 6.2 mass%, Ni: 1.6 mass%, P: 1.2 mass% Catalyst B is a guard catalyst with moderate HDS / HDO / HDN activity. Mo: 6.0 mass %, Ni: 1.8 mass % Catalyst C is a catalyst with high HDO / HDN / HDS activity. Mo: 19.7 mass %, Ni: 3.6 mass %, P: 2.0 mass %.

[0050] Catalyst, Feedstock and Test Conditions In the first test, the oil was assumed to be thermally stable, and the first reactor was loaded with HDM catalyst. However, the inlet to R1 clogged after 167 hours. The liquid product from the first test contained 2.6 mass% nitrogen, as shown in Table 3. The objective of the second test was to investigate whether the oil could be stabilized at 190 °C and 220 °C and 20 bar. The test continued for 431 hours without any observed pressure drop in the reactor. As shown in Table 3, the MCR decreased to 3.80-3.96 mass% compared to 9.81 mass% in the feed, indicating that the product was more thermally stable than the feed. The nitrogen, sulfur, and oxygen contents decreased to 8.3-8.8 mass%, 0.49-0.60 mass%, and 4.4-4.9 mass%, respectively. Meanwhile, the hydrogen content increased to 8.85-9.00 mass%. This confirmed the effect of removing heteroatoms while hydrogenating oil as an additional property of the stabilization reactor.

[0051] In the third pilot plant test, the pressure was increased to 120 bar, and the temperature in the first reactor was 220°C while the temperature in the second reactor was 100°C, resulting in the catalyst in the second reactor being deemed inactive at this temperature. Under these conditions, the product had a microcarbon residue (MCR) of 2.36% by weight and reduced nitrogen to 7.6% by weight, based on ASTM D4530. Increasing the temperature to 340°C in condition 2 and 360°C in condition 3 reduced the nitrogen content to 1.3% and 0.17%, respectively, while reducing the MCR to <0.05% by weight and the oxygen content to less than 1% by weight.

[0052] [Table 3]

[0053] Although the present invention has been described with reference to several embodiments and examples, those skilled in the art can freely combine any of the embodiments and features as desired. The full scope of the present invention is defined in the appended claims. All documents cited herein are incorporated by reference.

Claims

1. 1. A process for hydrotreating a nitrogen-enriched liquid oil stream containing at least 0.5 mass % nitrogen and having a carbonyl content of 0.5 mmol / g to 1.13 mmol / g, by continuous operation in a fixed bed reactor in the presence of a catalyst at a temperature of 80 to 250°C, a total pressure of 10 to 200 barg, and a liquid hourly space velocity (LHSV) of 0.1 to 6 h －１ reacting said nitrogen-enriched liquid oil stream with hydrogen, thereby forming a stabilized liquid oil stream.

2. 2. The method of claim 1, wherein the method has a hydrogen to liquid oil stream ratio, defined as the volumetric ratio of hydrogen to the flow of the liquid oil stream, of 100 to 8000 NL / L, such as 2000 to 5000 NL / L.

3. 3. The method of any one of claims 1 to 2, wherein the liquid oil stream contains at least 2% by mass of nitrogen (N), such as at least 5% by mass of N.

4. 4. The method of any one of claims 1 to 3, wherein the liquid oil stream contains at least 0.5% by mass oxygen (O), such as at least 2% by mass O, or at least 4% by mass O.

5. 5. A method according to any one of the preceding claims, wherein the liquid oil stream has a microcarbon residue (MCR) of 5 to 20 mass %, such as 5 to 15 mass %, as measured by ASTM D 4530.

6. 6. A method according to any one of claims 1 to 5, wherein the stabilised liquid oil stream has a microcarbon residue (MCR) of less than 5 mass %, such as less than 4.5 mass %, as measured by ASTM D 4530.

7. A method according to any one of claims 1 to 6, wherein the liquid oil stream is an oil stream derived from a thermochemical cracking process, such as pyrolysis or hydrothermal liquefaction.

8. the temperature is in the range of 180 to 220°C, for example 190 to 200°C; the pressure is in the range of 80 to 175 barg, for example 150 barg; and the LHSV is in the range of 0.2 to 4.0 h －１ , for example, 0.2 to 0.2 h －１ Or 0.8 to 1.0 h －１ , for example 0.9h －１ The method according to any one of claims 1 to 7, wherein

9. the temperature is in the range of 180 to 220°C, for example 190 to 200°C; the pressure is 15 to 80 barg, for example 50 barg; and the LHSV is 0.2 to 4.0 h －１ , for example, 0.2 to 2 h －１ Or 0.8 to 1.0 h －１ , for example 0.9h －１ The method according to any one of claims 1 to 7, wherein

10. 10. The method according to any one of claims 1 to 9, wherein the catalyst is a supported catalyst having a Mo content of 2 to 30 wt. % and optionally a P content of 0 to 3 wt. % based on the total weight of the catalyst.

11. 11. The method of claim 10, wherein the support is selected from alumina, silica, titania, or a combination thereof; optionally in combination with a molecular sieve having MFI, BEA, or FAU topology.

12. 12. The method according to any one of claims 1 to 11, wherein the catalyst is Ni-based, Mo-based, CoMo-based, NiMo-based, W-based, NiW-based or Ru-based, optionally in sulfided or reduced form.

13. 13. The method of any one of claims 1 to 12, further comprising a preceding step of pyrolysis of a solid renewable feedstock to produce said liquid oil stream.

14. The pyrolysis step comprises: pyrolysis, for example intermediate pyrolysis or delayed pyrolysis, to produce a pyrolysis oil stream; or - Hydrothermal liquefaction (HTL), producing an HTL oil stream; The method of claim 13, wherein

15. The solid renewable feedstock comprises: - Lignocellulosic-based biomass, including wood products, forestry waste, agricultural residues; and / or - municipal waste, in particular its organic components, which is defined as a feedstock containing materials from items discarded by society, such as mixed municipal waste as defined in EU Directive 2018 / 2001 (RED II), Annex IX, Part A; The method according to any one of claims 13 to 14.

16. 16. A method according to any one of claims 1 to 15, further comprising passing the stabilised liquid oil stream through a hydrodeoxygenation (HDO), hydrodenitration (HDN) or hydrodesulfurisation (HDS) step, suitably wherein the HDO is carried out at a higher temperature than the preceding step to form the stabilised liquid oil stream.

17. 17. The method of claim 16, further comprising passing the stabilized liquid oil stream through one or more metal guards active in hydrometallation (HDM) and / or hydrodeoxygenation (HDO) prior to the HDO step.

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