Low temperature stabilization of liquid oils

Abstract

The present invention relates to a process and an apparatus for hydrotreating a liquid oil stream, such as a pyrolysis oil stream, by continuously operating in a fixed bed reactor, in the presence of a reduced nickel (Ni) catalyst, the liquid oil stream is reacted with hydrogen at a temperature of 80-250 DEG C, a pressure of 10-200 barg, a liquid hourly space velocity (LHSV) of 0.1-6.0 h <-1 >, and a hydrogen / liquid oil ratio (defined as the volume ratio of hydrogen to liquid oil stream flow) of 100-8000 NL / L to form a stabilized liquid oil stream.

Description

[0001] The present invention relates to the field of hydroprocessing of liquid oils, such as pyrolysis oils, and more particularly to the stabilization of liquid oils by hydrotreating prior to upgrading by further hydroprocessing, such as hydrodeoxygenation (HDO). More particularly, the present invention relates to the stabilization of liquid oils produced by pyrolysis or hydrothermal liquefaction (HTL) of solid renewable feedstocks.

[0002] The field of renewable feedstocks is attracting significant attention worldwide. Using renewable feedstocks allows for the sustainable production of hydrocarbon products with boiling points in the transportation fuel range, particularly diesel, jet fuel suitable for sustainable aviation fuel (SAF), naphtha, and gasoline; as well as hydrocarbon feedstocks such as naphtha, ethane, propane, or butane for steam crackers used in polymer production.

[0003] Due to the wide variety and complex structure of renewable raw materials, their hydroprocessing is an extremely challenging task. Currently, it is generally believed that renewable raw materials are divided into three generations. The first generation of renewable raw materials refers to renewable raw materials that are already in liquid form, including virgin oils such as rapeseed oil and soybean oil. The second generation of renewable raw materials are waste oils and fats, such as waste cooking oil, animal fats and crude tall oil (CTO). The output of third-generation renewable raw materials is much greater than that of, for example, the second generation, that is, their supply is higher. The third generation of renewable raw materials includes solid renewable raw materials, including: i) solid waste, such as agricultural waste and forestry waste, such as lignocellulosic biomass such as grass; municipal waste, such as (unsorted) plastic waste; waste tires; and ii) low indirect land use change (ILUC) crops, such as castor, which have the advantage of not competing with food crops for space and can be grown under harsh climatic conditions. Although the source cost of solid renewable raw materials is lower than that of first- and second-generation raw materials and the output is larger, third-generation raw materials still face many challenges.

[0004] Due to the EU Renewable Energy Directive II (REDII), there is expected to be a higher demand for hydroprocessing of advanced renewable feedstocks, such as pyrolysis oils made from solid renewable feedstocks. Pyrolysis oils can contain very high oxygen contents, which need to be reduced for use as liquid fuels, i.e. hydrocarbon fuels with boiling points in the range of transportation fuels. Oxygen in hydrocarbon feedstocks is typically removed by a catalytic hydrodeoxygenation (HDO) process that uses high pressure (100-200 bar) and high temperature (350-400°C). However, although the oxygen content of HTL oil is generally lower than that of pyrolysis oil, liquid oils (such as pyrolysis oil or hydrothermal liquefaction oil, also referred to as HTL oil in the following) are very unstable and tend to polymerize upon heating, leading to rapid deactivation of the catalyst and clogging of the HDO reactor due to coking.

[0005] Liquid oils, often referred to as pyrolysis oils or HTL oils, can have a wide range of oxygen (O) contents, depending on the source (i.e., solid renewable feedstock) and the thermal decomposition process used to generate the liquid oil. For example, liquid oils produced from plastic or polymer feedstocks (also referred to herein as "waste plastic or polymer") can contain 0.05-15 wt% O (500 ppm wt to 15 wt%), while liquid feedstocks derived from, for example, lignocellulosic biomass or sewage sludge can contain 30-50 wt% O. Liquid oils produced from plastic or polymer feedstocks are also referred to as waste plastic pyrolysis oils (WPPO).

[0006] While it is desirable to upgrade liquid oils (also referred to in some cases as biocrude) into valuable hydrocarbon fuels, such as jet fuel for sustainable aviation fuel (SAF), as well as renewable diesel, renewable naphtha, and renewable gasoline, and optionally renewable marine fuel, liquid oils present significant technical and economic challenges due to low miscibility with other oils (e.g., petroleum fractions), low thermal and oxidative stability (e.g., instability at room temperature), high acidity and corrosiveness, a tendency to polymerize with increasing temperature, and coking.

[0007] Therefore, it is desirable to provide a method and apparatus that overcomes the aforementioned challenges and provides advantages over prior art methods.

[0008] US 3691066 A discloses a method for selective hydrogenation of unsaturated gasoline using a supported nickel catalyst at a temperature of 50-250° C. The total sulfur (S) content of the feedstock is 0.01-1.5 wt %, and the feedstock is obtained by thermal cracking of a high-sulfur, high-boiling-point petroleum fraction.

[0009] EP 2707460 A1 discloses a method for stabilizing pyrolysis oil, comprising hydrogenating the pyrolysis oil in the presence of a ruthenium metal catalyst at a temperature of at least about 70° C. and a pressure of at least about 600 psig (about 40 barg) to form a hydrogenated pyrolysis oil having a viscosity increase of less than 10%.

[0010] WO 2022063597, WO 2022023263, WO 2022023262, WO 2022144235 and WO 2021110395 disclose methods for processing pyrolysis oil from plastics, including selective hydrogenation.

[0011] US20014 / 0275666A1 discloses a two-stage process for processing bio-oil or pyrolysis oil. The clogging problem is addressed by placing a fractionation unit (distillation, Figure 4) upstream of the fixed-bed "stabilization" (first stage). Furthermore, Experiments AC (Table II) demonstrate the use of a NiMo catalyst to process the feed in a fixed-bed reactor.

[0012] WO 2022152900 A1 of the applicant discloses the use of NiMo catalysts for stabilizing liquid oils.

[0013] It has been found that methods and apparatus comprising providing a reduced nickel (Ni) catalyst can effectively stabilize various liquid oils at low temperatures (i.e., in the range of 80-250°C), including liquid oils with relatively low oxygen content (O) (0.05-15 wt%), such as some waste plastic pyrolysis oils or some HTL oils, and liquid oils with relatively high oxygen content (O) (30-50 wt%), such as 40-50 wt%), such as some pyrolysis oils from lignocellulosic biomass feedstocks or sewage sludge pyrolysis.

[0014] Thus, in a first aspect, the present invention provides a method for hydrotreating a liquid oil stream, as set forth in claim 1, by continuously operating in a fixed bed reactor in the presence of a reduced nickel (Ni) catalyst at a temperature of 80-250° C., a pressure of 10-200 barg, and a reaction time of 0.1-6.0 h. -1 The invention relates to a method for preparing a catalyst for reducing a Ni-containing gas by reacting a liquid oil stream with hydrogen at a liquid hourly space velocity (LHSV) of 100 NL / L and a hydrogen / liquid oil ratio of 100 to 8000 NL / L to form a stabilized liquid oil stream, wherein the hydrogen / liquid oil ratio is defined as the volume ratio of hydrogen to the flow rate of the liquid oil stream; wherein the reduced Ni catalyst is a supported catalyst having a Ni content of 2 to 30 wt %, such as 5 to 25 wt %, based on the total weight of the catalyst; and the support is selected from any one of the following: alumina (Al2O3), magnesium aluminum spinel (MgAl2O4) and combinations thereof; optionally in combination with a molecular sieve having a topological structure of MFI, BEA or FAU; and wherein the alumina is any one of the following:

[0015] - Alumina comprising 90-100 wt% gamma alumina and having: 230-250 m 2 / g BET surface area, 800-900 mL / kg total pore volume (PV), measured by mercury intrusion;

[0016] - Alumina comprising 90-100 wt% gamma alumina; and having: 165-185 m 2 / g BET surface area, 950-1100 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry;

[0017] - Alumina comprising 80-100 wt% theta alumina and 0-20 wt% alpha alumina; and having: 50-60 m 2 / g BET surface area, 600-700 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry.

[0018] It should be understood that the unit "barg" represents the pressure above atmospheric pressure (atmospheric pressure: about 1 bar). This pressure is also called "hydrogen pressure".

[0019] The term "first aspect" or "first aspect of the invention" refers to a method according to the invention. The term "second aspect" or "second aspect of the invention" refers to an apparatus, ie a process apparatus (system), according to the invention.

[0020] The term "comprising" includes "consisting only of", ie "consisting of.

[0021] The term "suitably" means "optionally", ie an optional embodiment.

[0022] The term "present invention" or simply "invention" may be used interchangeably with the term "this application" or simply "application".

[0023] The term "and / or" refers to any one of the three options associated with a given embodiment. The term "and / or" can be used interchangeably with the term "at least one of" the three options.

[0024] The article "a" or "an" is used to mean at least one.

[0025] The term "reduced Ni catalyst" can be used interchangeably with the term "monometallic (Ni) catalyst" or "monometallic Ni catalyst".

[0026] Additional definitions are provided in conjunction with one or more embodiments below.

[0027] In one embodiment, as defined in dependent claim 2, the Ni content is 10-15 wt%, and the alumina is an alumina comprising 90-100 wt% gamma alumina and having: 165-185 m 2 / g BET surface area, 950-1100 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry.

[0028] The related benefits are described in detail below.

[0029] The present invention stabilizes liquid oils (e.g., pyrolysis oils) with high oxygen contents of 30-50 wt% at low temperatures by converting at least the most reactive compounds in the pyrolysis oil (e.g., furfural, furans, aldehydes, ketones, and acids) into alcohols (e.g., efficiently converting carbonyl compounds into alcohols). During the stabilization process and / or in a subsequent hydroprocessing stage (e.g., hydrodeoxygenation (HDO)), the alcohols can be further converted into saturated organic compounds. Furthermore, the present invention can stabilize liquid oils (e.g., HTL oils, waste plastic pyrolysis oils, or waste tire pyrolysis oils) with oxygen contents as low as 0.05-15 wt% at low temperatures by converting at least the most reactive compounds in the HTL oil (e.g., dienes, more specifically conjugated dienes) (e.g., converting styrene into ethylbenzene). Thus, the present invention can stabilize pyrolysis oils by converting carbonyl groups into alcohols (thereby primarily breaking C=O bonds) and / or by converting styrene into ethylbenzene (thereby primarily breaking C=C bonds). As a result, the operating time before plugging problems (if any) occur can be extended, while catalyst coking and subsequent catalyst deactivation are suppressed and hydrogen starvation is avoided.

[0030] Thus, "liquid oil" or "liquid oil stream" refers to a feedstock containing compounds that react at temperatures above 80-250°C but below those that achieve essentially complete hydroprocessing and may react to form larger molecules, which may cause complete or partial plugging of reactors, pipes, heaters, heat exchangers, and catalysts. Examples of such mixtures include: feedstocks rich in the conjugated dienes or styrene and its homologues (produced by the thermochemical decomposition of plastic waste, municipal solid waste, refuse-derived fuels, and solid recovered fuels); feedstocks rich in carbonyl compounds and sugars (produced by the thermochemical decomposition of lignocellulosic biomass); feedstocks rich in nitrogen (produced by the thermochemical decomposition of nitrogen-rich biomass such as manure and sewage sludge); and similar compositions from other sources. The reactive compounds can react within the same functional group (e.g., diene with diene) or across functional groups (e.g., aldehyde with phenol).

[0031] The temperature range of 80-250°C covers both the inlet temperature of the liquid oil stream and the outlet temperature of the stabilized liquid oil stream. For example, the inlet temperature can be 80, 90, 100, 110, or 120°C. The process is exothermic, so the temperature may rise by about 100°C or more. The higher the inlet temperature, the easier it is for the process to ignite and initiate an exotherm. The outlet temperature can be, for example, 150, 160, 200, or 240°C. More generally, the temperature in a given step or its reactor (unit) refers to the inlet temperature in an adiabatic step or the reaction temperature in an isothermal step.

[0032] The term continuous operation, as is well known in the art, means that during a given production cycle, the input flow of liquid oil is constant and a stabilized flow of liquid oil is withdrawn as an output product. This is in contrast to batch operation (i.e., non-continuous operation), also well known in the art, in which all the liquid oil and catalyst are introduced at the beginning of the process and the output product is withdrawn after a period of time.

[0033] The present invention utilizes a continuous process because, unlike batch operations, it does not rely on the final product (stabilized liquid oil) to remain fluid. In batch operations, the liquid oil may initially be fluid, then solidify for a period of time at a first temperature, and then become fluid again when heated to a final, higher temperature. Furthermore, batch operations only provide a guide to initial catalyst activity, making it easy to overestimate catalyst activity, which is crucial for industrial applications.

[0034] Furthermore, there is a significant difference between the outlet temperatures above 250°C (e.g., 340°C or higher) in prior art processes (e.g., conventional hydrodeoxygenation) and the present invention, which operates at outlet temperatures of 250°C or lower (e.g., 200°C). For example, at approximately 200°C, carbonyl compounds are converted to alcohols, as will become clear in the discussion below. Some sugars may also be converted to diols, and some alcohols may be dehydrated. On the other hand, at approximately 340°C, phenol removal begins, and depending on the pressure and liquid space velocity (LHSV), oxygen in the liquid oil may also be removed.

[0035] The present invention also provides a method having a hydrogen / liquid oil ratio of 100-8000 NL / L, such as 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, or 7500 NL / L. As used herein, "hydrogen / liquid oil ratio" or "H2 / oil ratio" refers to the volumetric ratio of hydrogen to liquid oil flow. Liquid oil volume is measured at 15°C and 1 atmosphere based on field practice. It will be understood that the unit NL represents "standard" liters, i.e., the amount of gas that would occupy that volume at 0°C and 1 atmosphere.

[0036] In order to stabilize pyrolysis oil, the hydrogen consumption is usually between 100-350 NL / L, measured by the hydrogen / liquid oil ratio, but in order to avoid hydrogen deficiency, we found that the hydrogen / liquid oil ratio should be higher, that is, for liquid oil with low oxygen (O) content (such as HTL oil), the hydrogen / liquid oil ratio should be 100-8000 NL / L, such as 400-6000 NL / L, such as 400-600 NL / L, or 400-700 NL / L, such as 500-600 NL / L; or for liquid oil with high oxygen content (such as pyrolysis oil), the hydrogen / liquid oil ratio should be 1500-5000 NL / L. Since the stabilized liquid oil is preferably fed directly into the HDO reactor, as will be shown in the embodiments below, and hydrogen consumption is typically between 400-800 NL / L, we have found that for pyrolysis oil, to avoid hydrogen starvation, a more preferable hydrogen / liquid oil ratio is, for example, between 1500-5000 NL / L. For example, stabilizing the liquid oil requires 100-350 NL / L, while deoxygenating requires 400-800 NL / L. Therefore, the total hydrogen consumption in this particular case may be as high as 1150 NL / L. Adding H2 in excess of this amount (e.g., 1500-3500 NL / L, such as 200-3000 NL / L) can accelerate the reaction rate and / or equilibrium.

[0037] Therefore, the present invention can achieve low-temperature (80-250° C., such as 100-240° C.) stabilization of liquid oil. In addition, the present invention can not only stabilize liquid oil, thereby avoiding the above-mentioned clogging problem, but also achieve stabilization without causing catalyst deactivation and the risk of hydrogen starvation.

[0038] In one embodiment, as described in additional claim 3, the liquid oil stream contains at least 0.05 wt% oxygen (O), such as at least 0.1 wt% O, at least 0.5 wt% oxygen (O), at least 1 wt% O, at least 5 wt% O, at least 10 wt% O, at least 15 wt% O, at least 20 wt% O, at least 25 wt% O, at least 30 wt% O, at least 35 wt% O, at least 40 wt% O, or at least 45 wt% O; such as 0.05-50 wt% O, such as 0.05-15 wt% O, 30-50 wt% O, or 40-50 wt% O. Oxygen is suitably determined by standard elemental analysis.

[0039] Thus, in one embodiment, the liquid oil stream contains at least 20 wt% oxygen (O), such as at least 30 wt% O, or at least 45 wt% O. This oxygen content represents a particularly reactive liquid oil feed, as the oxygen content can serve as an indicator of the reactivity of the liquid oil. Thus, a highly reactive liquid oil stream may contain up to 45 wt% oxygen, or even higher; for example, a highly reactive liquid oil stream may contain 30-50 wt% O, such as 40-50 wt% O. For the purposes of this application, a liquid oil having this oxygen content (30-50 wt%) is considered a highly reactive liquid oil stream, particularly a highly reactive pyrolysis oil stream. In another embodiment, the liquid oil stream contains 0.05-15 wt% O. This is a less reactive liquid oil stream, but still requires stabilization. For the purposes of this application, a liquid oil having this oxygen content is considered a less reactive liquid oil stream, particularly a less reactive HTL oil stream or a less reactive pyrolysis oil stream. For example, the oxygen content of waste plastic pyrolysis oil may be as low as 500 ppmwt (0.05 wt%), while the oxygen content of waste tire pyrolysis oil may be 0.1-5 wt%. For the purposes of this application, a liquid oil with a moderate oxygen content (e.g., an oxygen content between 15 and 30 wt%, inclusive) is considered a moderately reactive liquid oil stream, which can be any of an HTL oil stream, a pyrolysis oil stream, and combinations thereof.

[0040] In one embodiment, as described in appended claim 4, the ratio of the carbonyl number (in mol / kg) of the liquid oil stream to the stabilized liquid oil stream measured by ASTM E 3146, i.e., the carbonyl number ratio, is 1.7 or higher, such as 2 or higher, such as 3 or higher.

[0041] It has been found that when the carbonyl ratio is 1.7 or higher (e.g., 2 or higher, such as 3 or higher), clogging of the subsequent HDO reactor can be avoided. The higher the carbonyl ratio, the more efficient the process is in breaking the C=O bonds and the better the stabilization effect, especially when using a highly reactive liquid oil, thereby producing a stabilized liquid oil stream that is much less reactive than the highly reactive liquid oil stream fed to the process. It has been found that the present invention provides a reduced nickel (Ni) catalyst, i.e., a monometallic catalyst (Ni), having a higher carbonyl ratio than when using a NiMo catalyst. Therefore, the present invention provides a more advantageous process, such as the attached Figure 2 shown.

[0042] In one embodiment, as described in appended claim 5, the stabilized liquid oil stream has a carbonyl number below 3.0 mol / kg, such as between 1.0 and 2.0 mol / kg, as measured by ASTM E 3146.

[0043] Compared to the stabilization method using NiMo-based catalysts, the carbonyl number ratio of the present invention is higher. Therefore, the carbonyl number of the stabilized liquid oil stream is also lower, such as the 1.0-2.0 mol / kg, such as 1.5-1.9 mol / kg, such as 1.6, 1.7 or 1.8 mol / kg. Figure 2 .

[0044] The process can be operated by controlling the carbonyl number in the stabilization reactor to maintain it below 3.0 mol / kg, for example, between 1.0 and 2.0 mol / kg, as it has been found that an increase in the carbonyl number to 3.0 or higher may lead to coking and thus plugging of the downstream HDO unit (reactor). In addition, the carbonyl number ratio should be appropriately monitored and maintained at 1.7 or higher to avoid coking and plugging of the downstream HDO reactor.

[0045] As noted above, in one embodiment, the liquid oil stream is a pyrolysis oil stream or a hydrothermal liquefaction oil (HTL oil) stream.

[0046] In one embodiment, the liquid oil stream is a pyrolysis oil stream comprising at least 0.5 mol / kg of one or more of the following: aldehyde compounds, ketones, alcohols, furfural, as determined by ASTM E3146-20.

[0047] The present invention includes: the reduced Ni catalyst is a supported catalyst, the Ni content of which is 2-30wt% of the total weight of the catalyst, for example 5-25wt%, and the carrier is selected from any one of the following: alumina (Al2O3), aluminum magnesium spinel (MgAl2O4) and a combination thereof; optionally combined with a molecular sieve having a topological structure of MFI, BEA or FAU.

[0048] The catalyst having this composition is suitable for stabilizing low-reactivity, medium-reactivity, and high-reactivity liquid oils and is therefore applicable to a variety of liquid oils with oxygen contents ranging from 0.05 to 50 wt%. Therefore, the present invention offers advantages and flexibility in stabilizing liquid oil streams (i.e., liquid oil feeds). For example, when the liquid oil feed is a low-reactivity liquid oil stream or a high-reactivity liquid oil stream, there is no need to replace the catalyst.

[0049] In one embodiment, the Ni content is any one of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 wt % based on the total weight of the catalyst, and the support is selected from any one of the following: alumina (Al2O3), aluminum magnesium spinel (MgAl2O4) and combinations thereof; optionally in combination with a molecular sieve having a topology of MFI, BEA or FAU.

[0050] The present invention includes that the aluminum oxide is any one of the following:

[0051] - an alumina comprising 90-100 wt% gamma alumina, for example 95-100 wt% gamma alumina, and having:

[0052] 230-250m 2 / g BET surface area,

[0053] 800-900 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry;

[0054] - an alumina comprising 95-100 wt% gamma alumina, for example 95-100 wt% gamma alumina, and having:

[0055] 165-185m 2 / g BET surface area,

[0056] 950-1100 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry;

[0057] - an alumina comprising 80-100 wt% theta alumina and 0-20 wt% alpha alumina, and having:

[0058] 50-60m 2 / g BET surface area,

[0059] 600-700 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry.

[0060] Mercury intrusion porosimetry was performed in accordance with ASTM D4284. Therefore, to determine the total pore volume and pore size distribution, mercury intrusion porosimetry was performed in accordance with ASTM D4284. BET surface area was measured in accordance with ASTM D4567-19, i.e., single-point surface area determination using the BET equation. The contents of alpha alumina, theta alumina, and gamma alumina were determined by XRD (X-ray diffraction). More specifically, XRD was used to determine, for example, the alumina phase: the sample was extracted and rinsed with xylene, vacuum-dried, and then subjected to metal / P capture analysis (XRF, X-ray fluorescence analysis according to EN ISO 12677:2011), SEM, carbon and sulfur (C+S; LECO analysis, ASTM E1915-13), and BET surface area analysis (ASTM D4567-19).

[0061] Catalysts containing these specific alumina supports are particularly suitable for stabilizing intermediates, particularly highly reactive liquid oils having an oxygen content of at least 30 wt% (e.g., at least 40 wt% or at least 45 wt%). For example, another indicator of the degree of stabilization is the density of the liquid oil. The higher the density, the higher the viscosity. Therefore, the lower the density of the stabilized liquid oil compared to the density of the liquid oil feed, the better the stability.

[0062] The present invention can stabilize various liquid oils from third-generation renewable raw materials, producing liquid oil streams with low oxygen content, such as 0.05-15 wt% O, and / or liquid oil streams with high oxygen content, such as 30-50 wt% O. For example, in the latter case, the density of the liquid oil is significantly reduced, the number of carbonyl groups is reduced, and the amount of oxygen added is reduced. Figure 1 and 2 shown.

[0063] It has been found that the density of the liquid oil fed to the stabilization process can be significantly reduced, in particular by using an alumina support having a medium BET surface area and a high pore volume, as described in the following embodiments. Thus, according to said additional claim 2, the Ni content is 10-15 wt%, and the alumina is an alumina comprising 90-100 wt% gamma alumina, for example 95-100 wt% gamma-alumina, and having: 165-185 m 2 / g BET surface area, 950-1100 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry.

[0064] Thus, even better results are achieved in reducing density, increasing the carbonyl number ratio or reducing the carbonyl number of the stabilized liquid oil. Figure 1 As shown, the density of the liquid oil delivered during the stabilization process can be further reduced. Although the density of some catalysts reaches a minimum after a certain time on stream (TOS), the density then increases again until it is slightly lower than but close to the feed density (feed density: 1.19, see Figure 2 Y-axis), but with a relatively low Ni content (10-15 wt%; D-low Ni, denoted as "Support D Low Metal" in the figure) or a high Ni content (20-25 wt%; D-high Ni, denoted as "Support D High Metal" in the figure), with a BET surface area of ​​165-185 m 2 / g with 90-100 wt% gamma alumina and a total pore volume (PV) of 950-1100 mL / kg (e.g. Figure 1 The catalyst (shown by the two lower lines in ) shows a surprisingly low density and reaches a plateau at this level, i.e., it remains at a low density. In addition, the carbonyl number ( Figure 2) is also the lowest. Therefore, its performance is superior to that of, for example, NiMo catalysts. In addition, its performance is also superior to that of other reduced Ni catalysts (i.e., monometallic catalysts, Ni). Therefore, the performance of the D-low Ni catalyst ("Carrier D Low Metal") in reducing the density of the liquid oil feed is at least comparable to that of a reduced Ni catalyst using the same alumina carrier but with almost twice the nickel content (D-High, i.e., "Carrier D High Metal"); despite the lower Ni content, it is superior in reducing the carbonyl number, as shown in the attached figure. Figure 2 As shown in Figure 2, the amount of metal required is also reduced relative to the total metal content of the NiMo catalyst. This means that the operating costs of the stabilized reactor are greatly reduced.

[0065] The support may comprise a molecular sieve having an MFI, BEA or FAU topology. As used herein, the term "MFI, BEA or FAU topology" refers to the structure specified and maintained by the International Zeolite Association Structure Committee in the Atlas of Zeolite Framework Types (http: / / www.iza-structure.org / databases / ), or, for example, the structure defined in the Atlas of Zeolite Framework Types (6th revised edition, 2007) compiled by Ch. Baerlocher, L.B. McCusker and D.H. Olson.

[0066] In one embodiment, as described in the appended claim 6, the temperature range is 80-225°C, such as 100-225°C; the pressure is 120-200 barg, such as 125-175 barg, such as 135-155 barg; the liquid hourly space velocity (LHSV) is 0.1-1.0h -1 , for example 0.2-0.6h -1 The hydrogen / liquid oil ratio is 1500-3500 NL / L, for example 2000-3000 NL / L, and the liquid oil stream contains 30-50 wt% O. Therefore, these process conditions are particularly favorable for highly reactive pyrolysis oil. Under these conditions, the cleavage of C=O bonds in the liquid oil is further ensured. Furthermore, as previously mentioned, this specific range of hydrogen / liquid oil ratio has the associated benefits of avoiding hydrogen starvation and improving reaction rate and / or equilibrium.

[0067] In one embodiment, as described in the appended claim 7, the temperature is 80-225°C, such as 100-200°C; the pressure is 40-180 barg, such as 40-60 barg or 70-180 barg, such as 100-150 barg; the LHSV is 1-3h -1 , for example 1.5-2.5h -1The hydrogen / liquid oil ratio is 400-700 NL / L, for example, 500-600 NL / L, and the liquid oil stream contains 0.05-15 wt% O. Therefore, these process conditions are particularly advantageous for less reactive HTL oils, waste plastic pyrolysis oils, or waste tire pyrolysis oils. Under these conditions, C=C bond cleavage in the liquid oil is further ensured. According to the present invention, by using a reduced nickel catalyst, the efficiency of C=C bond cleavage is significantly higher than that demonstrated using a NiMo-based catalyst, such as in the conversion of styrene to ethylbenzene. Furthermore, as previously mentioned, this specific hydrogen / liquid oil ratio range has the benefit of avoiding hydrogen starvation. The pressure, for example, is 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, or 170 barg. For some pyrolysis oils, such as waste plastic pyrolysis oil, a pressure in the range of 40-60 barg may be sufficient, but for some HTL oils, the required pressure may be higher, so the suitable pressure range is 70-180 barg.

[0068] A stabilized liquid oil stream is thereby obtained, which enables long-term stable operation of the subsequent upgrading steps and related units, in particular hydrodeoxygenation (HDO), as will also be apparent from the following embodiments.

[0069] In one embodiment, as described in the appended claim 8, the sulfur (S) content in the liquid oil stream containing 0.05-15wt% O is less than 100ppmwt, such as 1-90ppmwt, such as 5, 10, 20, 30, 40, 50, 60, 70, 80ppmwt.

[0070] The surface of the nickel catalyst is thus passivated by the sulfur in the liquid oil stream, forming a protective sulfur oxide layer on the active metal (Ni), thereby preventing its oxidation. Thus, the catalyst can be surface passivated by exposure to sulfur in the liquid oil. It has been found that, while the catalyst is still in a reduced state, only a small amount of sulfur is actually needed to inhibit the activity of the reduced nickel catalyst, thereby increasing its selectivity so that only dienes (diolefins) are hydrogenated at low temperatures, while monoolefins are not. This passivation is particularly important for liquid oils produced from plastic or polymer feedstocks; for such liquid oils, the surface passivation is performed in situ, i.e., during operation, because sulfur contents below 100 ppm wt may be encountered therein.

[0071] While it is known from the aforementioned US Pat. No. 3,691,066 and other publications that gasoline with a high sulfur content (0.01-1.5 wt% sulfur) produced from fossil sources can be hydrogenated over nickel catalysts without significant sulfur poisoning, surprisingly, according to the present invention, small amounts of sulfur do not impair the hydrogenation activity of the reduced nickel catalyst during the stabilization of liquid oils derived from, for example, plastic or polymer feedstocks. This eliminates the need for a desulfurization unit or desulfurization protection unit prior to (i.e., upstream of) the stabilization process. Furthermore, the halogens in liquid oils (particularly waste plastic pyrolysis oils) may contain halogens such as chlorine, and such halogens are expected to inhibit hydrogenation activity, for example due to the formation of nickel dichloride (NiCl).

[0072] In one embodiment, as described in the appended claim 9, the method further comprises a prior step of thermally decomposing a solid renewable feedstock to produce the liquid oil stream; wherein the liquid oil stream is a pyrolysis oil stream or a hydrothermal liquefaction oil (HTL oil) stream; and wherein the thermal decomposition step is:

[0073] - pyrolysis, such as fast pyrolysis, thereby producing said pyrolysis oil stream; or

[0074] - Hydrothermal liquefaction, thereby producing said HTL oil stream.

[0075] For convenience, the term "thermal decomposition" as used herein shall broadly refer to any decomposition process in which a material is partially decomposed at high temperatures (typically 250°C to 800°C, or even 1000°C) in the presence of substoichiometric amounts of oxygen (including in the absence of oxygen). The products are typically a mixture of liquid and gas phases, as well as a certain amount of solid char. The term shall be understood to include processes known as pyrolysis and hydrothermal liquefaction, carried out in the presence and absence of catalysts.

[0076] Thus, in particular embodiments, the thermal decomposition is pyrolysis, such as fast pyrolysis, as further defined below, thereby producing said pyrolysis oil stream.

[0077] It is understood that thermal decomposition is carried out in the thermal decomposition section. Therefore, pyrolysis is carried out in the pyrolysis section, while hydrothermal liquefaction is carried out in the hydrothermal liquefaction section.

[0078] As used herein, the term "section" refers to a physical section that contains a unit or combination of units for performing one or more steps and / or sub-steps.

[0079] For the purposes of the present invention, the pyrolysis section produces two main streams, namely a pyrolysis waste gas stream and a pyrolysis oil stream. The pyrolysis section can be in the form of a fluidized bed, a conveying bed or a circulating fluidized bed as is well known in the art. For example, the pyrolysis section can include a pyrolysis unit (pyrolysis reactor), a cyclone separator for removing particulate solids (such as coke), and a cooling unit for producing the pyrolysis waste gas stream and the pyrolysis oil stream (i.e., condensed pyrolysis oil). The pyrolysis waste gas stream contains light hydrocarbons (such as C1-C4 hydrocarbons), CO and CO2. The pyrolysis oil stream, also known as bio-oil or bio-crude oil, is a liquid substance rich in a mixture of molecules, typically consisting of more than two hundred different compounds, including aldehydes, ketones and / or other compounds, such as furfural with a carbonyl group, which is formed by depolymerization of the products of the pyrolysis treatment.

[0080] For the purposes of the present invention, pyrolysis is preferably fast pyrolysis, also known in the art as flash pyrolysis. Fast pyrolysis refers to the thermal decomposition of solid renewable raw materials under anaerobic conditions at a temperature of 350-650°C (e.g., about 500°C) with a reaction time of 10 seconds or less (e.g., 5 seconds or less, e.g., about 2 seconds). Fast pyrolysis can, for example, be carried out by autothermal operation, e.g., in a fluidized bed reactor. The latter is also known as autothermal pyrolysis, which is characterized in that air (optionally with an inert gas or recycled gas) is used as a fluidizing gas, or a mixture of air and an inert gas or recycled gas is used. Therefore, the partial oxidation of the pyrolysis compounds produced in the pyrolysis reactor (autothermal reactor) provides energy for pyrolysis while improving heat transfer. For detailed information on autothermal pyrolysis, please refer to the following literature: Robert Brown, "Heterodoxyin Fast Pyrolysis of Biomass":

[0081] https: / / dx.doi.org / 10.1021 / acs.energyfuels.0c03512

[0082] It will therefore be understood that for the purposes of the present invention, the use of autothermal pyrolysis, ie, autothermal operation, is one specific embodiment for performing fast pyrolysis.

[0083] There are several types of fast pyrolysis, all of which require the use of catalysts. Sometimes, an acidic catalyst is used in the pyrolysis reactor to upgrade the pyrolysis steam. This technique, known as catalytic fast pyrolysis, can be performed in either an in situ mode (where the catalyst is located within the pyrolysis reactor) or an ex situ mode (where the catalyst is placed in a separate reactor). The advantage of using a catalyst is that it lowers the activation energy of the reaction, significantly reducing the temperature required to perform the pyrolysis. It can also improve the selectivity of the desired pyrolysis oil compounds.

[0084] In some cases, hydrogen is added during the catalytic pyrolysis process, which is called reactive catalytic fast pyrolysis. If the catalytic pyrolysis is carried out under high hydrogen pressure (~>5 barg), it is usually called catalytic hydropyrolysis.

[0085] In one embodiment, as described in the appended claim 10, the pyrolysis stage is a fast pyrolysis stage, which is carried out in the absence of a catalyst and hydrogen, i.e. the fast pyrolysis stage is not catalytic fast pyrolysis, hydropyrolysis or catalytic hydropyrolysis. This makes the process simpler and less expensive.

[0086] In one embodiment, the pyrolysis off-gas stream comprises CO, CO2 and light hydrocarbons such as C1-C4, and optionally also comprises H2S.

[0087] In one embodiment, thermal decomposition is hydrothermal liquefaction. Hydrothermal liquefaction refers to processing biomass in a high temperature pressurized water environment for a sufficiently long time to decompose the solid polymer or biopolymer structure into a main liquid component, thereby thermochemically converting biomass into liquid fuel. Typical hydrothermal processing conditions are temperatures in the range of 250-375 ° C and operating pressures in the range of 40-220 bar. Compared with pyrolysis (such as fast pyrolysis), this technology has the advantages of lower operating temperature, higher energy efficiency and lower tar yield. For detailed information on biomass hydrothermal liquefaction, please refer to, for example, the following literature: Golakota et al., "A review of hydrothermal liquefaction of biomass", Renewable and Sustainable Energy Reviews, vol.81, Part 1, Jan.2018, p.1378-1392.

[0088] In one embodiment, the thermal decomposition is liquefaction. Liquefaction refers to the process of thermochemically converting biomass into liquid fuels under anhydrous conditions. Typical conditions are temperatures in the range of 250-375°C and operating pressures in the range of 40-220 bar, as described, for example, in WO21209555 A1.

[0089] In one embodiment, the pyrolysis further comprises feeding the solid renewable feedstock to a solid renewable feedstock preparation stage, which may include, for example, drying to remove moisture and / or pulverizing to reduce particle size. Any moisture / humidity in the solid renewable feedstock that evaporates, for example, in the pyrolysis stage, may condense in the pyrolysis oil stream and be entrained into the process, which may be undesirable. Furthermore, the heat used to evaporate the moisture removes heat required for pyrolysis. By removing moisture and also reducing the particle size of the solid renewable feedstock, the thermal efficiency of the pyrolysis stage can be improved.

[0090] In one embodiment, as described in the appended claim 11, the solid renewable raw material is lignocellulosic biomass, including wood products, forestry waste, and agricultural residues. In another embodiment, as described in the appended claim 11, the solid renewable raw material is sewage sludge, in particular its organic fraction. In another embodiment, as described in the appended claim 11, the solid renewable raw material is scrap tires. In another embodiment, as described in the appended claim 11, the solid renewable raw material is municipal waste, in particular its organic fraction. In another embodiment, as described in the appended claim 11, the solid renewable raw material is a plastic or polymer-derived raw material, i.e., waste plastic or polymer, including mixed or sorted waste containing at least 50 wt%, 80 wt%, or 90 wt% of plastics and other synthetic polymers. Any combination of the above raw materials is also contemplated.

[0091] For the purposes of this application, the term "sewage sludge" refers to residual semi-solid material produced as a by-product during industrial or municipal sewage treatment processes; for example, dewatered sludge comprises: 50-70 wt% organic matter and 30-50 wt% mineral components (including 1-4 wt% inorganic carbon), 1-10 wt% N, such as 3.4-4.0 wt% nitrogen (N), 0.5-2.5 wt% phosphorus (P).

[0092] For the purposes of this application, the term "municipal waste" is interchangeable with the term "municipal solid waste" and refers to raw materials containing items discarded by the public, such as mixed municipal waste with waste code 200301 in the European Waste Catalogue.

[0093] In particular embodiments, lignocellulosic biomass is forestry waste and / or agricultural residues, and includes biomass derived from plants, including grasses, such as native grasses (grasses derived from natural landscapes), wheat, such as wheat straw, oats, rye, reed grass, bamboo, sugarcane or sugarcane derivatives, such as bagasse, corn, and other grains.

[0094] As used herein, the term "lignocellulosic biomass" refers to biomass containing cellulose, hemicellulose and (optionally) lignin. The lignin or a substantial part thereof may have been removed, for example by a previous bleaching step.

[0095] In one embodiment, as described in additional claim 12, the process further comprises subjecting the stabilized pyrolysis oil stream to a hydrodeoxygenation (HDO) step, suitably wherein the HDO is carried out at a higher temperature and at an equal or lower pressure than in the preceding step forming the stabilized liquid oil stream.

[0096] Thus, any organic nitrogen present in the stabilized pyrolysis oil stream is removed, and a hydrotreated oil stream is produced, which can be further processed to produce hydrocarbon products with boiling points in the transportation fuel range, such as diesel, jet fuel (suitable for use as sustainable aviation fuel (SAF)), and naphtha. Further processing may include any of the following: hydrodewaxing, isomerization, hydrocracking, which are well known in the fossil petroleum refining art.

[0097] As mentioned previously, renewable feedstocks, including their intermediate products (e.g., liquid oils such as pyrolysis oil), typically contain significant amounts of oxygenates and unsaturated hydrocarbons. During the hydroprocessing of renewable feedstocks or liquid oils, oxygen is primarily removed in the form of water. This is known as the hydrodeoxygenation (HDO) pathway. Oxygen can also be removed via the dicarboxylic acid (DCO) pathway, which produces carbon dioxide instead of water:

[0098] HDO pathway:

[0099] Decarboxylation pathway:

[0100] During the stabilization of liquid oils, alcohols and other acids (such as fatty acids) present in them undergo transformations: alcohols can be converted to the corresponding alkanes or unsaturated organic compounds, which are then hydrogenated to the corresponding alkanes. Acids and other compounds containing carbonyl groups (such as aldehydes and ketones) are first converted to the corresponding alcohols via hydrogenation, which can then be converted to alkanes as described above. During the stabilization process, the oxygen atom in the carbonyl group of a given organic compound can be removed as HO or CO via the HDO and DCO reaction pathways described above. For example, in the case of phenol, the oxygen is removed directly, resulting in benzene and HO. Phenol's oxygen can also be removed via hydrogenation, where phenol is first converted to cyclohexanol and then to cyclohexane and HO.

[0101] According to the described reaction HDO and DCO pathways, alcohols and acids or other compounds with carbonyl groups remaining during the stabilization process will be converted into paraffins in the subsequent HDO stage.

[0102] Materials catalytically active in hydroprocessing, such as HDO, typically include an active metal (a sulfided base metal such as nickel, cobalt, tungsten, and / or molybdenum, but may also include elemental noble metals such as platinum and / or palladium) and a refractory support (such as alumina, silica, or titania, or combinations thereof).

[0103] Such hydroprocessing, referred to herein as HDO conditions, involves a temperature in the range of 250-400°C, e.g., 300-400°C, a pressure in the range of 30-250 bar, e.g., 50-150 bar, and a liquid hourly space velocity (LHSV) in the range of 0.1-2, optionally together with intermediate cooling by quenching with cold hydrogen, feed or product.

[0104] Catalytic materials active in hydrodewaxing (used herein interchangeably with the term hydroisomerization or simply isomerization) typically include an active metal (elemental noble metals such as platinum and / or palladium, or sulfided base metals such as nickel, cobalt, tungsten and / or molybdenum), an acidic support (typically a molecular sieve having high shape selectivity and having topologies such as MOR, FER, MRE, MWW, AEL, TON and MTT), and a refractory support (e.g., alumina, silica or titania, or combinations thereof).

[0105] The isomerization conditions include 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.

[0106] The materials catalytically active in hydrocracking are similar in nature to those catalytically active in isomerization and typically comprise an active metal (elemental noble metals such as platinum and / or palladium, or sulfided base metals such as nickel, cobalt, tungsten, and / or molybdenum), an acidic support (typically a molecular sieve with high cracking activity and a topology such as MFI, BEA, and FAU), and a refractory support (such as alumina, silica, or titania, or a combination thereof). The materials catalytically active in hydrocracking differ from those catalytically active in isomerization in the nature of the acidic support, which may have a different structure (even amorphous silica-alumina) or different acidities due to a different silica / alumina ratio.

[0107] Hydrocracking conditions include a temperature in the range of 250-400°C, a pressure in the range of 30-150 bar, a liquid hourly space velocity (LHSV) in the range of 0.5-8, optionally with intermediate cooling with cold hydrogen, feed or product

[0108] Other types of hydroprocessing are also contemplated, such as hydrodearomatization (HDA). The catalytically active species in hydrodearomatization typically comprise an active metal (typically an elemental noble metal such as platinum and / or palladium, but may also comprise sulfided base metals 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).

[0109] The hydrodearomatization conditions include a temperature in the range of 200-350° C., a pressure in the range of 20-100 bar, and a liquid hourly space velocity (LHSV) in the range of 0.5-8.

[0110] In one embodiment, as described in the appended claim 13, the method further comprises passing the stabilized liquid oil stream through one or more metal guards active in hydrodemetallization (HDM) and / or hydrodeoxygenation (HDO) prior to the hydrodeoxygenation (HDO) step.

[0111] Thus, a purified hydrotreated effluent stream is generated before it is sent to the subsequent hydrodeoxygenation (HDO) step. The term "metal guard bed active in HDM and / or HDO" is also referred to herein as "metal guard bed" and refers to a bed, i.e. a fixed bed, comprising a material active in hydrodemetallization (HDM) and / or hydrodeoxygenation (HDO), such as a catalyst active in HDM and / or HDO, which material may therefore have deoxidation activity in addition to removing, for example, phosphorus (P), iron (Fe), nickel (Ni), vanadium (V), silicon (Si), halogens or combinations thereof. A suitable guard bed for removing at least P and Fe is a porous material comprising alumina, said alumina comprising α-alumina, and said porous material comprising one or more metals selected from Co, Mo, Ni, W and combinations thereof, and said porous material having a BET surface area of ​​1 to 110 m 2 / g, suitably also having a total pore volume (measured by mercury intrusion) of 0.50-0.80 ml / g, and having a pore size distribution (PSD) in which at least 30 vol% of the total pore volume has a radius ≥ holes, suitably with a radius ≥ Holes with radii up to pores; for example, as disclosed in the applicant's patent application WO 2022008508. Another suitable guard bed is a catalyst comprising molybdenum supported on alumina, i.e., a Mo / Al2O3 catalyst. Another suitable catalyst is a catalyst having demetallization activity and moderate hydrodesulfurization activity, such as the commercially available TK-743 catalyst.

[0112] Hydrodemetallization (HDM) is a pretreatment process known in the art whereby free metals are generated which are then reacted with, for example, H2S to form metal sulfides. It should be understood that this is different from, for example, hydrodesulfurization (HDS), where heteroatoms (S) are removed as a gas.

[0113] In one embodiment, as described in appended claim 14, the method further comprises:

[0114] - providing supplemental hydrogen and supplying at least a portion thereof as said hydrogen to form said stabilized liquid oil stream; and / or

[0115] providing a recycle gas comprising CO and supplying at least a portion thereof (i.e. a portion of the recycle gas comprising CO) to the stabilized liquid oil stream before the HDO step, i.e. to a point downstream of the stabilization step but upstream of the HDO step, for example before passing the stabilized liquid oil stream through one or more metal guards active in hydrodemetallization (HDM) and / or hydrodeoxygenation (HDO).

[0116] It is generally desirable to introduce make-up hydrogen into the stabilization reactor, such as hydrogen produced within the plant or from an external source (i.e., hydrogen from outside the plant boundaries), or a combination of both. In addition to make-up hydrogen, it is generally desirable to introduce recycle gas into the stabilization reactor. Recycle gas can be, for example, hydrogen-rich gas generated in the process or plant, or a light hydrocarbon stream containing C1-C4 hydrocarbons, or a tail gas containing carbon oxides (CO2, CO), H2O, H2, and C1-C4 hydrocarbons. These recycle gases all have in common the presence of CO, albeit at lower concentrations.

[0117] It has been discovered that a problem with using a reduced nickel catalyst when feeding a portion of the liquid oil stream to the stabilization step is that when the gas contains CO, the nickel is removed as Ni(CO)4 (nickel carbonyl). Nickel carbonyl is harmful because it is extremely toxic and can be fatal if inhaled; it can cause severe skin burns and eye damage, and it is a flammable liquid and vapor. Therefore, the present invention eliminates the step of feeding recycle gas containing at least a small amount of CO to the stabilization reactor, which is common in the prior art. Make-up hydrogen without CO is fed to the stabilization reactor, while the recycle gas is fed downstream of the stabilization reactor and upstream of the HDO. This improves the safety of the process and equipment.

[0118] In one embodiment, the method further includes: before performing the stabilization treatment to form the stabilized liquid oil stream, subjecting the liquid oil stream to a purification step to remove impurities from the liquid oil stream. For example, a liquid oil stream provided as waste plastic pyrolysis oil may contain at least 10 ppm by weight of Cl due to imperfect sorting of the PVC product. Therefore, it is necessary, or may become necessary, to remove this impurity (Cl) from the liquid oil stream.

[0119] In one embodiment, the method further comprises, prior to said stabilization to form the stabilized liquid oil stream, diluting the liquid oil stream with an organic diluent.

[0120] In another general embodiment of the first aspect of the present invention, a method for hydrotreating a liquid oil stream is provided, wherein the liquid oil stream contains 30-50 wt% O, the method comprising: continuously operating in a fixed bed reactor in the presence of a reduced nickel (Ni) catalyst at a temperature of 80-250° C., for example, 100-225° C., and a pressure of 120-200 barg, for example, 125-175 barg, for 0.1-1.0 h -1 , for example 0.2-0.6h -1 and a hydrogen / liquid oil ratio of 1500-3500 NL / L, for example 2000-3000 NL / L, to form a stabilized liquid oil stream; wherein the reduced nickel catalyst is a supported catalyst having a Ni content of 2-30 wt %, for example 5-25 wt %, based on the total weight of the catalyst; and the support is selected from any one of the following: alumina (Al2O3), magnesium aluminum spinel (MgAl2O4) and combinations thereof; optionally in combination with a molecular sieve having a topology of MFI, BEA or FAU; and wherein the alumina is any one of the following:

[0121] - Alumina comprising 90-100 wt% gamma alumina and having: 230-250 m 2 / g BET surface area, 800-900 mL / kg total pore volume (PV), measured by mercury intrusion;

[0122] - Alumina comprising 90-100 wt% gamma alumina; and having: 165-185 m 2 / g BET surface area, 950-1100 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry;

[0123] - Alumina comprising 80-100 wt% theta alumina and 0-20 wt% alpha alumina; and having: 50-60 m 2 / g BET surface area, 600-700 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry.

[0124] Therefore, this method is particularly advantageous for highly reactive pyrolysis oils. Under these process conditions, the cleavage of C=O bonds in the liquid oil is further ensured. Furthermore, as previously mentioned, a specific hydrogen / liquid oil ratio range has the associated advantages of avoiding hydrogen starvation and improving reaction rate and / or equilibrium.

[0125] Any of the embodiments and associated benefits of the first aspect of the invention corresponding to a highly reactive liquid oil containing 30-50 wt% O may be used in conjunction with this general embodiment ("another general embodiment").

[0126] In another general embodiment of the first aspect of the present invention, a method for hydrotreating a liquid oil stream is provided, wherein the liquid oil stream contains 0.05-15 wt% O, the method comprising continuously operating in a fixed bed reactor in the presence of a reduced nickel (Ni) catalyst at a temperature of 80-225° C., for example, 100-200° C., and a pressure of 40-180 barg, for example, 40-60 barg or 70-180 barg, for 1-3 hours. -1 , for example 1.5-2.5h -1 and a hydrogen / liquid oil ratio of 400-700 NL / L, for example, 500-600 NL / L, to form a stabilized liquid oil stream; wherein the reduced nickel catalyst is a supported catalyst having a Ni content of 2-30 wt %, for example, 5-25 wt %, based on the total weight of the catalyst; and the support is selected from any one of the following: alumina (Al2O3), magnesium aluminum spinel (MgAl2O4) and combinations thereof; optionally in combination with a molecular sieve having a topology of MFI, BEA or FAU; and wherein the alumina is any one of:

[0127] - Alumina comprising 90-100 wt% gamma alumina and having: 230-250 m 2 / g BET surface area, 800-900 mL / kg total pore volume (PV), measured by mercury intrusion;

[0128] - Alumina comprising 90-100 wt% gamma alumina; and having: 165-185 m 2 / g BET surface area, 950-1100 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry;

[0129] - Alumina comprising 80-100 wt% theta alumina and 0-20 wt% alpha alumina; and having: 50-60 m 2 / g BET surface area, 600-700 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry.

[0130] Therefore, this method is particularly advantageous for treating less reactive HTL oils, waste plastic pyrolysis oils, or waste tire pyrolysis oils. Under these process conditions, the cleavage of C=C bonds in the liquid oil is further ensured. According to the present invention, using a reduced nickel catalyst, the C=C bond cleavage rate (exemplified by the conversion of styrene to ethylbenzene) is significantly higher than using a NiMo-based catalyst. Furthermore, as previously mentioned, a specific hydrogen / liquid oil ratio range offers the advantage of avoiding hydrogen starvation.

[0131] Any of the embodiments and associated benefits of the first aspect of the invention corresponding to less reactive liquid oils containing 0.05-15 wt% O may be used in conjunction with this general embodiment ("further general embodiment").

[0132] In a second aspect, the present invention also encompasses an apparatus for implementing the method according to any of the above embodiments.

[0133] Thus, as described in the appended claim 15, there is provided an apparatus for carrying out the method according to any of the above method embodiments, comprising:

[0134] - a stabilization reactor arranged as a fixed bed reactor and for continuous operation, said stabilization reactor also being arranged to receive a liquid oil stream and to react in the presence of a reduced nickel (Ni) catalyst at a temperature of 80-250°C, a pressure of 10-200 barg, for 0.1-6.0 h -1 The invention relates to a method for reacting a liquid oil stream with hydrogen at a liquid hourly space velocity (LHSV) of 100-8000 NL / L and a hydrogen / liquid oil ratio of 100-8000 NL / L, wherein the hydrogen / liquid oil ratio is defined as the volume ratio of hydrogen to the flow rate of the liquid oil stream; the stabilization reactor is further arranged to provide an outlet comprising a stabilized liquid oil stream; wherein the reduced Ni catalyst is a supported catalyst having a Ni content of 2-30 wt%, such as 5-25 wt%, based on the total weight of the catalyst; and the support is selected from any one of the following: alumina (Al2O3), magnesium aluminum spinel (MgAl2O4) and combinations thereof; optionally in combination with a molecular sieve having a topology of MFI, BEA or FAU; and wherein the alumina is any one of:

[0135] - an alumina comprising 90-100 wt% gamma alumina, and having:

[0136] 230-250m 2 / g BET surface area,

[0137] 800-900 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry;

[0138] - an alumina comprising 90-100 wt% gamma alumina, and having:

[0139] 165-185m 2 / g BET surface area,

[0140] 950-1100 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry;

[0141] - an alumina comprising 80-100 wt% theta alumina and 0-20 wt% alpha alumina, and having:

[0142] 50-60m 2 / g BET surface area,

[0143] 600-700 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry.

[0144] Any embodiment and associated benefits of the first aspect of the invention (the method) may be used in conjunction with the second aspect of the invention (the apparatus), and vice versa.

[0145] The present invention provides an excellent method and apparatus for stabilizing liquid oil.

[0146] Advantages of the present invention include:

[0147] A flexible process for converting third-generation renewable feedstocks into hydrocarbon products with boiling points in the transportation fuel range, particularly diesel, jet fuel for sustainable aviation, and naphtha. The process can stabilize a wide range of liquid oils (i.e., those with a wide range of oxygen contents) before subsequent hydrodeoxygenation (HDO) and any further processing to produce the aforementioned transportation fuels, as well as hydrocarbon feedstocks (e.g., naphtha, ethane, propane, or butane) for steam crackers used to produce polymers.

[0148] - At least for liquid oils with low oxygen content (0.05-15 wt% O): the conversion of styrene to ethylbenzene is much higher than when stabilised using NiMo based catalysts.

[0149] - At least for liquid oils with high oxygen content (30-50 wt% O): lower density values ​​are obtained by using a reduced nickel catalyst (monometallic nickel catalyst) and an alumina support with medium surface area and high pore volume; the carbonyl number is also lower in all stabilized samples prepared for liquid oil feeds compared to NiMo-based catalysts, indicating improved results.

[0150] Figure 1 The change in density over operating time during the stabilization of pyrolysis oil using different catalysts according to Example 2 is shown.

[0151] Figure 2 The carbonyl numbers of the pyrolysis oil feed and the pyrolysis oil stabilized with different catalysts according to Example 2 are shown. Example

[0152] Example 1: Styrene hydrogenation of low-reactivity liquid oil

[0153] Example 1 is a reaction according to one embodiment of the present invention involving a simulated feed representing a less reactive liquid oil. Two dilute feeds are provided:

[0154] Feed 1:

[0155] 6 / 94 (6 wt% plastic pyrolysis oil; 94 wt% white oil: CAS nr. 64742-82-1); oil containing 0.08 wt% oxygen (O); 1.3 wt% styrene.

[0156] Feed 2:

[0157] 12 / 88 (12 wt% plastic pyrolysis oil; 88 wt% white oil: CAS nr. 64742-82-1); oil containing 0.16 wt% oxygen (O); 2.4 wt% styrene.

[0158] Reduced Ni catalyst: Catalyst D in Table 3 - High Ni content - Example 2; and surface passivated with S supported on γ-alumina.

[0159] NiMo catalyst: Traditional NiMo formulation, sulfided NiMo: Ni content: approximately 3 wt% based on the total catalyst weight; Mo content: approximately 13 wt% based on the total catalyst weight. Support: γ-alumina, high surface area (as shown in Support A, Table 3 - Example 2).

[0160] The experiments were carried out in a fixed bed reactor containing a reduced nickel catalyst (pre-reduction) or a NiMo catalyst at a pressure of 50 bar and a temperature of 100-125°C (inlet / feed temperature); the liquid hourly space velocity (LHSV) was 2 h -1 , H2 / oil ratio is 500NL / L.

[0161] These test conditions were used to compare the styrene hydrogenation performance of the reduced Ni catalyst and the NiMo catalyst. The main results are reflected in the distillation curves of the product samples (not shown), in which styrene showed a plateau at 147°C and ethylbenzene showed a plateau at 137°C. Table 1 below shows the conversion performance estimated by GC-VUV analysis of the products (in the case of the NiMo catalyst test) or by visual inspection of the distillation curves of the Ni catalyst.

[0162] Table 1: Styrene conversion

[0163]

[0164] na: not obtained

[0165] The styrene conversion, an indicator of stabilization, is significantly higher when stabilized using the reduced nickel catalyst of the present invention compared to conventional NiMo formulations.

[0166] Example 2: Density and carbonyl number reduction of highly reactive liquid oils

[0167] Example 2 according to one embodiment of the present invention relates to the reaction of highly reactive liquid oil, more specifically highly reactive pyrolysis oil, which contains nearly 50 wt% oxygen, as shown in Table 2 below.

[0168] Table 2: Composition of liquid oil

[0169]

[0170]

[0171] The tests were conducted using a reduced nickel catalyst, i.e. a monometallic catalyst (Ni), on different supports (A, B, C, D - see Table 3 below), namely alumina (Al2O3) and magnesium aluminum spinel (MgAl2O4). On an alumina support (D), both high nickel content (about 22 wt% Ni) and low nickel content (about 13 wt% Ni) were tested. In addition, a NiMo-based catalyst on support A was also tested. The metal content is based on the total weight of the catalyst, so including the support:

[0172] Table 3: Catalysts used for stabilization

[0173]

[0174] To determine the total pore volume and pore size distribution, mercury intrusion porosimetry was performed according to ASTM D4284. The BET surface area was measured according to ASTM D4567-19, i.e., the surface area was determined by a single point using the BET equation. The contents of alpha alumina, theta alumina, and gamma alumina were determined by XRD (X-ray diffraction). More specifically, XRD was used to determine, for example, the alumina phase: the sample was extracted and rinsed with xylene, dried under vacuum, and then subjected to metal / P capture analysis (XRF, X-ray fluorescence analysis according to EN ISO 12677:2011), SEM, carbon and sulfur (C+S; LECO analysis, ASTM E1915-13), and BET surface area analysis (ASTM D4567-19).

[0175] The test was carried out in a fixed bed reactor containing a reduced nickel catalyst (pre-reduction) and the NiMo catalyst of Table 3 for a duration of about 10 days at a pressure of 135 bar, a temperature of 80-220° C., an inlet / feed temperature of 80° C.; LHSV=0.2 h -1 and H2 / oil ratio = 2500NL / L.

[0176] Figure 1 shows the change in liquid oil density (Y-axis; specific gravity (SG)) relative to the liquid oil feed during operation (X-axis; TOS=0h), Figure 2Shown is the carbonyl number of the feed (left bar graph) compared to the stabilized liquid oil samples in Table 3. The carbonyl number (carbonyl no) of the stabilized liquid oil stream was measured according to ASTM E 3146.

[0177] When using the monometallic Ni catalyst, the density values ​​of the liquid oil feed obtained are lower and at least comparable to those of the NiMo catalyst (Sample A - Comparative Example). Figure 1 As shown in the lower line, the monometallic Ni catalysts (sample D-low Ni content, sample D-high Ni content) containing alumina supports with medium surface area and high pore volume showed improved performance relative to the NiMo catalyst. Figure 2 As shown, all prepared samples exhibited lower carbonyl numbers compared to the liquid oil feed, indicating significantly improved liquid oil stability. Furthermore, in addition to improved performance in reducing liquid oil feed density, samples D-low Ni content ("Support D Low Metal") and D-high Ni content ("Support D High Metal"), particularly the former, exhibited the lowest carbonyl number and thus the highest carbonyl number ratio. Therefore, this supported catalyst (D-low Ni content, i.e., "Support D Low Metal") exhibits excellent stabilization performance, not only in terms of a lower stable density (the liquid oil maintains a lower density over extended run time), but also in terms of a lower carbonyl number.

Claims

1. A method for hydrotreating a liquid oil stream by continuously operating in a fixed bed reactor in the presence of a reduced nickel (Ni) catalyst at a temperature of 80-250° C., a pressure of 10-200 barg, and a reaction time of 0.1-6.0 h. -1 The invention relates to a method for preparing a catalyst for reducing a Ni-containing gas by reacting a liquid oil stream with hydrogen at a liquid hourly space velocity (LHSV) of 100 NL / L and a hydrogen / liquid oil ratio of 100 to 8000 NL / L to form a stabilized liquid oil stream, wherein the hydrogen / liquid oil ratio is defined as the volume ratio of hydrogen to the flow rate of the liquid oil stream; wherein the reduced Ni catalyst is a supported catalyst having a Ni content of 2 to 30 wt %, such as 5 to 25 wt %, based on the total weight of the catalyst; and the support is selected from any one of the following: alumina (Al2O3), magnesium aluminum spinel (MgAl2O4) and combinations thereof; optionally in combination with a molecular sieve having a topological structure of MFI, BEA or FAU; and wherein the alumina is any one of the following: - Alumina comprising 90-100 wt% gamma alumina and having: 230-250 m 2 / g BET surface area, 800-900 mL / kg total pore volume (PV), measured by mercury intrusion; - Alumina comprising 90-100 wt% gamma alumina; and having: 165-185 m 2 / g BET surface area, 950-1100 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry; - Alumina comprising 80-100 wt% theta alumina and 0-20 wt% alpha alumina; and having: 50-60 m 2 / g BET surface area, 600-700 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry.

2. The method according to claim 1, wherein the Ni content is 10-15 wt%, and the alumina is an alumina as described below, which contains 90-100 wt% gamma alumina and has: 165-185 m 2 The BET surface area was 2.174 nm / g and the total pore volume (PV) was 950-1100 mL / kg as measured by mercury intrusion porosimetry.

3. The method of any one of claims 1 to 2, wherein the liquid oil stream contains at least 0.05 wt% oxygen (O), such as at least 0.1 wt% O, at least 0.5 wt% (O), at least 1 wt% O, at least 5 wt% O, at least 10 wt% O, at least 15 wt% O, at least 20 wt% O, at least 25 wt% O, at least 30 wt% O, at least 35 wt% O, at least 40 wt% O or at least 45 wt% O; such as 0.05-50 wt% O, such as 0.05-15 wt% O, 30-50 wt% O or 40-50 wt% O.

4. The method of any one of claims 1 to 3, wherein the carbonyl number ratio of the liquid oil stream to the stabilized liquid oil stream, i.e., the carbonyl number ratio, in mol / kg, as measured by ASTM E 3146, is 1.7 or higher, such as 2 or higher, such as 3 or higher.

5. The method of claim 4, wherein the stabilized liquid oil stream has a carbonyl number of less than 3.0 mol / kg, such as between 1.0 and 2.0 mol / kg, as measured by ASTM E 3146.

6. The method according to any one of claims 1 to 5, wherein the temperature is 80-225°C, such as 100-225°C; the pressure is 120-200 barg, such as 125-175 barg; and the LHSV is 0.1-1.0 h -1 , for example 0.2-0.6h -1 ; The hydrogen / liquid oil ratio is 1500-3500NL / L, for example 2000-3000NL / L, and the liquid oil stream contains 30-50wt% O.

7. The method according to any one of claims 1 to 5, wherein the temperature is 80-225°C, such as 100-200°C; the pressure is 40-180 barg, such as 40-60 barg or 70-180 barg; the LHSV is 1-3h -1 , for example 1.5-2.5h -1 ; The hydrogen / liquid oil ratio is 400-700NL / L, for example 500-600NL / L, and the liquid oil stream contains 0.05-15wt% O.

8. The method according to claim 7, wherein the sulfur (S) content in the liquid oil stream containing 0.05-15 wt% O is less than 100 ppm wt, such as 1-90 ppm wt.

9. The method according to any one of claims 1 to 8, further comprising a prior step of thermally decomposing a solid renewable feedstock to produce the liquid oil stream; wherein the liquid oil stream is a pyrolysis oil stream or a hydrothermal liquefaction oil (HTL oil) stream; and wherein the thermal decomposition step is: - pyrolysis, such as fast pyrolysis, thereby producing said pyrolysis oil stream; or - Hydrothermal liquefaction, thereby producing said HTL oil stream.

10. A method according to claim 9, wherein the pyrolysis is a fast pyrolysis, suitably carried out in the absence of a catalyst and hydrogen.

11. The method according to any one of claims 9-10, wherein the solid renewable raw material is any one of the following: -Lignocellulosic biomass, including: wood products, forestry waste and agricultural residues; - sewage sludge, especially its organic fraction; - Waste tires; - municipal waste, in particular its organic fraction, where municipal waste is defined as raw material containing materials discarded by the public, such as mixed municipal waste with waste code 200301 in the European Waste Inventory; - feedstock of plastic or polymer origin, including mixed or sorted waste containing at least 50%, 80% or 90% by weight of plastics and other synthetic polymers; - combinations thereof.

12. The process according to any one of claims 1 to 11, further comprising subjecting the stabilised liquid oil stream to a hydrodeoxygenation (HDO) step, suitably wherein the HDO is carried out at a higher temperature and an equal or lower pressure than in the preceding step forming the stabilised liquid oil stream.

13. The method of claim 12, further comprising passing the stabilized liquid oil stream through one or more metal guards active in hydrodemetallization (HDM) and / or hydrodeoxygenation (HDO) prior to the HDO step.

14. The method according to any one of claims 12 to 13, further comprising: - providing supplemental hydrogen and supplying at least a portion thereof as said hydrogen to form said stabilized liquid oil stream; and / or - providing a recycle gas comprising CO and supplying at least a portion thereof to the stabilized liquid oil stream before the HDO step.

15. Apparatus for carrying out the method according to any one of claims 1 to 14, comprising: - a stabilization reactor arranged as a fixed bed reactor and for continuous operation, said stabilization reactor also being arranged to receive a liquid oil stream and to react in the presence of a reduced nickel (Ni) catalyst at a temperature of 80-250°C, a pressure of 10-200 barg, for 0.1-6.0 h -1 The invention relates to a method for reacting a liquid oil stream with hydrogen at a liquid hourly space velocity (LHSV) of 100-8000 NL / L and a hydrogen / liquid oil ratio of 100-8000 NL / L, wherein the hydrogen / liquid oil ratio is defined as the volume ratio of hydrogen to the flow rate of the liquid oil stream; the stabilization reactor is further arranged to provide an outlet comprising a stabilized liquid oil stream; wherein the reduced Ni catalyst is a supported catalyst having a Ni content of 2-30 wt%, such as 5-25 wt%, based on the total weight of the catalyst; and the support is selected from any one of the following: alumina (Al2O3), magnesium aluminum spinel (MgAl2O4) and combinations thereof; optionally in combination with a molecular sieve having a topology of MFI, BEA or FAU; and wherein the alumina is any one of: - Alumina comprising 90-100 wt% gamma alumina and having: 230-250 m 2 / g BET surface area, 800-900 mL / kg total pore volume (PV), measured by mercury intrusion; - Alumina comprising 90-100 wt% gamma alumina; and having: 165-185 m 2 / g BET surface area, 950-1100 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry; - Alumina comprising 80-100 wt% theta alumina and 0-20 wt% alpha alumina; and having: 50-60 m 2 / g BET surface area, 600-700 mL / kg total pore volume (PV), measured by mercury intrusion porosimetry.

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