Method for producing a liquid transport fuel component

Abstract

A process for producing at least one liquid transportation fuel component is provided. In this process, a paraffinic hydrocarbon is supplied and subjected to hydroisomerization treatment to obtain a hydroisomerization effluent. A recycle stream is separated from this hydroisomerization effluent and subjected to hydrocracking to obtain a recycle effluent. The hydroisomerization effluent and the recycle effluent are supplied to fractional distillation, and at least one liquid transportation fuel component is recovered from this fractional distillation.

Description

Technical Field

[0001] The present disclosure generally relates to processes for producing renewable fuel components. The present disclosure particularly relates to, but is not exclusive to, processes for producing at least one or more liquid transportation fuel components, preferably at least aviation fuel components.

Background Art

[0002] This section describes useful background information without admitting that any of the techniques described herein represent the state of the art.

[0003] There is an increasing need to reduce greenhouse gas emissions and / or carbon dioxide emissions in transportation, particularly in air transportation. Therefore, there is growing interest in renewable aviation fuels and aviation fuel components.

[0004] Processes have been proposed for producing aviation fuel components from renewable feedstocks. However, in this process, the yield of aviation fuel components is relatively low (compared to other fuel components). In addition, it is necessary to improve the quality of renewable aviation fuel components. In particular, there is interest in producing aviation fuel components that can be used in larger quantities as aviation fuel or even as is when appropriately blended with additives.

Summary of the Invention

[0005] It is an object to solve or mitigate at least some of the problems associated with the prior art. The object is to improve the quality of aviation fuel components obtainable from renewable resources. A further object is to enable an increase in the yield of aviation fuel components. Another object is to reduce the production of C1 - C4 hydrocarbons, particularly C1 - C2 hydrocarbons, in a process for producing renewable liquid transportation fuel components. Yet another object is to extend the life of a hydrogen isomerization catalyst in a process for producing renewable liquid transportation fuel components.

[0006] The appended claims define the scope of protection. In this specification and / or the drawings, descriptions of examples and techniques of devices, systems, products, and / or methods not included in the claims are presented as useful examples for understanding the present invention.

[0007] In a first exemplary embodiment, a process for manufacturing at least one liquid transportation fuel component is provided, the process comprising: providing a paraffinic hydrocarbon feed comprising at least 60 wt-% paraffin based on the total weight of the paraffinic hydrocarbon feed, wherein up to 30 wt-% of the paraffin is isoparaffin; subjecting the paraffinic hydrocarbon feed to hydroisomerization (HI) in a first reactor in the presence of a hydroisomerization catalyst to obtain a hydroisomerization effluent; subjecting the hydroisomerization effluent to fractionation to separate at least a recycle stream having a T5 temperature (5 vol% recovery, EN ISO 3405-2019) of 270 °C or higher and comprising C16 n-paraffin; subjecting a second reactor feed comprising the recycle stream to hydrocracking in a second reactor in the presence of a hydrocracking catalyst to obtain a recycle effluent; feeding the recycle effluent as a co-feed with the hydroisomerization effluent to the fractionation; and recovering at least one or more liquid transportation fuel components from the fractionation comprises.

[0008] The process of the present invention enables obtaining improved yields and / or quality of the recovered fuel components, particularly preferably the recovered aviation fuel components, while maintaining the amount of low-yield products (fuel gas) at a low level. In the process of the present invention, as defined, the recovery of the heavy fraction of the hydroisomerization (HI) effluent and its reuse for hydrocracking have proven successful in converting said heavy hydrocarbons into valuable fuel components, particularly in the aviation fuel range. It has proven extremely beneficial to subject the highly isomerized recycle stream to hydrocracking, particularly in the presence of a hydrocracking catalyst capable of both cracking and isomerization.

[0009] The inventors have found that the fuel components obtained by the process of the present invention have very beneficial properties. Compared with liquid fuel components obtained from conventional processes including hydrodeoxygenation of fatty feedstocks followed by hydroisomerization, the fuel components obtained by the process of the present invention can have, in particular, a high content of i-paraffins, particularly multi-branched i-paraffins, a low content of n-paraffins, and a modified carbon number and / or boiling point distribution. Generally, these improve the low-temperature properties of the fuel components obtained by this production method, and also improve the fluidity / mixability even at low temperatures. Therefore, the fuel components obtained by this process are desired and beneficial not only for use in fuel compositions but also in other wide-ranging applications.

[0010] The foregoing has illustrated various exemplary embodiments and forms without limitation. The foregoing embodiments are merely used to illustrate selected aspects or steps that may be utilized in various implementations. Some embodiments may be presented only with reference to specific exemplary aspects. It should be understood that the corresponding embodiments may also be applicable to other exemplary aspects.

Brief Description of the Drawings

[0011] Some exemplary embodiments will be described with reference to the accompanying drawings.

[0012]

Figure 1

Figure 2

[0013] In the following description, like reference numerals denote like elements or steps.

[0014] All standards mentioned in this document are, unless otherwise specified, the latest revised versions available at the filing date.

[0015] Unless otherwise specified, for distillation characteristics such as initial boiling point (IBP), final boiling point (FBP), T5 temperature (5 vol-% recovery), T95 temperature (95 vol-% recovery), and boiling range, EN ISO 3405-2019 is referred to. The IBP is the temperature at the instant when the first drop of condensate drips from the lower end of the condenser tube, and the FBP is the maximum reading of the thermometer obtained during the test, which typically occurs after all the liquid has evaporated from the bottom of the flask. For boiling point distribution, a GC-based method (simdis) ASTM D2887-19e1, or for gasoline-range hydrocarbons, ASTM D7096-19 may be referred to.

[0016] As used in the context of the present disclosure, an aviation fuel component refers to a hydrocarbon composition suitable for use in a fuel composition that meets the standard specifications of aviation fuel, such as those specified in ASTM D7566-21. Typically, such an aviation fuel component boils, i.e., has an IBP and an FBP, within a range of about 100°C to about 300°C, for example, within a range of about 150°C to about 300°C, as measured in accordance with EN ISO3405-2019.

[0017] As used in the context of the present disclosure, a diesel fuel component refers to a hydrocarbon composition suitable for use in a fuel composition that meets the standard specifications of diesel fuel, such as those specified in EN 590:2022 or EN 15940:2016+A1:2018+AC:2019. Typically, such a diesel fuel component boils, i.e., has an IBP and an FBP, within a range of about 160 °C to about 380 °C, as measured in accordance with EN ISO 3405-2019.

[0018] As used in the context of the present disclosure, a gasoline fuel component or naphtha refers to a hydrocarbon component suitable for use in a fuel composition that meets the standard specifications of gasoline fuel, such as those specified in EN 228-2012+A1-2017. Typically, such a gasoline fuel component boils, i.e., has an IBP and an FBP, within a range of about 25 °C to about 210 °C, as measured in accordance with EN ISO 3405-2019.

[0019] As used in the context of the present disclosure, a marine fuel component refers to a hydrocarbon component suitable for use in a fuel composition that meets the standard specifications of marine fuel, such as those specified in ISO 8217-2017. Typically, such a marine fuel component boils, i.e., has an IBP and an FBP, within a range of about 180 °C to about 600 °C, for example, about 180 °C to about 400 °C, as measured in accordance with EN ISO 3405-2019.

[0020] As used herein, hydrocarbon refers to a compound containing carbon and hydrogen. Hydrocarbons of particular interest herein include paraffins, n-paraffins, i-paraffins, mono-branched i-paraffins, multi-branched i-paraffins, olefins, naphthenes, and aromatics. As used herein, oxygenated hydrocarbon refers to a hydrocarbon containing covalently bonded oxygen.

[0021] As used herein, paraffin refers to acyclic alkanes, i.e., acyclic open-chain saturated hydrocarbons that are linear (normal paraffins, n-paraffins) or branched (isoparaffins, i-paraffins). In other words, paraffin as used herein refers to n-paraffins and / or i-paraffins.

[0022] In the context of the present disclosure, i-paraffin refers to a branched open-chain alkane, i.e., an acyclic open-chain saturated hydrocarbon having one or more alkyl side chains. Here, an i-paraffin having one alkyl side chain or branch is referred to as a monobranched i-paraffin, and an i-paraffin having two or more alkyl side chains or branches is referred to herein as a multi-branched i-paraffin. In other words, i-paraffin as used herein refers to monobranched i-paraffins and / or multi-branched i-paraffins. The alkyl side chains of i-paraffins may be, for example, C1-C9 alkyl side chains, preferably methyl side chains. The amounts of monobranched and multi-branched i-paraffins may be given separately. The term "i-paraffins" means, when present, the total amount of any monobranched and any multi-branched i-paraffins, which indicates the total amount of i-paraffins present regardless of the number of branches. Correspondingly, "paraffins" means, when present, the total amount of any n-paraffins, any monobranched i-paraffins, and any multi-branched i-paraffins.

[0023] In the context of the present disclosure, olefin refers to an unsaturated, linear, branched, or cyclic hydrocarbon excluding aromatic compounds. In other words, an olefin refers to a hydrocarbon having at least one unsaturated bond excluding unsaturated bonds in an aromatic ring.

[0024] As used herein, the term "cyclic hydrocarbon" refers to all hydrocarbons containing a cyclic structure, including cyclic olefins, naphthenes, and aromatics. As used herein, the term "naphthene" refers to cycloalkanes, i.e., saturated hydrocarbons containing at least one cyclic structure, regardless of the presence or absence of side chains. Since naphthenes are saturated compounds, they are compounds that do not contain an aromatic ring structure. As used herein, the term "aromatic" refers to hydrocarbons containing at least one aromatic ring structure, i.e., hydrocarbons having a delocalized alternating π-bond in a cyclic structure over the entire circumference of the cyclic structure.

[0025] In the context of the present disclosure, for gasoline fuel compositions, the contents of n - paraffins, i - paraffins, mono - branched i - paraffins, various multi - branched i - paraffins, olefins, naphthenes, and aromatics are expressed as weight % (wt - %) relative to the weight of the feed, stream, effluent, product, component or sample in question, or, when so defined, as weight % (wt - %) relative to the (total) weight of paraffins, or the (total) weight of i - paraffins of the feed, stream, effluent, product, component or sample in question. The said contents can be determined by the GC - FID / GC - MS method, preferably carried out as follows: The GC - FID disclosed in ASTM D6839 was used with parameters: column ZB - 160 m, inner diameter 0.25 mm, df 1.0 micron, or similar; oven 0 °C (2 minutes) - 1.5 °C / min to 300 °C (5 minutes); injector and detector 300 °C; carrier gas helium 1.0 ml / min; detector gases H2 35 ml / min and air 350 ml / min; makeup flow helium 30 ml / min; split flow 165:1 (165 ml / min). Individual compounds were identified using GC - MS (parameters: ion source 230, interface 280, scan 25 - 280 m / z, scan speed 303, scan event time 0.88). Commercially available tools (Shimadzu LabSolutions / GCMSSolutions and Agilent OpenLab) were used for the identification of the detected compounds or hydrocarbon groups, and for the determination of the mass concentration, the response coefficient with respect to n - heptane was applied to the area of the detected peak and normalized to 100 wt - % (for liquid volume concentration, the density coefficient was applied to the calculated mass concentration of the detected peak and normalized to 100 vol%). Olefinic naphthenes are described under the naphthene term. The quantification limit of individual compounds of this method is 0.1 wt - %.

[0026] In the context of the present disclosure, for other compositions that boil at 36 °C or higher (under standard atmospheric pressure), the contents of n-paraffin, i-paraffin, mono-branched i-paraffin, various multi-branched isoparaffins, naphthenes, and aromatics are expressed as weight percent (wt-%) relative to the degassed weight of the feed, stream, effluent, product, component, or sample in question, or, if so defined, as weight percent (wt-%) relative to the (total) weight of paraffins or the (total) weight of i-paraffins in the feed, stream, effluent, product, component, or sample in question. The said contents may be determined by the GC×GC-FID / GC×GC-MS method, preferably carried out as follows: The GC×GC (2D GC) method was carried out with the following modifications as generally disclosed in UOP 990-2011 and as described in the experimental section of the master's thesis of Nousiainen M., Comprehensive two-dimensional gas chromatography with mass spectrometric and flame ionization detectors in petroleum chemistry, University of Helsinki, August 2017. GC×GC was carried out in reverse mode, first using a semi-polar column (R×i17Sil), then a non-polar column (R×i5Sil), followed by an FID detector, using the following operating parameters: Carrier gas helium 31.7 cm / sec (column flow rate at 40 °C 1.60 mL / min), split ratio 1:350, injector 280 °C, column T program 40 °C (0 min) - 5 °C / min - 250 °C (0 min) - 10 °C / min - 300 °C (5 min), runtime 52 min, modulation time 10 sec, detector 300 °C with H2 40 mL / min and air 400 mL / min, makeup flow helium 30 mL / min, sampling rate 250 Hz, and injection size 0.2 microliters. Individual compounds were identified using GC×GC-MS with the following MS parameters: Ion source 230 °C, interface 300 °C, scan range 25 - 500 amu, event time (seconds) 0.05, scan speed 20000.For data processing including the identification of detected compounds or hydrocarbon groups, and for the measurement of mass concentration by applying a response factor to n-heptane for the volume of detected peaks and normalizing to 100 w-%, commercially available tools (LabSolutions from Shimadzu Corporation, GC Image from Zoex) were used. Olefins and naphthenes, and heteroatom species and aromatics were grouped together unless reported separately. The quantification limit for individual compounds by this method is 0.1 wt-%.

[0027] In the context of the present disclosure, various properties of feeds, streams, effluents, products, components, or samples are determined according to standard methods referred to or disclosed herein that are appropriately prepared. For example, cloud points are determined from degassed feeds, streams, effluents, products, components, or samples according to ASTM D 5771-17.

[0028] Typically, various paraffinic feeds, streams, effluents, and recovered products or fuel components as fractions thereof referred to herein can include, in addition to hydrocarbons, various trace amounts of, for example, heteroatom-containing hydrocarbons and inorganic compounds as impurities, and oxygen-containing hydrocarbon feeds can include various amounts of, for example, other heteroatom-containing hydrocarbons and inorganic compounds as impurities. Generally, impurity levels in the main process streams are highest in the first part of the process and then are negligible or even reduced below the detection limit in the recovered liquid transportation fuel components.

[0029] Typically, the various paraffinic feeds, streams, effluents, and recovered products or fuel components as fractions thereof referred to herein can include, in addition to hydrocarbons, various trace amounts of, for example, heteroatom-containing hydrocarbons and inorganic compounds as impurities, and oxygen-containing hydrocarbon feeds can contain various amounts of, for example, other heteroatom-containing hydrocarbons and inorganic compounds as impurities. Generally, impurity levels in the main process streams are highest in the first part of the process and then, in the recovered liquid transportation fuel components, are negligible or even reduced below the detection limit.

[0030] In the context of the present disclosure, the feeds to the reactors, particularly the first reactor and / or the second reactor, are defined, unless otherwise noted, such that the H2 that can be supplied to each reactor, for example, the H2 supplied to hydroisomerization and the H2 supplied to hydrocracking, are excluded from the definition of the feed.

[0031] As used herein, the hydroisomerization (HI) effluent refers, optionally, to the total HI effluent, the degassed HI effluent, or the degassed and stabilized HI effluent, and the term HI effluent can encompass each of these.

[0032] In the context of the present disclosure, CX+ paraffin, CX+ n-paraffin, CX+ i-paraffin, CX+ mono-branched i-paraffin, CX+ multi-branched i-paraffin, CX+ hydrocarbon, or CX+ fatty acid refers to paraffin, n-paraffin, i-paraffin, mono-branched i-paraffin, multi-branched i-paraffin, hydrocarbon, or fatty acid, respectively, having at least X carbon atoms, where X is any viable integer. It should be understood that not all compounds corresponding to the definitions necessarily exist.

[0033] In the context of the present disclosure, CY-paraffin, CY-n-paraffin, CY-i-paraffin, CY-mono-branched i-paraffin, CY-multi-branched i-paraffin, CY-hydrocarbon, or CY-fatty acid means paraffin, n-paraffin, i-paraffin, mono-branched i-paraffin, multi-branched i-paraffin, hydrocarbon, or fatty acid respectively, having up to Y carbon atoms, where Y is any feasible integer. It is understood that not all compounds corresponding to the definition necessarily exist.

[0034] In the context of the present disclosure, CX(Y)-CX(Z) (or CX(Y)~CX(Z)) paraffin, CX(Y)-CX(Z) n-paraffin, CX(Y)-CX(Z) i-paraffin, CX(Y)-CX(Z) mono-branched i-paraffin, CXY-CXZ multi-branched i-paraffin, CXY-CXZ hydrocarbon, or CXY-CXZ fatty acid means paraffin, the range of n-paraffin, i-paraffin, mono-branched i-paraffin, multi-branched i-paraffin, hydrocarbon, or fatty acid respectively, where XY and XZ are feasible end-point integer values, and the number of carbon atoms within such a range is as indicated by the end-point integer values and, if present, the integers between said end-point values. However, paraffin, n-paraffin, i-paraffin, mono-branched i-paraffin, multi-branched i-paraffin, hydrocarbon, or fatty acid may, in some cases, not necessarily exist for all said carbon atoms within the range, especially carbon atoms at the end-points or in the vicinity thereof, unless explicitly indicated. On the other hand, isomers may, by definition, be composed of a plurality of compounds having the same number of carbon atoms. For example, C15 isomers may be composed of methyltetradecane (with different positions of the methyl branch), dimethyltridecane (with different positions of the two methyl branches), etc., and "C15 isomers" are composed of the total amount of all such isomers.

[0035] Typically, it means the total amount as weight or volume of all paraffins, n - paraffins, i - paraffins, mono - branched i - paraffins, multi - branched i - paraffins, hydrocarbons, or fatty acids, as defined each time. For example, C15 - C22 n - paraffins refer to n - paraffins within that range, such as n - paraffins of C15, C16, C17, C18, C19, C20, C21, C22, even if the content of C15 n - paraffin is zero. In other words, the total amount is obtained by adding 0 (referring to the non - existent C15 n - paraffin) to the total weight of all other existing C15 - C22 n - paraffins.

[0036] Isomerization converts at least a certain amount of n - paraffins into i - paraffins, especially mono - branched i - paraffins. By (further) increasing the degree of isomerization, for example, by increasing the severity of hydro - isomerization as described below, more n - paraffins can be converted into i - paraffins, and mono - branched i - paraffins can be converted into i - paraffins having multiple branches, such as di - branched and / or tri - branched i - paraffins, and even i - paraffins containing three or more branches.

[0037] As used herein and in context, the degree of effective cracking refers to cracking that results in non - gaseous (NTP) cracking products, and in particular, cracking as the ratio of the C8 - C14 hydrocarbon content in the recycle stream to the C8 - C14 hydrocarbon content in the second reactor feed, as indicated.

[0038] In this specification, when a reaction step is defined as being carried out in a "reactor" such as, for example, a first reactor A and a second reactor B, such expression is used mainly for illustrative purposes. One skilled in the art will understand that any "reactor" may in fact be implemented as a reactor system composed of one or more reactors. Whether the reactor is actually arranged in a single reactor or in a plurality of reactors is an engineering issue and may be affected by practical issues such as the maximum height of the facility at the site, the diameter of the reactor, regulatory and maintenance issues at the site, wind conditions at the site, and / or available equipment. Similarly, "fractionation" can typically be carried out in a fractionation system including, for example, separation and distillation units, which can be arranged according to conventional engineering practices in the art.

[0039] Catalyst properties such as, for example, the total number of acidic sites refer, in the context of the present disclosure, to the catalyst properties at the start of the process, in an immediately usable state.

[0040] In this specification, the term catalyst deactivation refers to the decreased activity (reflected by the amount of unconverted feed in the reactor effluent) and / or decreased selectivity (reflected by the decreased amount of the desired reaction product in the reactor effluent) of the catalyst at a given time point (t n ) compared to the activity and / or selectivity of the catalyst at the start (t0) of the current process. As used herein, the term catalyst deactivation is not limited to a particular deactivation type or mechanism, but the catalyst deactivation observed in this process is generally considered to be due to poisoning and fouling phenomena and includes both reversible and irreversible deactivation.

[0041] As used herein, the term "renewable" refers to compounds or compositions that are available, derivable, or derived from plants and / or animals, including in whole or in part compounds or compositions that are available, derivable, or derived from fungi and / or algae. As used herein, renewable compounds or compositions may include genetically engineered compounds or compositions. Renewable feeds, ingredients, compounds, or compositions may also be referred to as biological feeds, ingredients, compounds, or compositions, or bio-based feeds, ingredients, compounds, or compositions.

[0042] As used herein, the term "fossil" refers to compounds or compositions that are available, derivable, or derived from naturally occurring non-renewable compositions such as, for example, crude oil, petroleum oil / gas, shale oil / gas, natural gas, or coal deposits, and combinations thereof, including hydrocarbon-rich deposits available from subterranean / underground sources.

[0043] The term "circular" generally refers to recycled materials derived from non-renewable resources. For example, the term "circular" may refer to recycled materials derived from waste plastics. The renewable, circular, and fossil compounds or compositions are considered to be different from each other based on their origin and impact on environmental issues. As such, they may be subject to different treatment within the framework of laws and regulations. Typically, renewable, circular, and fossil compounds or compositions are distinguished based on their origin and the information provided by their producers.

[0044] The renewable or fossil origin of any organic compound containing hydrocarbons can be chemically determined by suitable methods for analyzing the carbon content of renewable origin, such as, for example, DIN 51637 (2014), ASTM D6866 (2020), and EN 16640 (2017). The method is based on the fact that renewable or bio-based carbon atoms have a higher number of unstable radiocarbon ( 14 C) atoms compared to fossil-derived carbon atoms. Thus, 12C and 14 By analyzing the isotope ratio of C, it is possible to distinguish between renewable or biogenic carbon compounds and non-renewable or fossil-derived carbon compounds. Therefore, a specific ratio of said isotopes can be used as a "tag" to identify renewable carbon compounds and distinguish them from non-renewable carbon compounds. The isotope ratio does not change during the course of a chemical reaction. Therefore, the isotope ratio can be used to identify renewable compounds, components, compositions, and distinguish them from non-renewable fossil materials in reactor feeds, reactor effluents, separated product fractions, and various blends thereof. Numerically, the biogenic carbon content can be expressed as the amount of biogenic carbon in the material as a weight percentage of the total carbon (TC) in the material (in accordance with ASTM D6866 (2020) or EN 16640 (2017)). In the present specification, the term renewable preferably refers to a material having a biogenic carbon content of 50 wt-% or more, particularly 60 wt-% or more, or 70 wt-% or more, preferably 80 wt-% or more, more preferably 90 wt-% or more, or 95 wt-% or more, and even more preferably about 100 wt-%, based on the total weight of carbon in the material (EN 16640 (2017)).

[0045] The present disclosure provides a process for producing at least one liquid transportation fuel component, the process comprising the following: Providing a paraffinic hydrocarbon feed comprising at least 60 wt-% paraffins, based on the total weight of the paraffinic hydrocarbon feed, wherein up to 30 wt-% of said paraffins are isoparaffins; Subjecting the paraffinic hydrocarbon feed to hydroisomerization (HI) in a first reactor in the presence of a hydroisomerization catalyst to obtain a hydroisomerization effluent; Subjecting the hydroisomerization effluent to fractionation to separate a recycle stream comprising at least C16 n-paraffins and having a T5 temperature (5 vol% recovery, EN ISO 3405-2019) of 270 °C or higher; To obtain a recycled effluent, a step of subjecting a second reactor feed containing a recycle stream to hydrocracking in a second reactor in the presence of a hydrocracking catalyst; A step of feeding the recycled effluent as a co-feed with the hydroisomerization effluent to fractionation comprises.

[0046] Preferably, the process is a continuous process.

[0047] By using the process of the present invention, compared with conventional processes for the production of fuel components by hydrodeoxygenation (HDO) and hydroisomerization (HI) of renewable fats and oils, etc., without the need to reduce the HI capacity in the first reactor and / or improve the quality of the aviation fuel component, it is possible to obtain a higher yield of aviation fuel component throughout the life of the HI catalyst. Experimentally, it has been shown that up to 64 wt% of the recycle stream can still be converted into renewable aviation fuel components by test runs carried out according to this process. This increase in yield is thought to be due to the decomposition of heavy molecules in the recycle stream, particularly in the C8 - C14 range, without significantly reducing the degree of isomerization. Experimentally, it has been shown that up to 64 wt% of the recycle stream can still be converted into renewable aviation fuel components by test runs carried out according to this process. This increase in yield is thought to be due to the decomposition of heavy molecules in the recycle stream, particularly in the C8 - C14 range, without significantly reducing the degree of isomerization.

[0048] By the process of the present invention, even near the end of the operation, it is possible to produce an aviation fuel component having excellent low-temperature properties and thus can be used in aviation fuel at a high mixing ratio or as it is without mixing when appropriately additives are added. Also, the process of the present invention makes it possible to extend the life of the HI catalyst and allows the use of a wider range of feedstocks that are heavier and contain more impurities compared to conventional processes for the production of fuel components by HDO and HI of renewable fats and oils.

[0049] Furthermore, the process enables flexible adjustment of product selectivity for various liquid transportation fuel components, such as gasoline fuel components, aviation fuel components, diesel fuel components, and / or marine fuel components, even near the end of the life of the HI catalyst, e.g., based on market dynamics.

[0050] This process proposes subjecting the heavy fraction of the HI effluent, i.e., the recycle stream, to hydrocracking, which cracks longer paraffin chains into paraffins boiling in the aviation fuel range, for example, and further isomerizes the n-paraffins in the second reactor feed, as well as the n-paraffins formed during the cracking reaction, and further isomerizes the isoparaffins by increasing the number of branches in the isoparaffin molecules, for example, to produce multi-branched isoparaffins. Typically, the recycle stream subjected to hydrocracking contains compounds with boiling points above the target aviation fuel boiling range and / or n-paraffins, especially C16+ n-paraffins, which affect the low-temperature properties. By operating the process of the present disclosure, a high degree of isomerization can be achieved in the first reactor. This is beneficial for achieving the desired degree of effective cracking in the second reactor under milder operating conditions (compared to the second reactor feed with a lower degree of isomerization). Preferably, by operating the process of the present disclosure, the content of multi-branched isoparaffins in the HI effluent is also efficiently increased compared to their content in the paraffinic hydrocarbon feed, which can also beneficially contribute to the degree of effective cracking in the second reactor, especially to C8 - C14 hydrocarbons, but to lighter non-gaseous hydrocarbons. Multi-branched isoparaffins are also thought to increase the isoparaffin content of the recycle effluent (compared to the second reactor feed with a low or no content of multi-branched isoparaffins). Increasing the degree of effective cracking without excessive formation of gaseous hydrocarbons in the second reactor and increasing the isoparaffin content of the recycle effluent is considered beneficial for both the yield and quality of the recovered transportation fuel components, particularly preferably for the yield and quality of the recovered aviation fuel components. Hydrocracking can not only increase the yield of aviation fuel components but also improve their quality, such as their low-temperature properties, especially the freezing point and / or viscosity below freezing points such as -20°C.

[0051] During the continuous operation of the catalyst for hydrogen isomerization and hydrocracking, the catalyst gradually deactivates, for example, due to impurities or coking in the process stream. This process is very flexible and has various possibilities to adjust the yield and / or quality of the recovered liquid transportation fuel components and to extend the life of the HI and HC catalysts. Adjusting the amount of recycle stream subjected to hydrocracking and / or the amount of heavy (heavy molecules) removed from the process as diesel fuel, marine fuel, or other heavy product components is a convenient means to adjust the yield and / or quality of the recovered liquid transportation fuel components and to cope with catalyst deactivation and / or changes in market needs. In addition, when recycling the HI effluent stream, i.e., subjecting only the heavy fraction to hydrocracking, the gaseous impurities normally present in the gas phase of the HI effluent do not come into contact with the hydrocracking (HC) catalyst. Due to various possibilities, especially to compensate for the deactivation of the HI catalyst, it becomes possible to use paraffinic feeds with higher impurity contents compared to conventional processes for the production of liquid fuel components by HDO and HI of renewable oils. Also, the hydrocracking step enables the use of feeds containing heavier and longer-chain molecules compared to the conventional processes for producing liquid fuel components, typically diesel components, while being able to produce lower-boiling liquid transportation fuel components such as aviation fuel components and / or gasoline fuel components with good yields and quality.

[0052] In certain preferred embodiments of the present process, the second reactor feed further comprises a portion of the HI effluent (other than the recycle stream). In these embodiments, that portion can be obtained, for example, by simply splitting the total HI effluent or preferably the degassed HI effluent between the fractionation and the second reactor using a fixed or preferably gradually adjusted ratio. These embodiments provide additional flexibility in the operation of the process and the possibility to more precisely tune the process to meet the target yields and qualities of multiple recovered fuel components at once. In this way, it would be possible to avoid situations where the target yield and quality of one recovered fuel component are met while an excessive quality of another recovered fuel component occurs (such as producing a diesel fuel component with an unnecessarily low cloud point).

[0053] In the present process, the paraffinic hydrocarbons subjected to hydrogen isomerization in the first reactor contain at least 60 wt-% paraffins, based on the total weight of the paraffinic hydrocarbon feed, of which at most 30 wt-% are isoparaffins. This means that when the paraffinic hydrocarbon feed contains 60 wt-% paraffins based on the total weight of the paraffinic hydrocarbon feed, at most 30 wt-% of the total weight of the paraffins in the paraffinic feed, i.e., at most 18 wt-% based on the total weight of the paraffinic hydrocarbon feed, are isoparaffins. Preferably, the paraffinic hydrocarbons may contain at least 60 wt-%, preferably at least 70 wt-%, more preferably at least 80 wt-%, still more preferably at least 90 wt-% paraffins, based on the total weight of the paraffinic hydrocarbon feed. The paraffinic hydrocarbon feed of the present disclosure may contain at least 95 wt-% paraffins based on the total weight of the paraffinic hydrocarbon feed, or may consist essentially of paraffins. The paraffinic hydrocarbon feed of the present disclosure may contain olefins, preferably less than 5 wt-%, more preferably less than 1 wt-%, based on the total weight of the paraffinic hydrocarbon feed, and may contain minor amounts of aromatics and / or naphthenes.

[0054] The advantages of using a highly paraffinic hydrocarbon feedstock in this process are that paraffins are isomerized under relatively easy and mild conditions when subjected to HI, for example, compared to cyclic hydrocarbons. Also, paraffins decompose relatively easily and under mild conditions when subjected to hydrocracking.

[0055] Preferably at most 25 wt-%, more preferably at most 20 wt-%, and even more preferably at most 15 wt-% of the paraffins in the paraffinic hydrocarbon feed of the present disclosure are isoparaffins. For example, 1 wt-% to 30 wt-%, or 1 wt-% to 20 wt-%, or 2 wt-% to 30 wt-%, or 2 wt-% to 20 wt-% of the paraffins in the paraffinic hydrocarbon feed can be isoparaffins.

[0056] A high weight ratio (wt-%:wt-%) of n-paraffins to isoparaffins in the paraffinic hydrocarbon feed can contribute to the suppression of cracking side reactions during HI in the first reactor because n-paraffins tend to be more resistant to decomposition compared to isoparaffins of the same carbon number. However, the presence of a certain amount of isoparaffins in the paraffinic hydrocarbon feed is still beneficial. A hydrocarbon feed containing a certain amount of isoparaffins can result in an HI effluent containing more multi-branched isoparaffins compared to a similar feed without isoparaffins.

[0057] Preferably, the paraffinic hydrocarbon feed of the present disclosure comprises hydrocarbons having a carbon number in the range of C12 to C30, at least 70 wt-%, preferably at least 80 wt-%, more preferably at least 90 wt-%, even more preferably at least 95 wt-%, based on the total weight of the paraffinic hydrocarbon feed. In one particularly preferred embodiment, the paraffinic hydrocarbon feed comprises hydrocarbons having a carbon number in the range of C14 to C22, at least 70 wt-%, preferably at least 80 wt-%, more preferably at least 90 wt-%, even more preferably at least 95 wt-%, based on the total weight of the paraffinic hydrocarbon feed. A paraffinic hydrocarbon feed rich in C12-C30 hydrocarbons is preferred because it enables good yields of various types of two or more liquid transportation fuel components. C14-C22 hydrocarbons are particularly preferred for the same reason and also because they are readily available from conventional hydrodeoxygenation (HDO) processes of vegetable oils, animal fats and / or microbial oils, including fatty acids, for example.

[0058] To increase the yield of aviation fuel components and / or diesel fuel components, it is particularly preferred that the paraffinic hydrocarbon feed contains at least 50 wt-%, preferably at least 60 wt-%, more preferably at least 70 wt-%, even more preferably at least 80 wt-% or at least 90 wt-% of C16+ paraffins based on the total weight of the paraffins in the paraffinic hydrocarbon feed. In certain embodiments, the paraffinic hydrocarbon feed contains at least 50 wt-% of C17+ paraffins based on the total weight of the paraffins in the paraffinic hydrocarbon feed. Compositions of this kind can be achieved by appropriately selecting the heavier paraffinic hydrocarbon feeds from which they are produced, in particular by appropriately selecting feedstocks such as oxygenated hydrocarbons. Examples of suitable heavy oxygenated hydrocarbon feeds include oils from energy crops such as cruciferous plants, algal oils, crude tall oil (CTO), tall oil fatty acids (TOFA), tall oil pitch (TOP), and / or lignocellulosic origin feeds. C17+ paraffins can also be obtained by Fischer-Tropsch conversion of synthesis gas.

[0059] The paraffinic hydrocarbon feed may comprise any suitable paraffinic hydrocarbon composition or combinations thereof. Preferably, in this process, the step of providing a paraffinic hydrocarbon feed is the step of subjecting a hydrotreated feed to catalytic hydrotreating, preferably the step of subjecting an oxygen-containing hydrocarbon feed to catalytic hydrodeoxygenation, wherein the hydrotreated feed preferably comprises at least one or more of vegetable oils, animal fats, microbial oils, thermally liquefied organic wastes and residues, and / or enzymatically liquefied organic wastes and residues, more preferably an oxygen-containing hydrocarbon feed, and / or the step of subjecting synthesis gas to Fischer-Tropsch conversion to obtain a paraffinic FT effluent; the step of subjecting a paraffinic hydrotreated effluent and / or a paraffinic FT effluent to gas-liquid separation, optionally to paraffinic feed fractionation, to provide a paraffinic hydrocarbon feed. Gas-liquid separation means removing compounds that are gaseous at least at NTP.

[0060] For example, paraffinic FT effluents of fossil origin are readily available (in addition to those of renewable origin), but preferably the paraffinic hydrocarbon feeds of the present disclosure are at least partially renewable, i.e., contain bio-based components. In certain preferred embodiments, the bio-based carbon content of the paraffinic hydrocarbon feed is preferably measured according to EN 16640 (2017) and is at least 50 wt-%, preferably at least 70 wt-%, more preferably at least 90 wt-%, even more preferably at least 95 wt-%, or even about 100 wt-% based on the total weight of carbon (TC) of the paraffinic hydrocarbon feed.

[0061] In one embodiment, the paraffinic hydrocarbon feed comprises, consists essentially of, or consists of a degassed paraffinic Fischer-Tropsch effluent or a fraction thereof. The Fischer-Tropsch process typically involves the catalytic conversion of syngas, which contains carbon monoxide and hydrogen, into a Gaussian distribution of substantial hydrocarbon chains that are primarily n-paraffins, having a wide carbon chain length distribution such as C2 - C100+, typically about C5 - about C50. The FT effluent is typically highly paraffinic, containing primarily n-paraffins. The catalytic FT conversion of syngas results in a minor degree of isomerization, and the FT effluent typically contains up to about 10 wt-% isoparaffins, based on the total weight of the FT effluent. The syngas used in the FT process can be produced from renewable materials, natural gas, coal, or combinations thereof.

[0062] Preferably, the paraffinic hydrocarbon feed of the present disclosure is obtained, in particular, by subjecting a hydrotreating feed comprising at least one or more of vegetable oil, animal fat, microbial oil, thermally liquefied organic waste and residue and / or enzymatically liquefied organic waste and residue, more preferably at least one or more of vegetable, animal fat and / or microbial oil, to catalytic hydrotreating to obtain a hydrotreating effluent, then subjecting the hydrotreating effluent to gas-liquid separation, and optionally subjecting the hydrocarbon feed to fractional distillation to provide a degassed paraffinic hydrotreating effluent or a fraction thereof, and comprises, consists essentially of, or consists of a degassed paraffinic hydrotreating effluent or a fraction thereof.

[0063] The term "catalytic hydrotreatment" is often also referred to as "hydroprocessing", which means a catalytic process for treating organic materials using hydrogen molecules. Preferably, catalytic hydrotreatment removes oxygen from organic oxygen compounds as water, i.e., hydrodeoxygenation (HDO), removes sulfur from organic sulfur compounds as hydrogen sulfide (H2S), i.e., hydrodesulfurization (HDS), removes nitrogen from organic nitrogen compounds as ammonia (NH3), i.e., hydrodenitrogenation (HDN), removes halogen such as chlorine from organic chlorinated compounds as hydrochloric acid (HCl), hydrodechlorination (HDCl), and / or removes metals by hydrodemetallation, and / or hydrogenates olefin bonds if present in the hydrotreating feed. Depending on the composition of the hydrotreating feed, various reactions can occur or become dominant.

[0064] Preferably, the paraffinic hydrocarbon feed of the present disclosure comprises, in particular, the catalytic hydrodeoxygenation (HDO) of an oxygen-containing hydrocarbon feed comprising at least one or more of vegetable oils, animal fats and / or microbial oils to obtain an HDO effluent, then subjecting the paraffinic HDO effluent to gas-liquid separation, and optionally subjecting the hydrocarbon feed to fractional distillation to provide a degassed hydrodeoxygenation (HDO) effluent or a fraction thereof, and comprises or consists essentially of a degassed HDO effluent or a fraction thereof thus obtained. Nitrogen impurities are generally present in varying amounts in oxygen-containing hydrocarbon feeds comprising vegetable oils, animal fats and / or microbial oils, and are carried over and can be present in varying amounts in the degassed HDO effluent or a fraction thereof.

[0065] In one embodiment, providing a paraffinic hydrocarbon feed comprises subjecting an oxygen-containing hydrocarbon feed to hydrodeoxygenation in the presence of a hydrodeoxygenation catalyst, preferably in a hydrodeoxygenation (HDO) reactor, to obtain a hydrodeoxygenated effluent, and subjecting the hydrodeoxygenated effluent to vapor-liquid separation, optionally paraffinic feed fractionation, to obtain a degassed hydrodeoxygenated effluent or a fraction thereof as the hydrocarbon feed, wherein the hydrodeoxygenation is preferably carried out at a temperature in the range of 200 °C to 500 °C, a pressure in the range of 1 MPa to 20 MPa, an H2 partial pressure at the inlet of the reactor in the range of 1 MPa to 20 MPa, a weight hourly space velocity in the range of 0.1 to 10 kg of oxygen-containing hydrocarbon feed / kg catalyst / hour, and a ratio of H2 to oxygen-containing hydrocarbon feed in the range of 50 to 2000 normal liters of H2 per liter of oxygen-containing hydrocarbon feed. Preferably, the oxygen-containing hydrocarbon feed comprises at least one or more of vegetable oil, animal fat and / or microbial oil. The hydrodeoxygenation is preferably carried out as described in prior art documents such as Finnish Patent Invention No. 100248, European Patent Application Publication No. 1741768, European Patent No. 2155838, or Finnish Patent Invention No. 1292201.

[0066] Optional paraffinic feed fractionation is typically carried out in a fractionation unit different from the fractionation unit used to recover liquid transport fuel components and / or separate recycle streams. Optional paraffinic feed fractionation can be considered separate from the fractionation of this process, where the fractionation of this process includes fractions for recovering liquid transport fuel components and / or separating recycle streams.

[0067] Preferably, the HDO catalyst is a sulfided catalyst containing at least one or more metals from Group VIII of the periodic table and / or Group VIB of the periodic table, preferably at least one or more of Ni, Mo, W, and / or Co, more preferably Ni and / or Co and Mo and / or W, for example at least one or more of NiMo, CoMo, NiCoMo, NiW, and / or NiMoW. These catalysts are efficient, readily available, and sufficiently resistant to typical impurities in fatty acid feedstocks. When a catalyst having dewaxing properties such as a catalyst containing NiW is used in hydrodeoxygenation as a hydrodeoxygenation catalyst or as a co-catalyst, an HDO effluent having a somewhat high isoparaffin content can be obtained.

[0068] In this process, the paraffinic hydrocarbon feed is subjected to hydroisomerization in a first reactor in the presence of an HI catalyst to obtain an HI effluent. Generally, in the context of the present disclosure, the HI of the paraffinic hydrocarbon feed in the first reactor is operated such that the isomerization reaction is dominant while the cracking reaction is controlled or suppressed.

[0069] Preferably, the hydroisomerization in the first reactor is carried out at a temperature in the range of 200°C to 500°C, preferably 230°C to 500°C, more preferably 250°C to 450°C, even more preferably 280°C to 400°C, a pressure in the range of 1 MPa to 10 MPa, preferably 2 MPa to 8 MPa, or 3 MPa to 10 MPa, an H2 partial pressure at the reactor inlet in the range of 1 MPa to 10 MPa, preferably 2 MPa to 8 MPa, a weight hourly space velocity of paraffinic hydrocarbon feed / kg catalyst / hour in the range of 0.1 to 10, preferably 0.2 to 8, more preferably 0.4 to 6 kg, and a ratio of H2 to paraffinic hydrocarbon feed in the range of 10 to 2000, preferably 50 to 1000 normal liters of H2 / liter of paraffinic hydrocarbon feed.

[0070] In one embodiment, the hydrogen isomerization in the first reactor is carried out at a temperature in the range of 200°C to 500°C, a pressure in the range of 1 MPa to 10 MPa, an H2 partial pressure at the reactor inlet in the range of 1 MPa to 10 MPa, a weight hourly space velocity of paraffinic hydrocarbon feed in the range of 0.1 to 10 kg / kg catalyst / hour, and a ratio of H2 to paraffinic hydrocarbon feed in the range of 10 to 2000 normal liters of H2 / paraffin hydrocarbon feed.

[0071] In a particularly preferred embodiment, the hydrogen isomerization in the first reactor is a hydrogen isomerization carried out at a temperature in the range of 230°C to 500°C, a pressure in the range of 2 MPa to 8 MPa, an H2 partial pressure at the first reactor inlet in the range of 2 MPa to 8 MPa, a weight hourly space velocity of paraffinic hydrocarbon feed in the range of 0.2 to 8 kg / kg catalyst / hour, and a ratio of H2 to paraffinic hydrocarbon feed in the range of 50 to 1000 normal liters of H2 / paraffin hydrocarbon feed.

[0072] The HI effluent is preferably subjected to gas-liquid separation, i.e., at least removal of compounds that are gaseous at NTP, such as NH3 and / or H2S, which may be present in the gas phase of the HI effluent. This can be done, for example, as an integral step within the first reactor or as part of the fractionation before leading the HI waste liquid to fractionation.

[0073] The degree of isomerization of the HI effluent can be improved by increasing the severity of HI, for example, by at least one or more of the following: a decrease in WHSV, an increase in temperature, and / or an increase in pressure. When using fresh HI catalyst, very severe HI conditions can be achieved at lower temperatures, and / or pressures, and / or higher WHSV. As the life of the HI catalyst approaches its end, higher temperatures, and / or pressures, and / or lower WHSV may be required to achieve moderately severe HI. In this specification, as wt-% of paraffin in the liquid effluent, a total i-paraffin content in the range of 50 wt-% to 85 wt-% and a multi-branched i-paraffin content of up to 25 wt-%, or a total i-paraffin content in the range of 85 to 95 wt-% and a multi-branched i-paraffin content in the range of 25-% to 55 wt-%, or a liquid effluent having a total i-paraffin content of 95 wt-% and a multi-branched i-paraffin content exceeding 55 wt-% are generally considered to have a low degree of severity, or a moderate degree of severity, or a high degree of severity, respectively, although these content ranges are for illustrative purposes only in order of magnitude, may overlap to some extent, and may vary depending on the case.

[0074] Preferably, the hydrogen isomerization in the first reactor is such that the ratio of the wt-% amount of isoparaffin based on the total weight of paraffins in the paraffinic hydrocarbon feed to the wt-% amount of isoparaffin based on the total weight of paraffins in each HI effluent is at least 2, or at least 4, or at least 6, or at least 8, or at least 10, or at least 12, and / or the ratio of the wt-% amount of multi-branched isoparaffin based on the total weight of paraffins in the paraffinic hydrocarbon feed to the wt-% amount of branched isoparaffin based on the total weight of paraffins in each hydrotreated effluent is at least 2, or at least 4, or at least 6, or at least 8, or at least 10, or at least 12, and / or each HI effluent (in total) contains less than 20 wt-%, or less than 10 wt-%, preferably less than 5 wt-%, more preferably less than 3 wt-% of C1-C4 hydrocarbons based on the total weight of each HI effluent. These can be achieved particularly when operating the first reactor within the HI operating conditions and / or when using the HI catalyst and / or paraffinic hydrocarbon feed as defined herein.

[0075] Typically, the HI effluent may contain at least 60 wt-%, preferably at least 70 wt-%, more preferably at least 80 wt-%, even more preferably at least 90 wt-% or at least 95 wt-% of paraffins based on the total weight of the HI effluent. In certain embodiments, the HI effluent may consist essentially of paraffins.

[0076] Typically, based on the total weight of paraffins in the HI effluent, at least 50 wt-%, preferably at least 60 wt-%, more preferably at least 70 wt-%, even more preferably at least 80 wt-% of isoparaffins, and optionally, based on the total weight of paraffins in the HI effluent, at least 5 wt-%, more preferably at least 10 wt-%, even more preferably at least 15 wt-%, or at least 20 wt-% of multi-branched isoparaffins are included. Typically, when the hydrotreating in reactor A and / or B is hydroisomerization, the HI effluent contains at most 75 wt-%, or at most 70 wt-%, or at most 60 wt-%, for example at most 50 wt-%, or at most 40 wt-%, in some cases at most 30 wt-%, or even at most 20 wt-% of multi-branched isoparaffins based on the total weight of paraffins in the HI effluent. Typically, the HI liquid has a cloud point (ASTM D 5771-17) below 0 °C, preferably below -5 °C, more preferably below -8 °C, even more preferably below -10 °C, or below -15 °C.

[0077] The presence of multi-branched isoparaffins in the HI effluent is considered beneficial as it can beneficially contribute to an effective degree of cracking in the second reactor. In particular, when a desired degree of effective cracking to C8 - C14 hydrocarbons, but also to lighter non-gaseous hydrocarbons, is achieved in the second reactor under milder operating conditions, excessive cracking can be avoided and the formation of gaseous hydrocarbons can be reduced. Also, an increase in the content of multi-branched isoparaffins in the HI effluent is considered beneficial in terms of improving the low-temperature properties of the recovered liquid transportation fuels, particularly those of the aviation fuel components and / or diesel fuel components, and / or the RON of gasoline fuel components. Without being bound by any theory, multi-branched isoparaffins are likely to form two branched paraffin molecules instead of one branch and one n-paraffin during cracking in the subsequent hydrotreating reactor, thus increasing the isoparaffin content of the hydrotreating effluent.

[0078] This process consists of subjecting a second reactor feed containing a recycle stream to hydrocracking in a second reactor in the presence of a hydrocracking (HC) catalyst to obtain a recycle effluent. By hydrocracking the isomerized heavy paraffins in the recycle stream, the yield of aviation fuel components is improved, providing flexibility in the use of various paraffinic hydrocarbon feeds, particularly oxygen-containing hydrocarbon feeds converted thereto. Generally, the hydrocracking in the second reactor is operated such that the cracking reactions, particularly those enhancing the degree of effective cracking, are more numerous than the hydroisomerization in the first reactor. Preferably, in the hydrocracking in the second reactor, the cracking reactions, particularly those enhancing the degree of effective cracking, are predominant, but generally there is no excessive cracking or excessive formation of fuel gas.

[0079] The second reactor feed preferably is in a de-aerated state, i.e., it may further comprise a portion of the HI effluent (excluding the recycle stream) after subjecting the HI effluent to gas-liquid separation to remove compounds that are gaseous at least at NTP. In these embodiments, the portion can be obtained, for example, by simply splitting the total HI effluent or preferably the de-aerated HI effluent between the fractionation and the second reactor using a fixed or preferably gradually adjusted ratio. These embodiments provide further flexibility in operating the process, including the further possibility of adjusting the ratio and quality of the recovered fuel components, as described above. The amount of such a portion of the HI effluent fed to the second reactor may vary, but generally is a very minor amount. Thus, in certain preferred embodiments of this process, the second reactor feed further comprises less than 50 wt%, preferably less than 30 wt%, more preferably less than 10 wt% of the HI effluent, preferably in a de-aerated state, based on the total weight of the second reactor feed.

[0080] In certain preferred embodiments, the second reactor feed consists essentially of a recycle stream and optionally a portion of the hydroisomerization effluent (other than the recycle stream).

[0081] In this process, the hydrocracking in the second reactor has a temperature in the range of 200°C to 450°C, preferably 220°C to 430°C, more preferably 280°C to 350°C, a pressure in the range of 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa, more preferably 2.5 MPa to 7 MPa, an H2 partial pressure at the inlet of the second reactor in the range of 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa, more preferably 2.5 MPa to 7 MPa, a weight hourly space velocity in the range of 0.1 to 10 kg, preferably 0.2 to 8 kg, more preferably 0.4 to 6 kg, even more preferably 0.5 to 1.5 kg of the second reactor feed / kg catalyst / hour, and an H2 / second reactor feed ratio in the range of 10 to 2000, preferably 50 to 1000 normal liters of H2 / liter of the second reactor feed. Typically, in this process, the hydrocracking in the second reactor is at a temperature in the range of 200°C to 450°C, a pressure in the range of 0.4 MPa to 8 MPa, an H2 partial pressure at the inlet of the second reactor in the range of 0.4 MPa to 8 MPa, a pressure in the range of 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa, a second reactor feed / kg catalyst / hour in the range of 0.1 kg to 10 kg, and a ratio of H2 to the second reactor feed in the range of 10 to 2000, preferably 50 to 1000 normal liters of H2 / liter of the second reactor feed.

[0082] According to a preferred embodiment, the hydrocracking in the second reactor is carried out at a temperature in the range of 220 °C to 430 °C, a pressure in the range of 1 MPa to 7 MPa, a weight hourly space velocity in the range of 0.2 to 8 kg of second reactor feed / kg of catalyst / hour, and a ratio of H2 to the second reactor feed in the range of 50 to 1000 normal liters of H2 / liter of the second reactor feed. In a more preferred embodiment, the hydrocracking in the second reactor is carried out at a temperature in the range of 280 to 350 °C, a pressure in the range of 2.5 to 7 MPa, an H2 partial pressure at the inlet of the second reactor in the range of 2.5 MPa to 7 MPa, a weight hourly space velocity in the range of 0.4 to 6 kg of second reactor feed / kg of catalyst / hour at a pressure in the range of 2.5 MPa to 7 MPa, and a ratio of H2 to the second reactor feed in the range of 50 to 1000 normal liters of H2 / liter of the second reactor feed. Operating the HC at a sufficiently high pressure and a lower temperature better suppresses the aromatization side reaction or promotes dearomatization.

[0083] Preferably, in the hydrocracking in the second reactor, the ratio of the wt-% amount of isoparaffin to the total weight of paraffin in the recycle effluent is at least 0.5, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1.0 relative to the wt-% amount of isoparaffin to the total weight of paraffin in the second reactor feed; and / or the ratio of the C8 - C14 hydrocarbon content in the recycle effluent to the C8 - C14 hydrocarbon content in the second reactor feed is at least 1.1, preferably at least 1.3, more preferably at least 1.5, still more preferably at least 1.8, or at least 2.0.

[0084] In certain preferred embodiments, the ratio of the wt-% amount of C1-C4 hydrocarbons produced during hydrocarbon cracking in the (total) recycle effluent (step ii) or the total hydrocarbon cracking effluent (step I) in the second reactor to the content of C1-C4 hydrocarbons in the (total) HI effluent is 1.1 to 5.0, preferably 1.1 to 4.0, more preferably 1.2 to 3.0; and / or the (total) recycle effluent consists of less than 20 wt-%, or less than 10 wt-%, or less than 5 wt-% C1-C4 hydrocarbons relative to the total weight of the recycle effluent.

[0085] These can be achieved especially when using the second reactor feed and / or when operating the second reactor within the hydrocracking operating conditions defined above and / or in the presence of an HC catalyst as defined below, especially a non-sulfided bifunctional HC catalyst as defined below, preferably a non-sulfided bifunctional HC catalyst containing at least one noble metal of Group VIII, more preferably Pt and / or Pd.

[0086] Typically, the recycle effluent contains at least 60 wt-%, preferably at least 70 wt-%, more preferably at least 80 wt-%, even more preferably at least 90 wt-% or at least 95 wt-% paraffin, respectively, relative to the total weight of the recycle effluent, and the recycle effluent may even consist essentially of paraffin.

[0087] According to certain preferred embodiments, the recycle effluent (step ii) contains at least 50 wt-%, preferably at least 60 wt-%, more preferably at least 70 wt-%, even more preferably at least 80 wt-% isoparaffin relative to the total weight of the paraffin in the recycle effluent, and / or contains at least 3 wt-%, or at least 5 wt-%, or preferably at least 10 wt-%, even more preferably at least 15 wt-%, or at least 20 wt-% multi-branched isoparaffin, respectively, relative to the total weight of the paraffin in the recycle effluent.

[0088] Preferably, when comparing the temperatures at the reactor inlets, the first reactor is operated at a higher temperature than the second reactor. The temperatures being compared are the temperatures at the inlets of the first reactor and the second reactor, respectively, at a predetermined point in time that includes a short time interval. In other words, in this context, no comparison is made between the highest temperatures during the entire operation from the start to the stop of the process.

[0089] By operating the first reactor and the second reactor within the operating condition ranges defined above, particularly by operating the first reactor at a higher temperature than the second reactor, a high degree of isomerization is achieved in the first reactor, while in the second reactor, thermal decomposition is controlled, reduced, or minimized, and the content of multi-branched isoparaffins in the HI effluent can be increased. At the same time, in the second reactor, milder operating conditions, particularly at a low temperature, may achieve a desired degree of effective decomposition, thereby improving the yields of hydrocarbons in the aviation fuel and gasoline boiling ranges without excessive thermal decomposition leading to gas formation.

[0090] This step consists of subjecting the HI effluent to fractional distillation to separate a recycle stream consisting of at least C16 n-paraffins and having a T5 temperature (5 vol-% recovery, EN ISO 3405-2019) of 270 °C or higher from the fractional distillation. The HI effluent can be fed directly to the fractional distillation, or after being degassed, i.e., by subjecting the HI effluent to gas-liquid separation to remove compounds that are gaseous at least at NTP, and then fed to the fractional distillation. Alternatively, preferably, the degassed HI effluent can be split between the fractional distillation and the second reactor, and generally the major part is fed to the fractional distillation as discussed above.

[0091] Preferably, the recycle stream has a T5 temperature of 275 °C or higher. In certain preferred embodiments, the recycle stream has a T5 temperature in the range from 270 °C to less than 300 °C, preferably in the range from 270 °C to less than 295 °C, more preferably in the range from 270 °C to less than 290 °C; and / or an initial boiling point (IBP, EN ISO 3405-2019) of less than 290 °C, preferably less than 288 °C, more preferably less than 285 °C, or less than 280 °C. The recycle stream may have the FBP of the total feed subjected to fractionation, i.e., the recycle stream may contain the heavy bottoms of the total feed subjected to fractionation.

[0092] The T5 temperature of the recycle stream is preferably selected such that if there is C16 n-paraffin present in the total feed subjected to fractional distillation, for example, C16 n-paraffin present in the HI effluent, at least a portion thereof is recovered in the recycle stream. The recovery of C16 n-paraffin in the recycle stream can be achieved by appropriately selecting the T5 temperature and / or IBP of the recycle stream. Although the boiling point of C16 n-paraffin is 287 °C (atmospheric pressure), since fractional distillation such as distillation separation is not completely sharp, C16 n-paraffin can be recovered in the temperature range near its boiling point.

[0093] Since C16 n-paraffins have a relatively high melting point, it is beneficial to recycle at least a portion of the C16 n-paraffins to a second reactor for hydrocracking. Thus, for example, if a significant amount of C16 n-paraffins are present in the recovered aviation fuel components, there is a possibility that they cannot be used in the aviation fuel composition because of their poor low-temperature properties, particularly low freezing points, and / or low kinematic viscosities at sub-zero temperatures such as -20 °C or -40 °C, i.e., high kinematic viscosities. In any case, the C16 n-paraffins in the recovered aviation fuel components impair their low-temperature properties, i.e., increase one or more of the cloud point, freezing point, pour point, and / or low-temperature filter plugging point, and / or increase the kinematic viscosity below the freezing point, as compared to aviation fuel components with a low C16 n-paraffin content or no C16 n-paraffin content. Preferably, the recycle stream contains at least 20 wt% or at least 30 wt%, more preferably at least 40 wt% or at least 50 wt% of the C16 n-paraffins in the total feed to the fractionation. The amount of n-paraffins containing C16 n-paraffins in the total feed to the fractionation may increase due to deactivation of the HI catalyst and may also be produced by cracking in the second reactor.

[0094] In a particularly preferred embodiment, the recycle stream contains at least 85 wt%, preferably at least 90 wt%, more preferably at least 95 wt% C16+ paraffins relative to the total weight of the paraffins in the recycle stream. Subjecting C16+ paraffins to hydrocracking in the second reactor is beneficial in terms of increasing the yield of aviation fuel components and / or improving the quality. C16+ normal paraffins have poor low-temperature properties, and C18+ normal paraffins generally boil outside the aviation fuel boiling range.

[0095] Typically, the recycle stream comprises at least 60 wt%, preferably at least 70 wt%, more preferably at least 80 wt%, even more preferably at least 90 wt% or at least 95 wt% paraffin, based on the total weight of the recycle stream, or the recycle stream may even consist essentially of paraffin. In particularly preferred embodiments, the recycle stream has an isoparaffin content of at least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt%, or at least 80 wt%, and / or consisting of up to about 100 wt%, or at most 98 wt-% isoparaffin, based on the total weight of the paraffin in the recycle stream, and / or at least 5 wt-%, or at least 10 wt-%, preferably at least 15 wt-%, or at least 20 wt-% of multi-branched isoparaffin, based on the total weight of the paraffin in the recycle stream. Typically, the recycle stream contains at most 95 wt%, or at most 90 wt%, or at most 80 wt%, or at most 70 wt%, for example at most 60 wt%, or at most 50 wt%, or at most 40 wt%, in some cases at most 30 wt%, and even at most 20 wt% multi-branched isoparaffin, based on the total weight of the paraffin in the recycle stream, typically in the range of 5 wt% to 95 wt%, preferably 5 wt% to 80 wt%, or 5 wt% to 70 wt%, for example 10 wt% to 70 wt%, or 15 wt% to 65 wt%. Typically, the recycle stream has a cloud point of less than 0 °C, preferably less than -5 °C, more preferably less than -8 °C, even more preferably less than -10 °C, even more preferably less than -20 °C, even more preferably less than -30 °C (ASTM D 5771-17). Typically, the recycle stream has a higher i-paraffin content and / or a higher multi-branched i-paraffin content than the HI effluent (total HI effluent or degassed HI effluent), preferably expressed as wt-% i-paraffin or multi-branched i-paraffin, respectively, based on the total weight of the paraffin in each stream or effluent.

[0096] This type of recycle stream has a particularly beneficial composition in terms of the degree of effective cracking in hydrocracking, and long paraffins that form hydrocarbons boiling in the aviation fuel range and the gasoline boiling range crack more easily than short paraffins, and isoparaffins are expected to crack more easily than n-paraffins. The relative uniformity of the recycle stream composition facilitates the optimization of hydrocracking conditions in the second reactor. Further, these embodiments facilitate the easy separation, by mere splitting from the recycle stream, of components that can be separated from such a recycle stream, such as, to name just a few, diesel fuel components, marine fuel components, base oil components, and / or transformer oil components.

[0097] Both the hydroisomerization (HI) catalyst and the hydrocracking (HC) catalyst can be disposed in one or more catalyst layers within their respective reactors. The HI catalyst and the HC catalyst can each be disposed in at least one or more fixed beds. The HI catalyst may be a conventionally used HI catalyst, and the HC catalyst may be a conventionally used HC catalyst. Preferably, the HI catalyst in the first reactor is a bifunctional HI catalyst, and more preferably a non-sulfided bifunctional HI catalyst. More preferably, the HI catalyst in the first reactor and the HC catalyst in the second reactor are a bifunctional HI catalyst and an HC catalyst, respectively, and more preferably, a non-sulfided bifunctional HI catalyst and an HC catalyst, respectively.

[0098] The bifunctional HI catalyst and the HC catalyst include metal sites for catalyzing (de)hydrogenation reactions and acid sites for catalyzing isomerization and cracking reactions. The bifunctional HI catalyst and the bifunctional HC catalyst are well known in the petroleum refining field and the renewable fuel production field. The bifunctional hydrotreating catalyst is preferred because it has excellent catalytic performance that results in a synergistic effect between the metal sites and the acid sites. The bifunctional HI and HC catalysts are also beneficial in that the access and diffusion of molecules to the catalyst sites can be controlled by appropriately selecting the porous properties of the catalyst, particularly the pore size, pore dimensions, and / or interconnectivity of the pores of the catalyst.

[0099] In certain particularly preferred embodiments, the HI catalyst is a non-sulfided bifunctional HI catalyst, and the HC catalyst is a non-sulfided bifunctional HC catalyst, and the non-sulfided bifunctional catalysts independently of each other comprise at least one or more metals selected from the noble metals of Group VIII of the Periodic Table, more preferably from Pt and / or Pd, and at least one or more acidic porous materials, and wherein the paraffinic hydrocarbon feed and the second reactor feed each contain less than 50 wt-ppm, preferably less than 30 wt-ppm, more preferably less than 10 wt-ppm (weight ppm, calculated as elemental S) of sulfur as measured in accordance with ISO 20846-2019.

[0100] The sulfur content can be determined in accordance with ISO 20846-2019 for liquids and ASTM-D6667 for gaseous fractions.

[0101] The non-sulfided bifunctional catalyst does not need to be sulfided during operation to maintain activity and can thus keep the sulfur content of various process streams low, and is preferred because inefficient separation and recovery of H2S from various process streams is not required. In particular, non-sulfided bifunctional catalysts containing noble metals can be more active at lower temperatures and show higher selectivity towards isomerization reactions than sulfided catalysts, but are more susceptible to deactivation by H2S.

[0102] Preferably, each of the paraffinic hydrocarbon feeds contains sulfur measured in accordance with ISO 20846-2019 of less than 50 wt-ppm, preferably less than 30 wt-ppm, more preferably less than 10 wt-ppm (weight ppm, calculated as elemental S). The very low sulfur content of the stream entering the first reactor A is beneficial in that very little or essentially no H2S is formed in the HI in the first reactor and thus is not present in the HI effluent. In such embodiments, the gas-liquid separation of the HI effluent prior to feeding to the second reactor is not necessary to protect the HC catalyst in the second reactor, but nevertheless, the gas-liquid separation of the HI effluent can optionally be carried out. Thus, the overall process is more simplified and a liquid transport fuel component with an ultra-low sulfur content can be obtained. Further, since there is less H2S present, less corrosion is expected over the long term and, for some of the equipment materials, even less stringent corrosion resistance requirements may apply.

[0103] For example, various types of bifunctional HI catalysts and HC catalysts, such as HI catalysts and HC catalysts, having various metals or combinations of metals, various metal loadings, various acid strengths, and / or total acid values, and / or various porosities are commercially available.

[0104] The bifunctional HC catalyst and the bifunctional HI catalyst are similar in that they include a metal site that can catalyze the (de)hydrogenation of the corresponding n / i-olefin from n / i-paraffin, and an acid site that can catalyze the protonation of n / i-olefin to n / i-carbocation, the isomerization of n-carbocation and further i-carbocation, and / or the decomposition of n / i-carbocation to lighter n / i-olefin and lighter n / i-carbocation, and the deprotonation of n / i-carbocation to n / i-olefin. The hydrogenation of various n / i-olefins is catalyzed again by the metal site of these bifunctional catalysts to form n / i-paraffin. Whether the isomerization reaction or the decomposition reaction is dominant, for example, under any operating conditions and any feed composition, can be affected particularly by the properties of the bifunctional catalyst contacted with the feed. Such properties of the bifunctional catalyst include, for example, the total acid value of the catalyst, the number of Bronsted acid sites, the strength and / or density of the acid sites, and the metal content in the catalyst.

[0105] Preferably, the bifunctional HI and HC catalysts each independently contain at least one or more metals selected from Group VIII of the Periodic Table, preferably selected from the noble metals of Group VIII, more preferably selected from Pt and / or Pd. The noble metal can provide a higher selectivity for the isomerization reaction under the conditions of the first reactor and has a high activity at a lower operating temperature, compared with a catalyst containing only non-noble metals, especially in the bifunctional HI catalyst, and thus is preferred. The high activity at a lower temperature provides a wider temperature range within which the temperature can be adjusted (usually increased) during operation. The gradual deactivation of the catalyst that occurs when the process is operated for a longer time can be compensated to some extent by increasing the temperature in the reactor.

[0106] Preferably, the bifunctional HI and HC catalysts each independently include at least one or more porous acidic materials having a microporous, mesoporous, or hierarchical structure (micro-mesoporous). Various zeolite-type materials such as SAPO and zeolites are available, which provide the desired acidity and porous properties.

[0107] In certain embodiments, the HI catalyst is a bifunctional HI catalyst, preferably a non-sulfided bifunctional HI catalyst, and is selected from the following at least one or more metals selected from Group VIII of the Periodic Table, preferably noble metals of Group VIII, more preferably at least one or more of Pt and / or Pd; and at least one or more acidic porous materials selected from zeolites and / or zeolite-type materials, preferably at least one or more of the zeolites and / or zeolite-type materials are acidic porous materials having a framework type selected from AEL, ATO, AFO, MRE, MTT, MTW, TON, MRT, MOR, FER, and / or MWW, preferably at least one or more acidic porous materials selected from SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, ZSM-48, NU-10, ZBM-30, IZM-2, EU-2, and / or mordenite, more preferably at least one or more acidic porous materials selected from SAPO-11, SAPO-41, ZSM-23, and / or ZSM-48; and optionally at least one or more of alumina, silica, amorphous silica-alumina, titanium alumina, titania, and / or zirconia and is selected from bifunctional hydroisomerization catalysts, preferably non-sulfided bifunctional hydroisomerization catalysts, containing the same.

[0108] By selecting this catalyst, the isomerization selectivity in the first reactor is improved, and a larger amount of isoparaffins, particularly multi-branched isoparaffins, can be obtained, and these isoparaffins are hydrocracked at a lower temperature in the second reactor. The aforementioned SAPO and zeolite have acidity and porosity characteristics that enable the isomerization of long-chain n-paraffins containing multi-branches, such as C16+ paraffins, and are commercially available.

[0109] In particular, for the hydrocracking reaction in the second reactor of the present process, bifunctional HI catalysts have been found to be very beneficial because they have isomerization activity in addition to cracking activity and can be particularly effective in effective cracking. As a further advantage, bifunctional HC catalysts containing at least one or more metals selected from Group VIII noble metals, preferably Pt and / or Pd, provide high activity at relatively low temperatures compared to HC catalysts containing non-noble metals, and thus even better control of thermal cracking has been found. At low temperatures, the thermodynamic equilibrium tends to shift towards dearomatization, thus reducing the formation of aromatics by side reactions. By feeding a bifunctional HC catalyst to the second reactor, it is not necessary to make the isoparaffin content (weight ratio wt-% of isoparaffin to the total weight of paraffins) in the recycle effluent significantly lower than the HI effluent, and it can be the same or even higher.

[0110] Thus, in one embodiment, the hydrocracking catalyst is a bifunctional hydrocracking catalyst, preferably a non-sulfided bifunctional hydrocracking catalyst, and the following selected from Group VIII of the Periodic Table, preferably Group VIII Mo, Co, and / or W, preferably Ni, Mo, Co, W, Pt, and / or Pd, more preferably Pt and / or Pd; and At least one or more acidic porous materials selected from zeolites and / or zeolite-type materials and / or amorphous silica-alumina, preferably at least one or more of the zeolites and / or zeolite-type materials having a framework type selected from MFI, BEA, FAU, MOR, FER, AEL, AFI, ATO, AFO, MRE, MTT, MTW, TON and MRT, preferably SAPO-5, SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, ZSM-43, ZSM-48, IZM-2, mordenite, beta-zeolite, Y-type zeolite, and / or amorphous silica alumina, more preferably at least one or more acidic porous materials selected from SAPO-5, SAPO-11, ZSM-23, beta-zeolite, Y-type zeolite, and / or amorphous silica-alumina; and Optionally at least one or more of alumina, silica, amorphous silica-alumina, titanium alumina, titania and / or zirconia It is selected from bifunctional hydroisomerization catalysts, preferably non-sulfided bifunctional hydroisomerization catalysts. In certain embodiments, the HI catalyst in the first reactor, the HI catalyst in the second reactor, and the HC catalyst in the second reactor have different acid-related properties. For example, the acid-related properties of an acidic porous material such as zeolite can include the nature, number, and distribution according to the relative strength of acid sites, and can be determined by well-known methods, such as adsorption-desorption methods in which the release of an adsorbed basic substance such as ammonia or pyridine at high temperature indicates the presence of strong acid sites. As an example of an adsorption-desorption method that can be used, for example, temperature-programmed desorption of ammonia performed according to the procedure described by Niwa et al. (Niwa, M., Katada, N. Measurements of acidic property of zeolites by temperature programmed desorption of ammonia. Catalysis Surveys from Asia 1, 215-226 (1997)) can be mentioned. Yet another well-known method for measuring the acidic properties of zeolites, including the strength of the acid, is, for example, the method described by Heeribout et al. (Heeribout L., Semmer V., Batamack P., Doremieux-Morin C., Fraissard J. Bronsted acid strength of zeolites studied by 1H NMR: scaling, influence of defects. Microporous and Mesoporous Materials, Volume 21, Issues 4-6, May 1998, Pages 565-570) and is carried out according to the procedure described therein. 1 1H-NMR method. In certain embodiments, the bifunctional HC catalyst in the second reactor has a higher number of Bronsted acid sites compared to the bifunctional HI catalyst in the first reactor, as determined by NH3-TPD. In certain embodiments, the bifunctional HC catalyst has a higher total number of acid sites compared to the bifunctional HI catalyst, as determined by NH3-TPD.

[0111] In certain preferred embodiments, the bifunctional HC catalyst of the second reactor has a high content (wt-%) of Group VIII noble metals as compared to the bifunctional HI catalyst of the first reactor. In these embodiments, a better or higher yield of aviation fuel components was achieved at a lower temperature as compared to other similar processes using a bifunctional HC catalyst having a lower content of said noble metal as compared to the bifunctional HI catalyst.

[0112] In this process, a paraffinic hydrocarbon feed is contacted with HI in the presence of an HI catalyst, and a second reactor containing a recycle stream, and optionally the HI effluent is subjected to hydrocracking in the presence of an HC catalyst. The HI catalyst and the HC catalyst can have similar or identical components. According to a preferred embodiment, the HI catalyst and the HC catalyst are different from each other. The HI catalyst and the HC catalyst may be different from each other, for example, by at least one or more selections of catalyst components, acid value, and / or metal loading, but it is also possible to use the same catalyst as the HI catalyst in the first reactor and the same catalyst as the HC catalyst in the second reactor. Not only the catalyst, but also the operating conditions and the composition of the feed contribute to which reaction becomes dominant. For example, when the recycle stream is contacted with the HC catalyst under hydrocracking conditions, more decomposition is expected as compared to the case where the paraffinic hydrocarbon feed is contacted with the HI catalyst under HI conditions, even if the catalyst is the same. Preferably, when the paraffinic hydrocarbon feed is contacted with the HI catalyst under HI conditions, isomerization of this feed is more dominant than decomposition, and when the recycle stream (second reactor feed) is contacted with the HC catalyst under hydrocracking conditions, decomposition of this feed is more dominant than isomerization.

[0113] The HI catalyst and the HC catalyst may be in a state where they can be used as they are, or in order to obtain a usable fresh or regenerated HI catalyst and / or B, for example, reduction, sulfidation, and / or passivation with a nitrogen-containing compound such as an amine or ammonia is carried out. They may be treated by any conventional method to adjust properties such as selectivity and / or activity before or during startup. In this specification, the hydrotreated HI catalyst, HC catalyst, fresh catalyst, and regenerated catalyst generally mean catalysts in a usable state.

[0114] In certain embodiments, following hydrocracking, further hydroisomerization is carried out in the presence of additional HI catalyst. The additional HI can be achieved, for example, by placing additional HI catalyst in at least one separate bed in a second reactor and / or a subsequent third reactor.

[0115] The additional HI catalyst may be an HI catalyst as described above in relation to the HI catalyst in the first reactor. Preferably, the additional HI catalyst is a bifunctional HI catalyst, more preferably a non-sulfided bifunctional HI catalyst. The HI catalyst in the first reactor and the optional additional HI catalyst in the second reactor and / or the third reactor may have different properties and / or compositions, or they may have the same properties and compositions, i.e., they may be different catalysts or the same catalyst. To simplify the process, it is preferred that the additional HI catalyst is the same catalyst as the HI catalyst. In these embodiments, the HC catalyst is preferably different from the HI catalyst and any additional HI catalyst.

[0116] Those skilled in the art are well aware of the method of selecting the HI conditions and the hydrocracking conditions, preferably within the ranges of the HI conditions and the hydrocracking conditions defined above, taking into account the selected HI catalyst, the composition of the paraffinic hydrocarbon feed, and the targeted degree of isomerization, as well as the targeted content of multi-branched isoparaffins in the HI effluent; and taking into account the selected hydrocracking (HC) catalyst, the composition of the second reactor feed, the targeted degree of effective cracking, the targeted degree of isomerization, and the targeted content of multi-branched isoparaffins in the effluent of the second reactor. When selecting or adjusting the operating conditions of the first reactor and / or the second reactor, to some extent, the aging or deactivation of the catalyst can also be considered. During the continuation of the operation, the HI catalyst and the HC catalyst are gradually deactivated, for example, by impurities or coking in the process stream. When the catalyst is deactivated, the catalyst activity decreases, the selectivity is affected, and at a certain point, the desired characteristics of the HI effluent and / or the recycle effluent cannot be achieved. Also, changes in the paraffinic hydrocarbon feed composition during operation can lead to deviations from the desired characteristics. In such cases, at least one or more operating conditions of the first reactor and / or the second reactor, including, for example, the temperature, pressure, WHSV, and / or H2 partial pressure at the inlet of the first reactor and / or the second reactor, are preferably adjusted within the operating condition ranges defined above to compensate for the deactivation of the catalyst so that the desired characteristics of the HI effluent and / or the recycle effluent can be reached again. Typically, this means increasing the temperature and / or decreasing the WHSV and / or adjusting the H2 supply ratio to the paraffinic hydrocarbon and / or increasing the pressure. However, there are limits, for example, where it is not possible to increase the temperature and / or decrease the WHSV without impairing the yield and / or quality of the recovered liquid transportation fuel components. For example, if the operating temperature is increased to a sufficiently high value, the pyrolysis side reaction increases, the production of gaseous hydrocarbons increases, and thus the yield of the liquid product decreases. Therefore, it is usually beneficial to start the operation of the HI reactor (the first reactor) at a low temperature. For example, using the lowest temperature feasible within the specified range provides the widest window for increasing the temperature as the catalyst gradually deactivates.In addition, although the HC catalyst generally deactivates at a slower pace compared to the HI catalyst, since it gradually deactivates during continuous operation, similar considerations are also required when adjusting the operating conditions of the second reactor.

[0117] The active sites of the catalyst may be occupied by impurities or coke in the process stream, the catalyst pores may be blocked, and it may become unavailable for catalysis. For example, coke is caused by coke-forming compounds such as olefins, aromatics, and naphthenes, and when impurities are present in the paraffinic hydrocarbon feed, the formation of coke may be promoted by other impurities. For impurities that cause reversible catalyst deactivation, monitoring the total content of impurities in the feed may be sufficient. For some other impurities, especially those that cause irreversible catalyst deactivation, monitor the content of one or more such impurities in the paraffinic hydrocarbon feed, calculate the value received as the cumulative amount of such impurities from the start of operation of the HI catalyst to a predetermined point in time, and compare the received value with a value that reflects catalyst deactivation that is so high that it can no longer be foreseen to meet the desired target yield and / or quality of the fuel component, based on, for example, past data or a model based on past data.

[0118] Preferably, this step comprises monitoring at least one or more parameters that typically indicate the deactivation of the HI catalyst and / or the HC catalyst, receiving at least one or more values, comparing the received values with predetermined values, and based on that comparison, adjusting at least one or more operating conditions in the first reactor and / or the second reactor, preferably within the range of the operating conditions defined above for hydrogen isomerization and hydrocracking respectively.

[0119] Therefore, according to one preferred embodiment, the process further comprises monitoring to receive at least one or more values of at least one of the following parameters: The content of impurities in the paraffinic hydrocarbon feed, preferably the content of at least one or more of N, S, O, P, Si, Cl, Fe, alkali metals, alkaline earth metals, and / or coke-forming compounds in the paraffinic hydrocarbon feed; said species or impurities are known catalyst deactivators, particularly deactivators of non-sulfided bifunctional HI catalysts containing noble metals. Also, said species or impurities are generally present in various amounts in feeds derived from vegetable oils, animal fats and oils, microbial oils, thermally and / or enzymatically liquefied organic wastes and residues, and feeds derived from the Fischer-Tropsch process, and thus, in certain embodiments, can be carried over and present in the paraffinic hydrocarbon feed in various amounts. Typically, elemental impurities, even if not present as such in the paraffinic feed, their content indicates the presence of compounds containing said impurities. Elemental impurities and coke-forming compounds can be determined by standard laboratory analysis. An increase in the content of these impurities may increase catalyst deactivation. In some cases, an increase in the content of NH3 and / or H2S in the gas phase of the HI effluent may indicate an increase in catalyst exposure to said impurities. An increase in the content of these impurities may lead to progressive catalyst deactivation. The physicochemical properties of the hydrogen isomerization effluent and / or recycle effluent, preferably at least one or more of cloud point, freezing point, pour point, plugging point, kinematic viscosity, density, and / or distillation characteristics; an increase in any of cloud point, freezing point, pour point, plugging point, kinematic viscosity, and / or density may indicate an increase in catalyst deactivation. Distillation characteristics that indicate catalyst deactivation upon increase include T5, T50, FBP, etc. As further distillation characteristics, a shift in the boiling point distribution towards higher boiling compounds may suggest catalyst deactivation. To some extent, it may indicate or correlate with the content of isoparaffins or multi-branched isoparaffins in the physicochemical, HI effluent and / or recycle effluent. The compositional characteristics of the hydrogen isomerization effluent and / or recycle effluent, preferably at least one or more of the content of isoparaffin, the content of C8-C14 hydrocarbons, the content of multi-branched isoparaffin, and / or the content of C1-C4 hydrocarbons in the hydrogen isomerization effluent and / or recycle effluent; a decrease in the content of isoparaffin, multi-branched isoparaffin, and / or C8-C14 hydrocarbons may indicate an increase in catalyst deactivation. The content of isoparaffin or multi-branched isoparaffin may indicate or correlate to some extent with the physicochemical properties of the HI effluent and / or recycle effluent. The content of C1-C4 hydrocarbons decreases as catalyst deactivation progresses. However, increasing the operating temperature to compensate for catalyst deactivation may increase the C1-C4 hydrocarbon content. The yield of at least one or more of the recovered liquid transport fuel components and / or separated recycle streams, preferably the yield of the recovered aviation fuel components; an increase in the yield of high-boiling hydrocarbons and an increase in the amount of the separated recycle stream may indicate an increase in catalyst deactivation. At least one or more of the physicochemical properties of the recovered liquid transport fuel components and / or separated recycle streams, preferably at least one or more of the cloud point, freezing point, pour point, clogging point, kinematic viscosity, density, research octane number (RON), cetane number, and / or distillation characteristics; a decrease in cetane may indicate an increase in catalyst deactivation. Among the distillation characteristics, for example, an increase in T5, T50, T95, and / or FBP, or a shift of the boiling point distribution towards high-boiling compounds may indicate catalyst deactivation. It may indicate or correlate to some extent with the content of isoparaffin or multi-branched isoparaffin in the recovered liquid transport fuel components and / or separated recycle streams with certain physicochemical properties. At least one compositional property of the recovered liquid transportation fuel component and / or the separated recycle stream, preferably the content of isoparaffin and / or the content of multi-branched isoparaffin in the recovered fuel component and / or the separated recycle stream; A decrease in the content of isoparaffin, multi-branched isoparaffin and C8-C14 hydrocarbons may indicate an increase in catalyst deactivation. The content of isoparaffin or multi-branched isoparaffin may indicate or correlate to some extent with the physicochemical properties of the recovered liquid transportation fuel component and / or the separated recycle stream. The temperature difference can be monitored relatively easily, and a decrease in the temperature difference is considered to be a typical sign of catalyst deactivation. Compare the received value with a predetermined value, and based on the comparison, adjust at least one operating condition in the first reactor and / or the second reactor, preferably adjust at least one of temperature, pressure, weight hourly space velocity (WHSV), and H2 relative to the paraffinic hydrocarbon feed ratio, more preferably increase the temperature and / or pressure in the first reactor and / or the second reactor, and / or decrease the WHSV in the first reactor and / or the second reactor.

[0120] For example, different parameters can be monitored during the process or different predetermined values can be selected according to the changes in the target product and quality.

[0121] In certain preferred embodiments, the process typically consists of monitoring at least two or at least three of the above parameters that indicate deactivation of the HI catalyst and / or the HC catalyst. For example, good low-temperature properties of the HI effluent (e.g., cloud point, pour point, and / or sub-freezing viscosity) can be achieved by an increase in the amount of shorter carbon chains caused by an increase in decomposition occurring in the first reactor (e.g., caused by a temperature increase) instead of sufficient degree of isomerization. Therefore, it is beneficial to monitor at least two, three, or more parameters to better understand the catalyst deactivation situation.

[0122] Monitoring can be carried out continuously, repeatedly, continuously, periodically, intermittently, discontinuously, or as one-time monitoring. Monitoring can be performed online, for example, using sensors or sensors in any of a process stream, a supply tank, and / or a product tank, including a slipstream arrangement, or can be performed offline based on samples taken from any of a process stream, a supply tank, and / or a product tank. The monitoring frequency and method of one or more parameters can be carried out independently of other monitoring parameters. That is, a certain parameter can be continuously monitored online, for example, and other parameters can be periodically monitored offline, for example.

[0123] Monitoring can be discontinuous or one-time monitoring, particularly in embodiments where the adjustment of one or more operating conditions of the first reactor and / or the second reactor is carried out based on past process data, such as a model based on past process data. For example, the content of one or more known catalyst deactivation impurities can be determined from samples from each of the fresh supply tanks used in the process, and a temperature rise profile based on the determined content of one or more impurities can be programmed for the first reactor based on past process data. Therefore, the adjustment of operating conditions to obtain or maintain the desired properties and / or yields of the HI effluent, recycle effluent, separated recycle stream, and / or recovered liquid fuel component(s) can be carried out, for example, based on past process data from previous processes carried out using similar feeds and similar qualitative and quantitative predictions for the recovered liquid transportation fuel component, and / or a model, such as a theoretical model or a model based on past process data, and the received value(s) obtained for the monitoring parameters exemplified above.

[0124] When the operating conditions in the first reactor and / or the second reactor are adjusted to their feasible limits, preferably within the ranges of the hydroisomerization conditions or hydrocracking conditions respectively defined above, it is necessary to replace the catalyst with a new one or to regenerate it in order to reach the target levels of the degree of isomerization and / or the degree of effective cracking again. As described above, the process of the present invention enables the improvement of the catalyst life, i.e., the extension of the catalyst replacement / regeneration interval, and / or the use of feedstocks with heavy impurity loads.

[0125] This process includes a fractional distillation in which at least one or more liquid transportation fuel components are recovered and a recycle stream can be separated. The amount of the separated recycle stream, the amount of the separated recycle stream, and the amount of the recycle stream supplied to the second reactor vary within a wide range. For example, additional liquid streams or cuts such as side cuts can optionally be separated and / or recovered from the fractional distillation and optionally recycled to the process.

[0126] Preferably, the recycle stream and the HI effluent subjected to the fractional distillation are in a weight ratio of 1:10 to 10:1, preferably 1:5 to 5:1. Preferably, the ratio is the recycle stream to the HI effluent. The ratio of the recycle stream to the HI effluent preferably approaches the lower limit when treating a paraffinic hydrocarbon feed that boils at a low temperature, and preferably approaches the upper limit when treating a paraffinic hydrocarbon feed that boils at a high temperature, for example, a feed containing paraffins heavier than C18.

[0127] The fractional distillation of this process can be constituted by any of the conventionally used fractional distillation techniques. Preferably, the fractional distillation includes distillation such as atmospheric distillation or vacuum distillation, optionally. Before the fractional distillation, gas-liquid separation as described below, for example, may be performed.

[0128] Fractionation can be carried out in a fractionation system including one or more fractionation units. For example, gas and light naphtha can be separated in a prefractionator, while liquid transport fuel components and recycle streams are recovered and separated from a main distillation unit downstream of the prefractionator. As an alternative example, a single fractionation unit can also be used.

[0129] As described above, the recycle effluent and / or the HI effluent can be combined or separately subjected to gas-liquid separation. The gas-liquid separation can be carried out, for example, as an integral process within each reactor or in a fractionation system. Typically, the gas-liquid separation is carried out at a temperature in the range of 0 °C to 500 °C, such as 15 °C to 300 °C, or 15 °C to 150 °C, preferably 15 °C to 65 °C, such as 20 °C to 60 °C, and preferably at the same pressure as the pressure of the reactor from which the effluent is derived. Typically, the pressure during gas-liquid separation is in the range of 0.1 MPa to 20 MPa, preferably 1 MPa to 10 MPa, or 3 MPa to 7 MPa.

[0130] According to certain embodiments of the present process, different products can be recovered from the fractionation as liquid transport fuel components, depending, for example, on selected operating conditions, the composition of the used paraffinic feed, and / or market demand at a given point in time.

[0131] Liquid transport fuel components and any additional products separated and / or recovered from fractionation can include, for example, gasoline fuel components that boil in the range of about 25°C to about 200°C, aviation fuel components that boil in the range of about 100°C to about 300°C, such as in the range of about 150°C to about 300°C, recycle streams having a T5 temperature of at least 270°C, diesel fuel components that boil in the range of about 160°C to about 380°C, and / or marine fuel components that boil in the range of about 180°C to about 600°C, such as about 180°C to about 400°C (boiling within the range determined according to EN ISO 3405 - 2019). In certain embodiments, gasoline fuel components that boil in the range of about 25°C to about 200°C, aviation fuel components that boil in the range of about 100°C to about 300°C, such as in the range of about 150°C to about 300°C, and recycle streams having a T5 temperature of at least 270°C are first recovered and / or separated from fractionation, and then diesel fuel components that boil in the range of about 160°C to about 380°C, and / or marine fuel components that boil in the range of about 180°C to about 600°C (boiling within the range determined according to EN ISO 3405 - 2019) are recovered from the separated recycle stream. Additional products can be split or further separated from fractionation, for example from the recycle stream, and recovered. Examples of such further products include solvents, electro-technical fluids, and components of base oils.

[0132] By this process, it is possible to produce low-viscosity aviation fuel components having a very low freezing point and, in particular, a lower kinematic viscosity at -20°C compared to aviation fuel components produced by conventional HDO of fatty feedstocks followed by HI, i.e., without subjecting to hydrocracking as in this process.

[0133] Thus, in a preferred embodiment of this process, at least one of the liquid transport fuel components recovered from fractionation has a density at 15°C of 730 - 772 kg / m 3within the range of (EN ISO 12185-1996), the T10 temperature is at most 205 °C (EN ISO 3405-2019), the final boiling point is at most 300 °C (EN ISO 3405-2019), the flash point is at least 38 °C (IP 170-2013, Abel closed-cup method), and the freezing point is at most -40 °C (IP 529-2016), and it is an aviation fuel component. In these embodiments, the recovered aviation fuel component is of high quality and can be incorporated in a greater amount in the aviation fuel composition. Typically, the recovered aviation fuel component has T10 and T90 temperatures within the range of 120 °C to 295 °C, preferably within the range of 130 °C to 295 °C, as measured according to EN ISO 3405-2019.

[0134] The process of the present invention enables the recovery of at least aviation fuel components in surprisingly high yields even towards the end of the life cycle of the HI catalyst. In a preferred embodiment of the process of the present invention, the aviation fuel components are recovered in a yield of at least 30 wt-%, preferably at least 40 wt-%, more preferably at least 50 wt-%, for example 30 wt-% to 90 wt-%, based on the total weight of the paraffinic hydrocarbon feed. This is believed to be possible due to the high content of C8 - C14 hydrocarbons and isoparaffins in the separately fed feed, a significant proportion of which are multi-branched isoparaffins. In a preferred embodiment, the aviation fuel components have a difference between the T90 temperature and the T10 temperature determined according to EN ISO3405-2019 of at least 70 °C, preferably at least 75 °C, more preferably at least 80 °C, even more preferably at least 85 °C, typically at most 180 °C, for example in the range of 80 °C to 150 °C, preferably 80 °C to 130 °C. In these embodiments, the aviation fuel components can be recovered in improved yields while achieving the desired low-temperature properties, density and flash point properties. If the quality of the total feed supplied to the fractionation is poor, it is necessary to greatly limit the FBP to meet the requirements of the low-temperature properties, which also limits the T90 temperature and narrows the T90 - T10 difference. However, here, the process of the present invention provides excellent properties such as modified distillation characteristics since the degree of isomerization can be high, especially the content of highly multi-branched i-paraffins, and the amount of carbon atoms can be more evenly distributed particularly in the range of C6 - C18.

[0135] Typically, in this process, at least one or more of an aviation fuel component, a diesel fuel component, a gasoline fuel component, and / or a marine fuel component are recovered from the fractionation, preferably at least the aviation fuel component, more preferably at least the aviation fuel component and the diesel fuel component, and even more preferably at least the aviation fuel component, the diesel fuel component, and the gasoline fuel component are recovered from the fractionation. Generally, it is preferred to at least periodically recover at least one heavy product such as a diesel fuel component, a marine fuel component, and / or a base oil component from the fractionation. In this way, the heaviest components can be removed from the recycle loop.

[0136] In certain preferred embodiments, the recovered liquid transport fuel components have a biogenic carbon content (EN 16640 (2017)) of at least 50 wt-%, preferably at least 70 wt-%, more preferably at least 90 wt-%, even more preferably at least 95 wt-%, or even about 100 wt-%, based on the total weight of carbon (TC) in each of the recovered liquid transport fuel components. The biogenic carbon content in the recovered liquid transport fuel components is mainly affected by the biogenic carbon content in the paraffinic hydrocarbon feed and, in preferred embodiments, by the oxygen-containing hydrocarbon feed subjected to HDO. However, the amount of, for example, a fossil hydrocarbon diluent fed to the HDO reactor can affect the biogenic carbon content of the recovered liquid transport fuel components.

[0137] Typically, the liquid transportation fuel components recovered have an improved (increased) isoparaffin content, particularly a multi-branched isoparaffin content, compared to the corresponding components obtained by subjecting fatty feedstocks to conventional HDO followed by HI, i.e., without subjecting them to hydrocracking in this process. Typical aviation fuel components recovered from this step may include at least 85 wt-%, preferably at least 87 wt-%, more preferably at least 90 wt-%, still more preferably at least 92 wt-% of C6 - C18 i-paraffins based on the total weight of the aviation fuel components; and / or at least 58 wt-%, preferably at least 60 wt-%, more preferably at least 62 wt-% of C6 - C18 multi-branched i-paraffins based on the total weight of the aviation fuel components. Typical diesel fuel components recovered from this step may include at least 70 wt-%, preferably at least 75 wt-%, more preferably at least 80 wt-%, still more preferably at least 90 wt-% of C15 - C22 i-paraffins based on the weight of the diesel fuel components; and / or at least 60 wt-%, preferably at least 63 wt-%, more preferably at least 65 wt-% of C15 - C22 multi-branched i-paraffins based on the weight of the diesel fuel components. Typical gasoline fuel components recovered from this step may include at least 50 wt-%, preferably at least 55 wt-%, more preferably at least 60 wt-%, still more preferably at least 65 wt-% of C4 - C9 i-paraffins based on the weight of the gasoline fuel components; and / or at least 5 wt-%, preferably at least 6 wt-%, more preferably at least 7 wt-%, even more preferably at least 10 wt-% or at least 11 wt-% of C6 - C9 multi-branched i-paraffins based on the weight of the gasoline fuel components.

[0138] In this process, even if each of the gasoline fuel components, aviation fuel components, and diesel fuel components can be recovered simultaneously, they are recovered as moderately broad fractions. When optimizing the yield of aviation fuel components, the diesel fuel components may be recovered as a narrower cut or not recovered at all.

[0139] As shown in the examples, the products recovered from this manufacturing method have excellent properties. The recovered liquid transportation fuel components are suitable for use as blend components in fuel compositions and, when appropriately added, can be used directly as fuel, i.e., as unblended components. The recovered liquid transportation fuel components, and optionally, various other uses, such as raw materials for industrial conversion processes, preferably pyrolysis raw materials, such as steam cracking raw materials, and / or catalytic cracking raw materials, heat transfer media suitable for transformer oil, switchgear oil, shock absorber oil, insulating oil, hydraulic oil, gear oil, transmission oil, degreasing compositions, penetration oils, rust preventive compositions, multi-purpose oils, metalworking oils, rolling oils, especially for aluminum, cutting oils, drilling oils, solvents, lubricating oils, extender oils, carriers, dispersant compositions, demulsifiers, extractants, coating liquids or pastes in paint compositions, adhesives, resins, varnishes, printing pastes or inks, detergents, cleaning agents, plasticized oils, turbine oils, hydrophobized compositions, agriculture, crop protection liquids, construction, concrete release agents, electronic devices, medical devices, automotive, electrical, textile, packaging, paper, cosmetic and / or pharmaceutical industry compositions, and / or in the manufacture of their intermediates. The relatively high degree of isomerization and the high proportion of shorter carbon chains obtained by this manufacturing method are expected to improve the fluidity, pumping and mixing characteristics, and blendability of the recovered components and / or fractions. These are generally desirable beneficial properties, especially in a wide range of applications including spraying, injection, and / or miscibility with other components.

[0140] Schematic of the process Figure 1 schematically shows a process according to an exemplary embodiment of a mode executed according to an exemplary embodiment. In Figure 1, an oxygen-containing hydrocarbon feed 110 is supplied to an HDO reactor 120, where it is hydrodeoxygenated in the presence of an HDO catalyst 130 to obtain a hydrodeoxygenated effluent (HDO effluent) 140. The obtained HDO effluent 140 is subjected to gas-liquid separation 150, and at least a compound that is gaseous in NTP 160 is separated from the HDO effluent to obtain a degassed HDO effluent 170. This degassed HDO effluent is, in this exemplary embodiment, a paraffinic hydrocarbon feed as defined herein. The degassed HDO effluent 170 is then supplied to a first reactor 180, where the degassed HDO effluent 170 is subjected to hydroisomerization in the presence of an HI catalyst 190 to obtain an HI effluent 200. The obtained HI effluent 200 is subjected to gas-liquid separation 210, and at least a compound that is gaseous in NTP 220 is separated from the HI effluent 200 to obtain a degassed HI effluent 230. In Figure 1, the degassed HI effluent 230 is supplied to a distillation unit 240. The distillation unit 240 may be composed of a single column or may be composed of a pre-distillation column and a main distillation column, from which a plurality of streams or cuts can be obtained. From the distillation in Figure 1, a gasoline fuel component 250, an aviation fuel component 260, and / or a diesel fuel component 270 are recovered. Further, a recycle stream 280 having a T5 boiling point of 270 °C or higher is separated. The recycle stream 280 is supplied to a second reactor 290 in Figure 1, where hydrocracking is performed in the presence of an HC catalyst 300 to obtain a recycle effluent 310. In Figure 1, the recycle effluent 310 is subjected to gas-liquid separation 320, and at least a compound that is gaseous in NTP 330 is separated from the recycle effluent 310 to obtain a degassed recycle effluent 340. The degassed recycle effluent 340 is then supplied as a co-feed to the distillation unit 240 for fractionation together with the degassed HI effluent 230. In certain embodiments, a portion of the HI effluents 200, 230 can be supplied as a co-feed 500 together with the recycle stream 280 to the hydrocracking in the second reactor 290.

[0141] Without being limited to the exemplary embodiment of FIG. 1, in certain preferred embodiments of the present process in which at least an aviation fuel component is recovered from the fractionation, it includes monitoring a parameter including at least one of the following that preferably indicates the deactivation of the HI catalyst: temperature, for example, the temperature monitored at the inlet of the first reactor 180, the WHSV in the first reactor 180, the temperature difference across the first reactor 180 or on the bed of the HI catalyst 190, the cloud point and / or pour point of the degassed HI catalyst 190. For example, the temperature monitored at the inlet of the first reactor 180, the WHSV of the first reactor 180, the temperature difference across the first reactor 180 or on the catalyst bed of the HI catalyst 190, the cloud point and / or pour point of the degassed HI effluent 230, the cloud point and / or pour point of the recycle stream 280 or the diesel fuel component 270, the freezing point and / or at least one or more distillation characteristics of the aviation fuel component 260, and the corresponding received values of these are compared with predetermined values. The parameter to be monitored, for example, for the cloud point of the degassed HI effluent 230, the predetermined value is, for example, a maximum of -5 °C, and for the cloud point of the recycle stream 280 or the diesel fuel component 270, the predetermined value is, for example, a maximum of -15 °C (ASTM D 5771-17); for the freezing point of the aviation fuel component 260, the predetermined value is, for example, a maximum of -40 °C (IP 529-201); for the distillation characteristics of the aviation fuel component 260, the predetermined value is, for example, at T10, 205 °C, or the difference between T90 - T10 is, for example, a minimum of 22 °C (EN ISO 3405-2019); for the distillation characteristics of the diesel fuel component 270, the predetermined value is, for example, at T95, a maximum of 360 °C (EN ISO 3405-2019). The parameters indicating the deactivation of the HC catalyst can be similarly monitored by referring only to the second reactor 290, the catalyst bed of the HC catalyst 300 therein, and the degassed recycle effluent 340 exiting therefrom.The received value may be compared with a predetermined value, and based on the comparison, at least one or more operating conditions in the first reactor and / or the second reactor may be adjusted. Preferably, the temperature, pressure, weight hourly space velocity (WHSV), H2 supply ratio to paraffinic hydrocarbons, H2 supply ratio to the second reactor, and / or H2 partial pressure at the inlet of the first reactor and / or the second reactor. After adjustment, the monitored parameter and the predetermined value may remain unchanged, or, for example, depending on whether the same product and its quality are still targeted, different parameters may be monitored and / or different predetermined values may be selected.

[0142] Figure 2 schematically shows a comparative process that also includes a hydrocracking step. This process was used in Example 1 of the comparative example. In Figure 2, an oxygen-containing hydrocarbon feed 110 is supplied to an HDO reactor 120, where it is subjected to hydrodeoxygenation treatment in the presence of an HDO catalyst 130 to obtain a hydrodeoxygenation treatment effluent (HDO effluent) 140. The obtained HDO effluent 140 is subjected to gas-liquid separation 150, and at least a compound that is gaseous at NTP 160 is separated from the HDO effluent to obtain a degassed HDO effluent 170. This degassed HDO effluent 170 is, in this comparative example, a paraffinic hydrocarbon feed as defined herein. The degassed HDO effluent 170 is then supplied to a first reactor 180 in Figure 2, where the degassed HDO effluent 170 is subjected to hydroisomerization in the presence of an HI catalyst 190 to obtain an HI effluent 200. The obtained HI effluent 200 is subjected to gas-liquid separation 210, and at least a compound that is gaseous at NTP 220 is separated from the HI effluent 200 to obtain a degassed HI effluent 230. In Figure 2, the degassed HI effluent 230 is supplied to a second reactor 290, where it is subjected to hydrocracking in the presence of an HC catalyst 300 to obtain a hydrocracking effluent 350. The hydrocracking effluent 350 is subjected to gas-liquid separation 360, and at least a compound that is gaseous at NTP 370 is separated from the hydrocracking effluent 350 to obtain a degassed hydrocracking effluent 380. In Figure 2, the degassed hydrocracking effluent 380 is supplied to a distillation unit 240. The distillation unit 240 may consist of a single column or may be composed of a pre-column and a main column, where it is fractionated into several streams or cuts. From the distillation in Figure 2, a gasoline fuel component 390, an aviation fuel component 400, and a diesel fuel component 410 are recovered.

[0143] Example 1 1. Simulation As disclosed in FI100248 and EP1396531, in order to explain the advantages of this process compared to the conventional HVO process in which a fatty raw material is subjected to a hydrodeoxygenation (HDO) step followed by a hydroisomerization (HI) step and then fractionated to recover at least aviation fuel components, simulations were carried out using Aspen Plus V10.0 software.

[0144] The oxygen-containing hydrocarbon feed supplied to HDO consisted of 100% animal fat, and the highly paraffinic hydrocarbon feed (consisting of about 98 wt-% paraffin) supplied to HI was composed of 59 wt-% C17 - 18 normal paraffins, about 29 wt-% C15 - 16 normal paraffins, about 4 wt-% C17 - 18 isoparaffins, and about 2 wt-% C15 - 16 isoparaffins. Approximately 97 wt-% of the paraffinic hydrocarbons supplied to HI were C14 - C22 hydrocarbons, and about 1 wt-% were cyclic hydrocarbons.

[0145] Reference Example 1 (Tables 1 and 2) shows the typical product distribution recovered from the fractionation of a conventional HVO process operated in the winter-grade renewable diesel production mode. That is, a medium-severe HI step is included following the HDO step. Reference Example 2 (Tables 1 and 2) shows the typical product distribution recovered from the fractionation of an HVO process in which a highly severe HI process using a fresh catalyst is carried out following an HDO step similar to that of Reference Example 1.

[0146] In INV (Tables 1 and 2), the process shown in Figure 1 was used, the HDO and HI steps were carried out in the same manner as in Reference Example 1, and then the HI effluent was separated from the recycle effluent coming from a hydrocracking reactor supplied with the recycle stream (a part of the diesel components recovered from the fractionation). In the Comparative Example (Tables 1 and 2), the process shown in Figure 2 was used, the HDO and HI steps were carried out in the same manner as in Reference Example 1, and then the HI effluent was hydrocracked and fractionated.

[0147] The components shown in Table 1 were separated and recovered. Tables 1 and 2 show that in the INV process, compared to the processes of Reference Example 2 and the Comparative Examples, without sacrificing the total yield of the liquid product and the properties of other liquid products, the yield of high-quality sustainable / renewable aviation fuel (SAF) components (71.6 wt-%) increased significantly. Furthermore, in the INV process, the yield of the gasoline component was almost five times higher. As an important advantage over the process of Reference Example 2, the improvement in yield and product quality was achieved while avoiding the limitations of the process of Reference Example 2, i.e., without the need to use high severity HI, especially at high temperature and / or low WHSV compared to normal medium to high severity HI conditions, and / or without the need to use fresh HI catalyst. The product properties achieved by the INV process are at a similarly high level as those achieved by the Comparative Examples, and the aviation fuel component obtained by INV has a slightly better (- lower) kinematic viscosity at -40.

[0148]

Table 1

[0149]

Table 2

[0150] Example 2 Test Run 2.1 Production of Liquid Transportation Fuel Components An oxygen-containing hydrocarbon raw material containing animal fats and vegetable oils was first pretreated to remove impurities using a normal bleaching protocol. The bleached oxygen-containing hydrocarbon feedstock was subjected to hydrodeoxygenation treatment at about 320 °C and about 50 bar using a NiMo sulfide catalyst on alumina with a WHSV of 0.3 - 1 / h and a hydrogen flow rate of 500 - 1000 Nl / l. To obtain a paraffinic hydrocarbon feed, gas and water were separated from the liquid stream and discarded. A typical exemplary composition of a paraffinic hydrocarbon feed from a mixture of animal and vegetable oils is, based on the total weight of the paraffinic hydrocarbon feed, about 99 wt% paraffins, about 9 wt% total isoparaffins, about 2 wt% multi-branched isoparaffins, about 90 wt% n-paraffins, and the total amount other than paraffins (e.g., cyclic). The total amount of C12 - C30 hydrocarbons is about 99 wt-%, and the total amount of C14 - C20 hydrocarbons is about 98 wt-%.

[0151] The obtained paraffinic hydrocarbon feed was subjected to hydroisomerization in the presence of a non-sulfided bifunctional hydrogen isomerization catalyst (Pt / SAPO). The conditions of the HI reactor were set to low severity to obtain Stream 1 and high severity to obtain Stream 2. The HI effluent was subjected to gas-liquid separation (degassing) and stabilization treatment to remove gas, and a light naphtha fraction (first-pass gasoline fuel component) was recovered to obtain Stream 1 and Stream 2. Fractionation was continued, and heavy bottom fractions were recovered from the stabilized Stream 1 and Stream 2 as recyclable streams that can be used as (first-pass) aviation fuel components and (first-pass) diesel fuel components, respectively. The characteristics of the various streams and products are shown in Table 3.

[0152]

Table 3

[0153] The characteristics of recycle stream 1 enable it to be used as a diesel fuel component, for example, in summer diesel fuel, and the characteristics of recycle stream 2 enable it to be used as a diesel fuel component, for example, in winter diesel fuel.

[0154] A portion of recycle stream 1 and recycle stream 2 was subjected to hydrocracking using a non-sulfided bifunctional noble metal catalyst on an acidic substance. The temperature of the hydrocracking step was varied to be lower than, the same as, or higher than that of the hydroisomerization step. The characteristics of the total liquid product recovered from the hydrocracking (i.e., the degassed recycle effluent), and the yield of the total liquid product (as wt-% of the second reactor feed including H2) are shown in Table 4. The compositional characteristics of the hydrocracking product (degassed recycle effluent) are shown in Table 5.

[0155]

Table 4

[0156] From Table 4, it can be seen that in each test run of Table 4, the liquid yield is high, and the higher the HC temperature, the slightly lower the liquid yield. Furthermore, all of the recycle effluents recovered from the test runs had significantly lower cloud points and lower concentrations compared to their respective recycle streams. The decrease in cloud point was more dramatic in the recycle effluent derived from recycle stream 1, which originally had a higher cloud point (than recycle stream 2).

[0157]

Table 5

[0158] From Table 5, it can be seen that each recycle effluent derived from recycle stream 1 has an efficiently reduced C15 - C18 hydrocarbon content, a reduced n - paraffin content, and a significantly increased multi - branched i - paraffin content compared to recycle stream 1. The aromatic compound content in these recycle effluents is at the same level (the highest HC temperature) or lower than that in recycle effluent 1, indicating dearomatization at a low HC temperature. Each recycle effluent derived from recycle stream 2 where the C15 - C18 content was measured had an efficiently reduced C15 - C18 content compared to recycle stream 2. Each regenerated effluent derived from recycle stream 2 where the n - paraffin content was measured had a slightly increased n - paraffin content compared to recycle stream 2. In most of the recycle effluents derived from recycle stream 2, the multi - branched i - paraffin content increased compared to recycle stream 2. The recycle effluent from the test run using the highest HC temperature had a slightly reduced multi - branched i - paraffin content compared to recycle stream 2. The aromatic compound content in the recycle effluents derived from recycle stream 2 decreased, indicating that efficient dearomatization occurred in the HC. However, in test run 3 containing HC at the highest temperature (352°C), the aromatic compound content slightly increased, which is presumably due to the combination of high T and low pressure. Overall, these results show that the hydrocracking of the recycle stream under various hydrocracking conditions reduced the C15 - C18 content from 95 wt - % to less than 90% and further to less than 40 wt - %, and the hydrocracking not only decomposed the mono - iP molecule into one n - paraffin and one iso - paraffin but also efficiently increased the degree of isomerization of the multi - branched i - paraffin content. This effect can also be inferred from the physicochemical properties of the recycle effluents reported in Table 4.

[0159] The yields of recoverable C1 - C4 gas, C5 + gas, gasoline, aviation fuel, and diesel fuel components were calculated from the simdis analysis of the recycle effluent and are shown in Table 6.

[0160]

Table 6

[0161] From Table 6, it can be seen that the lower hydrocracking temperature has a slightly higher liquid yield than the higher hydrocracking temperature. Generally, the 150 - 300 fraction yield (i.e., the boiling range of aviation fuel) was at a good level, especially when the WHSV was low. The yield of the IBP - 150 fraction showed a more significant decrease, while at the same time the yield of the 300 fraction increased. Surprisingly, even when the highly isomerized and multi - branched recycle stream 2 was hydrocracked, the C1 - C4 yield remained low. The gas yield increased only in the test run 3 containing HC with the combination of the highest temperature (352 °C) and the lowest pressure (20 bar). Thus, adjusting the operating conditions of hydrocracking seems to provide a convenient method for adjusting the yields of different liquid transportation fuel components according to, for example, market needs.

[0162] 2.2 Characteristics of the recovered liquid transportation fuel components The recycle effluent from the hydrocracking test run was fractionated to recover gasoline fuel components, aviation fuel components, and diesel fuel components. Further, for one of the recycle effluents, fractionation was carried out in an optimized way to increase the yield of aviation fuel components (test run 8 with optimized fractionation, TR8o). Some product characteristics are shown in Table 7.

[0163] [Table 7]

[0164] From Table 7, it can be seen that the distillation characteristics of the gasoline, aviation fuel, and diesel fuel components recovered from the recycle effluent of the selected test runs meet their respective regulations.

[0165] The properties of the aviation fuel components obtained from TR15 and the aviation fuel components obtained from fraction-optimized TR8 (TR8o) were analyzed. Table 8 reports the physicochemical properties, and Table 9 reports the details of the composition by carbon number analyzed by GCxGC-FID / GCxGC-MS. The conventional HDO of fatty feedstocks and the highly severe HI process, i.e., paraffinic renewable jet fuel components obtained without hydrocracking, were used as a reference (RRJF).

[0166]

Table 8

[0167]

Table 9

[0168] In Table 9, nP represents n-paraffin, mono-iP represents mono-branched i-paraffin, iP-dime represents i-paraffin with two (methyl) branches, iP-trime represents i-paraffin with three (methyl) branches, and iP-tetrame represents i-paraffin with four (methyl) branches.

[0169] From the aviation fuel component analysis (Table 8), it can be seen that the aviation fuel components recovered from the test run have excellent low-temperature properties, especially the freezing point and kinematic viscosity at -20°C. From the composition analysis reported in Table 9, it became clear that for the aviation fuel components recovered from the test run, the wt-% amounts are evenly distributed among carbon numbers in the range of C6 - C18: compared with 71.9 wt-% of the reference RRJF, 52.8 wt-% of C15 - C18 paraffins were obtained for TR8o and 41.9 wt-% for TR15. This contributes, for example, to a more balanced distillation curve and combustion behavior, and a lower density. The detailed composition analysis of the TR8o aviation fuel components revealed that the nP content is very low and the iP content, especially the multi-branched iP content, is very high, which is reflected in the excellent freezing point and kinematic viscosity below the freezing point.

[0170] The characteristics of the diesel fuel components of TR8, TR8o, TR14, TR15, and TR16 were analyzed and shown in Table 10. The normal HDO of the fatty raw material and the HI process of medium severity, i.e., the winter-grade paraffinic renewable diesel fuel component obtained without hydrocracking, were used as references (reference RDW). The Arctic fossil diesel fuel component was used as another criterion, similar to recycle stream 2 (before hydrocracking).

[0171]

Table 10

[0172] * Calculated assuming the calorific value of the TR8 diesel fuel component and Ref RDW is 44.0 MJ / kg.

[0173] From Table 10, it can be seen that the diesel fuel components recovered from the test run have improved low-temperature characteristics in terms of cloud point compared to the reference renewable winter diesel and recycle stream 2. Surprisingly, each component of the diesel fuel recovered in the test run had a significantly higher viscosity at 40 °C and also a higher density, especially compared to the criteria for winter diesel fuel. This means that the diesel fuel components recovered from the test run may be blended in a higher proportion into diesel fuels that meet the 15-degree density requirement (820 - 845 kg / m 3 ) of Table 1 of EN 590-2022. The resulting diesel fuel components are also effective for Arctic-grade diesel fuels (Table 3 of EN 590-2022), efficiently improving the fuel viscosity (at 40 °C) and spray behavior within the fuel system, leading to improved fuel consumption. The compositional analysis of the diesel fuel components recovered from the test run (results not reported) showed a higher total iso-paraffin and multi-branched iso-paraffin content compared to the reference RDW, contributing to the excellent cloud point and viscosity characteristics seen in Table 10.

[0174] The characteristics of the gasoline fuel components of TR8, TR15, and TR8o were analyzed and reported in Table 11. The conventional HDO and medium-severity HI processes for fatty feeds, i.e., paraffinic renewable gasoline fuel components obtained without hydrocracking, were used as references (reference RG).

[0175] [Table 11]

[0176] * Calculated based on the wt-% amounts of n-paraffins, i-isoparaffins, and multi-branched i-paraffins with each carbon number measured by GC-FID / GC-MS. ** Blend RON (bRON) was measured from blends with commercially available gasoline components with a high i-paraffin content according to EN ISO 5164-2014 (equivalent to ASTM D2699-18), and blend MON (bMON) was measured according to EN ISO 5163-2014 (equivalent to ASTM D2700-19).

[0177] From Table 11, it can be seen that the determined bRON and bMON octane numbers were highly improved in the gasoline fuel components recovered from the test run compared to the reference renewable gasoline fuel components (reference RG). Furthermore, each component of the gasoline fuel recovered from the test run had a significantly higher content of C4-C9 i-paraffins compared to the reference renewable gasoline components. This suggests that not only were the paraffin molecules decomposed by hydrocracking, but the degree of isomerization was also improved. The average carbon number of C4-C9 decreased, especially in n-paraffins. Both the improvement in the degree of isomerization and the shortening of n-paraffins are considered to contribute to the improvement of the octane number. Due to the improved characteristics, this gasoline fuel component can be mixed with gasoline fuel at a higher ratio than the reference renewable gasoline fuel component.

[0178] In summary, each liquid fuel component recovered from the test run has improved properties for use in a fuel composition, at least in terms of improved isomerization degree, which generally also improves properties at low temperatures and fluidity / mixability. These and other improved properties of the liquid fuel components recovered from the test run are also desired and beneficial in a wide range of other applications, particularly those involving spraying, injection, and / or miscibility with other components.

[0179] Various embodiments are presented. It should be understood that in this specification, the words "comprise", "include", and "contain" are each used as open-ended expressions that do not intend exclusivity.

[0180] The foregoing description has provided a complete and beneficial explanation of the best mode currently contemplated by the inventors for carrying out the invention by way of certain embodiments and non-limiting examples of embodiments. However, it will be apparent to those skilled in the art that the invention is not limited to the details of the embodiments shown above, and that other embodiments, or combinations of different embodiments, can be implemented using equivalent means without departing from the features of the invention.

[0181] Furthermore, some of the features of the foregoing disclosed exemplary embodiments can be advantageously used without the corresponding use of other features. Thus, the foregoing description is considered to merely illustrate the principles of the invention and not to limit it. Accordingly, the scope of the invention is limited only by the appended claims.

Claims

1. 1. A process for producing at least one liquid transportation fuel component, said process comprising: providing a paraffinic hydrocarbon feed comprising at least 60 wt-% paraffins based on the total weight of the paraffinic hydrocarbon feed, wherein at most 30 wt-% of said paraffins are isoparaffins; subjecting said paraffinic hydrocarbon feed to hydroisomerization in the presence of a hydroisomerization catalyst in a first reactor to obtain a hydroisomerized effluent; subjecting the hydroisomerization effluent to fractionation to separate from the fraction at least a recycle stream comprising C16 n-paraffins and having a T5 temperature of 270°C or greater (5 vol% recovery, EN ISO 3405-2019); subjecting the second reactor feed comprising the recycle stream to hydrocracking in a second reactor in the presence of a hydrocracking catalyst to obtain a recycle effluent; feeding the recycle effluent to the fractionation as a co-feed with the hydroisomerization effluent; and recovering at least one or more liquid transportation fuel components from said fractionation; A process involving:

2. The hydroisomerization in the first reactor is carried out at a temperature in the range of 200°C to 500°C, preferably 230°C to 500°C, more preferably 250°C to 450°C, even more preferably 280°C to 400°C, a pressure in the range of 1 MPa to 10 MPa, preferably 2 MPa to 8 MPa, or 3 MPa to 10 MPa, a H 2 O 3 at the first reactor inlet in the range of 1 MPa to 10 MPa, preferably 2 MPa to 8 MPa. 2 2. The process of claim 1, carried out at a partial pressure, a weight hourly space velocity in the range of 0.1 to 10, preferably 0.2 to 8, more preferably 0.4 to 6 kg paraffinic hydrocarbon feed / kg catalyst / hour, and a H2 / paraffinic hydrocarbon feed ratio in the range of 10 to 2000, preferably 50 to 1000 normal litres H2 / litre paraffinic hydrocarbon feed.

3. The hydrocracking in the second reactor is carried out at a temperature in the range of 200°C to 450°C, preferably 220°C to 430°C, more preferably 280°C to 350°C, a pressure in the range of 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa, more preferably 2.5 MPa to 7 MPa, a H 2 O 3 at the inlet of the second reactor in the range of 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa, more preferably 2.5 MPa to 7 MPa. 2 Partial pressure of H in the range of 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa, more preferably 2.5 MPa to 7 MPa 2 10. The process of claim 1, carried out at a partial pressure of 0.1 to 10 kg, preferably 0.2 to 8 kg, more preferably 0.4 to 6 kg, even more preferably 0.5 to 1.5 kg second reactor feed / kg catalyst / hr, a weight hourly space velocity of 0.1 to 10 kg, preferably 0.2 to 8 kg, more preferably 0.4 to 6 kg, even more preferably 0.5 to 1.5 kg second reactor feed / kg catalyst / hr, and a H2 / second reactor feed ratio in the range of 10 to 2000, preferably 50 to 1000 normal litres H2 / litre second reactor feed.

4. 10. The process of claim 1, wherein said first reactor is operated at a higher temperature than said second reactor.

5. The process of claim 1, wherein the recycle stream comprises at least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt%, even more preferably at least 80 wt% isoparaffins based on the total weight of paraffins in the recycle stream, and / or at least 5 wt%, preferably at least 10 wt%, more preferably at least 15 wt%, even more preferably at least 20 wt% multi-branched isoparaffins based on the total weight of paraffins in the recycle stream.

6. The process of claim 1, wherein the recycle stream has a cloud point below 0°C, preferably below -5°C, more preferably below -8°C, and even more preferably below -10°C (ASTM D 5771-17).

7. 2. The process of claim 1, wherein the recycle stream has a T5 temperature (ENISO 3405-2019) in the range of from 270°C to less than 300°C, preferably in the range of from 270°C to less than 295°C, more preferably in the range of from 270°C to less than 290°C, and / or an initial boiling point (IBP, ENISO 3405-2019) of less than 290°C, preferably less than 288°C, more preferably less than 285°C or less than 280°C.

8. The process of claim 1, wherein the recycle effluent and the hydroisomerization effluent are fed to fractional distillation in a weight ratio of 1:10 to 10:1, preferably 1:5 to 5:

1.

9. The process of claim 1, wherein the second reactor feed further comprises a portion of the hydroisomerization effluent.

10. To receive at least one or more values ​​of the following parameters: the content of impurities in the paraffinic hydrocarbon feed, preferably the content of at least one or more of N, S, O, P, Si, Cl, Fe, alkali metals, alkaline earth metals, and / or coke-forming compounds in the paraffinic hydrocarbon feed; NH in the vapor phase of the hydroisomerization effluent 3 and / or H 2 S, and / or NH in the gas phase of the recycled effluent 3 and / or H 2 S content physicochemical properties of the hydroisomerization effluent and / or the recycle effluent, preferably at least one or more of cloud point, freezing point, pour point, cold filter plugging point, kinematic viscosity, density, and / or distillation properties; compositional characteristics of the hydroisomerization effluent and / or the recycle effluent, preferably at least one or more of the content of isoparaffins, the content of C8 to C14 hydrocarbons, the content of multi-branched isoparaffins, and / or the content of C1 to C4 hydrocarbons in the hydroisomerization effluent and / or the recycle effluent; at least one or more yields of said recovered liquid transportation fuel components and / or said separated recycle stream, preferably a yield of said recovered aviation fuel components. at least one or more physicochemical properties of the recovered liquid transportation fuel components and / or the separated recycle stream, preferably at least one or more of cloud point, freezing point, pour point, cold filter plugging point, kinematic viscosity, density, research octane number (RON), cetane number, and / or distillation properties; at least one or more compositional characteristics of the recovered liquid transportation fuel components and / or the separated recycle stream, preferably the isoparaffin content and / or the hyperbranched isoparaffin content in the recovered fuel components and / or the separated recycle stream; and / or a temperature differential on the first reactor or over a catalyst bed therein, and / or a temperature differential on the second reactor or over a catalyst bed therein; monitoring at least one or more values ​​of comparing the received value with a predetermined value, and adjusting at least one or more operating conditions in the first reactor and / or the second reactor based on the comparison, preferably temperature, pressure, weight hourly space velocity (WHSV), H2O2 to the paraffinic hydrocarbon feed. 2 adjusting the ratio of H to second reactor feed, the ratio of H to second reactor feed, and / or the H partial pressure at the inlet of the first reactor and / or the second reactor, respectively, more preferably by increasing the temperature and / or pressure in the first reactor and / or the second reactor, and / or decreasing the WHSV in the first reactor and / or the second reactor, respectively. The process of claim 1 comprising:

11. A process as described in claim 1, wherein following the hydrocracking, further hydroisomerization is carried out in the presence of a further hydroisomerization catalyst, and said further hydroisomerization is preferably carried out under operating conditions as described in claim 2.

12. The method of claim 1, wherein the hydroisomerization catalyst and / or the further hydroisomerization catalyst is a bifunctional hydroisomerization catalyst, preferably a non-sulfided bifunctional hydroisomerization catalyst; at least one or more metals selected from Group VIII of the Periodic Table, preferably from the noble metals of Group VIII, more preferably from Pt and / or Pd; at least one or more acidic porous materials selected from zeolites and / or zeolite-type materials, preferably the at least one or more zeolites and / or zeolite-type materials have a framework type selected from AEL, ATO, AFO, MRE, MTT, MTW, TON, MRT, MOR, FER, and / or MWW, preferably the acidic porous material is selected from SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, ZSM-48, NU-10, ZBM-30, IZM-2, EU-2, and / or mordenite, more preferably the acidic porous material is at least one or more acidic porous materials selected from SAPO-11, SAPO-41, ZSM-23, and / or ZSM-48; and Optionally, at least one or more of alumina, silica, amorphous silica-alumina, titanium alumina, titania, and / or zirconia; The process of claim 1 comprising:

13. The method of claim 12, wherein the hydrocracking catalyst is a bifunctional hydrocracking catalyst, preferably a non-sulfided bifunctional hydrocracking catalyst; at least one metal selected from Group VIII of the periodic table, Mo, Co, and / or W, preferably Ni, Mo, Co, W, Pt and / or Pd, more preferably Pt and / or Pd; and At least one acidic porous material selected from zeolites, zeolite-type materials, and / or amorphous silica-alumina, preferably the at least one zeolite or zeolite-type material has a framework type selected from MFI, BEA, FAU, MOR, FER, AEL, AFI, ATO, AFO, MRE, MTT, MTW, TON, and / or MRT, preferably SAPO-5, SAPO-11, SAPO-2, SAPO-3, SAPO-4, SAPO-5, SAPO-6, SAPO-7, SAPO-8, SAPO-9, SAPO-10, SAPO-11, SAPO-12, SAPO-13, SAPO-14, SAPO-15, SAPO-16, SAPO-17, SAPO-18, SAPO-19, SAPO-20, SAPO-21, SAPO-22, SAPO-23, SAPO-24, SAPO-25, SAPO-26, SAPO-27, SAPO-28, SAPO-29, SAPO-30, SAPO-31, SAPO-32, SAPO-33, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-38, SAPO-39, SAPO-40, SAPO-41, SAPO-42, SAPO-43, SAPO-44, SAPO-45, SAPO-46, SAPO-47, SAPO-48, SAPO-49, SAPO-50, SAPO-51, SAPO-52, SAPO-53, SAPO-54, SAPO-55, SAPO-56, SAPO-57, SAPO-58, SAPO-59, SAPO-59, SAPO-59, SAPO-59, SAPO-59, SAPO-59, SAPO-59, SAPO-56, SAPO-59, SAPO-59, SAPO-59 At least one or more acidic porous materials selected from APO-31, SAPO-41, ZSM-22, ZSM-23, ZSM-43, ZSM-48, IZM-2, mordenite, β-zeolite, Y-type zeolite, and / or amorphous silica-alumina, more preferably at least one or more acidic porous materials selected from SAPO-5, SAPO-11, ZSM-23, β-zeolite, Y-type zeolite, and / or amorphous silica-alumina; and Optionally, at least one of alumina, silica, titanium alumina, titania, and / or zirconia. The process of claim 1 comprising:

14. The process of claim 1 , wherein the hydroisomerization catalyst and the hydrocracking catalyst are different from each other.

15. The paraffinic hydrocarbon feed comprising: at least 70 wt-%, preferably at least 80 wt-%, more preferably at least 90 wt-%, even more preferably at least 95 wt-% paraffins of the total weight of the paraffinic hydrocarbon feed; and / or at most 25 wt-%, preferably at most 20 wt-%, more preferably at most 15 wt-% isoparaffins of the total weight of paraffins in the paraffinic hydrocarbon feed; and / or at least 70 wt-%, preferably at least 80 wt-%, more preferably at least 90 wt-%, even more preferably at least 95 wt-% C12 to C30 hydrocarbons based on the total weight of the paraffinic hydrocarbon feed; and / or at least 70 wt-%, preferably at least 80 wt-%, more preferably at least 90 wt-%, even more preferably at least 95 wt-% C14 to C22 hydrocarbons based on the total weight of the paraffinic hydrocarbon feed; The process of claim 1 comprising:

16. The step of providing the paraffinic hydrocarbon feed comprising: subjecting the hydrotreatment feed to catalytic hydrotreatment to obtain a paraffinic hydrotreatment effluent; and subjecting said paraffinic hydroprocessing effluent to gas-liquid separation and optionally paraffinic feed fractionation to provide said paraffinic hydrocarbon feed; The process of claim 1 comprising:

17. The step of providing the paraffinic hydrocarbon feed comprising: subjecting the hydrotreatment feed to catalytic hydrotreatment to obtain a paraffinic hydrotreatment effluent, wherein the hydrotreatment feed preferably comprises at least one or more of vegetable oils, animal fats and oils, microbial oils, thermally liquefied organic wastes and residues, and / or enzymatically liquefied organic wastes and residues; and / or subjecting the synthesis gas to a Fischer-Tropsch (FT) transformation to obtain a paraffinic FT effluent; subjecting said paraffinic hydrotreating effluent and / or said paraffinic FT effluent to gas-liquid separation and optionally to paraffinic feed fractionation to provide said paraffinic hydrocarbon feed; The process of claim 1 comprising:

18. The method of claim 17, wherein providing the paraffinic hydrocarbon feed comprises subjecting the oxygenated hydrocarbon feed to catalytic hydrodeoxygenation, and the hydrodeoxygenation is carried out in the presence of a hydrodeoxygenation catalyst at a temperature in the range of 200°C to 500°C, a pressure in the range of 1 MPa to 20 MPa, a H 2 O 3 at the inlet of the reactor in the range of 1 MPa to 20 MPa. 2 partial pressure, 0.1-10 kg oxygenated hydrocarbon feed / kg catalyst / hour, and H 2 / Oxygenated hydrocarbon feed ratio is 50 to 2000 normal liters H 2 17. The process of claim 16, wherein the oxygenated hydrocarbon feed is in the range of 1 / 1 / 2 gallon per liter.

19. The process of claim 17, wherein the hydrodeoxygenation catalyst is a sulfided catalyst comprising at least one or more metals from Group VIII of the Periodic Table and / or from Group VIB of the Periodic Table, preferably at least one or more of Ni, Mo, W, and / or Co, more preferably at least one or more of Ni and / or Co and Mo and / or W, such as NiMo, CoMo, NiCoMo, NiW, and / or NiMoW.

20. The process of claim 1, wherein the biogenic carbon content (EN 16640 (2017)) of the paraffinic hydrocarbon feed is at least 50 wt%, preferably at least 70 wt%, more preferably at least 90 wt%, even more preferably at least 95 wt%, or about 100 wt%, based on the total weight of carbon (TC) in the paraffinic hydrocarbon feed.

21. 2. The process of claim 1, wherein at least one or more of an aviation fuel component, a diesel fuel component, a gasoline fuel component, and / or a marine fuel component are recovered from the fractionation, preferably at least an aviation fuel component, more preferably at least an aviation fuel component and a diesel fuel component, even more preferably at least an aviation fuel component, a diesel fuel component, and a gasoline fuel component.

22. At least one of the liquid transportation fuel components recovered from the fractional distillation has a density at 15°C of 730 to 772 kg / m 3 (EN ISO 12185-1996), a T10 temperature of at most 205°C (EN ISO 3405-2019), a final boiling point of at most 300°C (EN ISO 3405-2019), a flash point of at least 38°C (IP 170-2013), and a freezing point of at most -40°C (IP 529-2016).

23. The process of claim 1, comprising recovering aviation fuel components from the fractional distillation in a yield of at least 30 wt %, preferably at least 40 wt %, more preferably at least 50 wt %, for example 30 wt % to 90 wt %, based on the total weight of the paraffinic hydrocarbon feed.

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