Method for producing a liquid transport fuel component

Abstract

A process for producing at least one liquid transportation fuel component is provided, in which, in a first operating mode, a paraffinic hydrocarbon feed is converted to a hydroisomerization effluent, fractionated, and its fractions are returned to the fractionation via a hydrocracking reactor, from which a liquid transportation fuel component, preferably an aviation fuel component, is recovered. In this process, parameters indicating deactivation of the hydroisomerization catalyst are monitored, and when these reach a predetermined value, the process is switched to a second operating mode in which the hydroisomerization waste liquid is subjected to hydrocracking and the resulting hydrocracking waste liquid is fractionated to obtain a liquid transportation fuel component, preferably an aviation fuel component.

Description

Technical Field

[0001] The present disclosure generally relates to processes for producing renewable fuel components. The present disclosure relates in particular, but not exclusively, to processes for producing at least one or more liquid transportation fuel components, preferably at least aviation fuel components. Also disclosed are systems and computer programs that can be used to carry out the process.

Background Art

[0002] This section provides 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 increasing 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). Also, there is a need 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 in aviation fuel or even as is when appropriately blended with additives.

Summary of the Invention

[0005] It is an object to solve or at least 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, especially C1-C2 hydrocarbons, in the process for producing renewable liquid transportation fuel components. Yet another object is to extend the lifespan of the hydroisomerization catalyst in the process for producing renewable liquid transportation fuel components.

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

[0007] In a first exemplary aspect, a process for producing at least one liquid transportation fuel component is provided, the process comprising: 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 the paraffins are isoparaffins; subjecting the paraffinic hydrocarbon feed to hydroisomerization in a first reactor in the presence of a hydroisomerization catalyst to obtain a hydroisomerization effluent; i) 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 from the fractionation; ii) 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; iii) 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; and A step of monitoring a parameter indicating deactivation of the hydrogen isomerization catalyst A to receive a value; A step of comparing the received value with a predetermined value; and When the received value reaches the predetermined value, the following from steps i), ii), iii): I) A step of subjecting the second reactor B feed containing the hydrogen isomerization effluent to hydrocracking in a second reactor B in the presence of a hydrocracking catalyst B to obtain a hydrocracked effluent; II) A step of subjecting the hydrocracked effluent to fractional distillation and recovering at least one or more liquid transportation fuel components from the fractional distillation are included.

[0008] In certain embodiments, in steps iii) and II), 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 preferably recovered from the fractional distillation, at least the aviation fuel component, more preferably at least the aviation fuel component and the diesel fuel component, or at least the aviation fuel component and the gasoline fuel component.

[0009] In certain preferred embodiments, in steps iii) and II), an aviation fuel component having a density at 15°C (EN ISO 12185-1996) in the range of 730 to 772 kg / m 3 , a T10 temperature (EN ISO 3405-2019) of at most 205°C, a final boiling point (EN ISO 3405-2019) of at most 300°C, a flash point (IP 170-2013, Avel close-cup method) of at most 38°C, and a pour point (IP 529-2016) of at most -40°C is at least recovered from the fractional distillation.

[0010] It is particularly suitable for the production of aviation fuel components. By this process, aviation fuel components can be obtained in a higher yield as compared to the conventional processes for producing fuel components by hydrodeoxygenation (HDO) and hydroisomerization (HI) of renewable fats and oils. Further, the process of the present invention produces aviation fuel components with improved quality that can be used in a greater amount in aviation fuel or even as such when appropriately additives are added, as compared to the aviation fuel components produced by the above conventional processes. Furthermore, the process of the present invention extends the life of the hydroisomerization (HI) catalyst and enables the utilization of a wider range of feeds including heavier and more impure feeds as compared to the above conventional processes.

[0011] In a second exemplary aspect, a system for producing at least one liquid transport fuel component is provided, the system being configured to carry out a process using i), ii), iii) or I), II), III) of the system, the system comprising: means configured to supply 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 the paraffins are isoparaffins; a first reactor configured to subject the paraffinic hydrocarbon feed in the first reactor to hydroisomerization in the presence of a hydroisomerization catalyst to obtain a hydroisomerization effluent; i) subjecting the hydroisomerization effluent to fractionation and separating at least a recycle stream having a T5 temperature (5 vol% recovery, EN ISO 3405-2019) of 270 °C or higher from the fractionation, and subjecting the recycle effluent to fractionation (ii) and (iii) below); and II)) a fractionation system configured to subject the hydrocracking effluent to fractionation for fractionation; ii) To obtain a recycled effluent, subject a second reactor feed comprising a recycle stream to hydrocracking in a second reactor in the presence of a hydrocracking catalyst; and I) A second reactor configured to subject a second reactor feed comprising a hydroisomerization effluent to hydrocracking in a second reactor in the presence of a hydrocracking catalyst to obtain a hydrocracking effluent; iii) A conduit configured to supply the recycled effluent and the hydroisomerization effluent to a fractionation system, and III) to supply the hydrocracking effluent to a fractionation system; Means configured to recover at least one or more liquid transportation fuel components from the fractionation system; and Monitoring a parameter indicative of deactivation of the hydrogen isomerization catalyst to receive a value; comparing the received value with a predetermined value; and when the received value reaches the predetermined value, switching from i), ii), iii) to I), II), III) of the (system) so as to configured control device including.

[0012] According to a third exemplary aspect, when executed by a processor of a control device in a system for producing at least one liquid transportation fuel component, in the process according to the first exemplary aspect, the control device is caused to compare the received value with a predetermined value and, when the received value reaches the predetermined value, switch from i), ii), iii) to I), II). A computer program product is provided that includes instructions for causing the computer program product to perform the steps of comparing the received value with a predetermined value and switching from i), ii), iii) to I), II) in at least the process according to the first, second, or third exemplary aspect in a control device or control equipment in a system for producing at least one liquid transportation fuel component.

[0013] The computer program product according to the third exemplary embodiment enables more precisely operating the process defined by the first exemplary embodiment, monitoring more different parameters, comparing the obtained values with a huge dataset, using the obtained values in a complex model, more quickly adjusting and / or switching the process based on the comparison, improving and / or adjusting the yield and / or quality of the recovered liquid transportation fuel components as needed, and enhancing the safety of the present process, which are just some of the advantages.

[0014] In the foregoing, various exemplary embodiments and implementations without constraints are illustrated. The foregoing embodiments are merely used to illustrate selected embodiments or steps that can be utilized in various implementations. Some embodiments may be presented only with reference to specific exemplary embodiments. It should be understood that the corresponding embodiments can also be applied to other exemplary embodiments.

Brief Description of the Drawings

[0015] Some exemplary embodiments will be described with reference to the accompanying drawings.

[0016]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0017] In the following description, like reference numerals indicate like elements or steps.

[0018] All standards mentioned in this book are, unless otherwise specified, the latest revised versions available at the filing date.

[0019] 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 moment 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, usually occurring 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 hydrocarbons in the gasoline range, ASTM D7096-19 may be referred to.

[0020] 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 ISO 3405-2019.

[0021] 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.

[0022] As used in the context of the present disclosure, gasoline fuel components or naphtha refer to hydrocarbon components suitable for use in fuel compositions that meet the standard specifications of gasoline fuels, such as those specified in EN 228 - 2012+A1 - 2017. Typically, such gasoline fuel components, when measured in accordance with EN ISO 3405 - 2019, boil within the range of about 25°C to about 210°C, i.e., have an IBP and an FBP.

[0023] As used in the context of the present disclosure, marine fuel components refer to hydrocarbon components suitable for use in fuel compositions that meet the standard specifications of marine fuels, such as those specified in ISO 8217 - 2017. Typically, such marine fuel components, when measured in accordance with EN ISO 3405 - 2019, boil within the range of about 180°C to about 600°C, for example, about 180°C to about 400°C, i.e., have an IBP and an FBP.

[0024] 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, oxygen - containing hydrocarbons refer to hydrocarbons containing covalently - bonded oxygen.

[0025] As used herein, paraffin refers to an acyclic alkane, i.e., an acyclic open - chain saturated hydrocarbon that is linear (normal paraffin, n - paraffin) or branched (isoparaffin, i - paraffin). In other words, as used herein, paraffin refers to n - paraffins and / or i - paraffins.

[0026] In the context of the present disclosure, i-paraffins refer to branched acyclic alkanes, i.e., acyclic open-chain saturated hydrocarbons 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, herein, i-paraffins refer 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 i-paraffin and any multi-branched i-paraffin, 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-paraffin, any monobranched i-paraffin, and any multi-branched i-paraffin.

[0027] In the context of the present disclosure, olefins refer to unsaturated, straight-chain, branched, or cyclic hydrocarbons excluding aromatic compounds. In other words, olefins refer to hydrocarbons having at least one unsaturated bond excluding unsaturated bonds in an aromatic ring.

[0028] As used herein, cyclic hydrocarbons refer to all hydrocarbons containing a cyclic structure, including cyclic olefins, naphthenes, and aromatics. As used herein, naphthenes refer 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, aromatics refer to hydrocarbons containing at least one aromatic ring structure, i.e., hydrocarbons having a cyclic structure with delocalized alternating π bonds over the entire circumference of the cyclic structure.

[0029] In the context of the present disclosure, for a composition that boils 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 % (wt-%) relative to the degassed 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 in the feed, stream, effluent, product, component, or sample in question. The contents can 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 run 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 microliter. 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.Data processing including the identification of detected compounds or hydrocarbon groups, and the measurement of mass concentration by applying the response factor to n-heptane for the volume of detected peaks and normalizing to 100 w-% were performed using commercially available tools (LabSolutions from Shimadzu Corporation, GC Image from Zoex). Olefins and naphthenes, and heteroatomic species and aromatics were grouped together unless reported separately. The quantification limit for individual compounds by this method is 0.1 wt-%.

[0030] 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, appropriately prepared. For example, cloud point is determined from a degassed feed, stream, effluent, product, component, or sample according to ASTM D5771-17.

[0031] 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.

[0032] In the context of the present disclosure, feeds to reactors, particularly the first reactor and / or the second reactor, are defined such that H2 that may be supplied to each reactor, for example, H2 supplied to hydroisomerization and H2 supplied to hydrocracking, are excluded from the definition of the feed.

[0033] As used herein, the hydrogen isomerization (HI) effluent, optionally, refers to the total HI effluent, the degassed HI effluent, or the degassed and stabilized HI effluent, and the term HI effluent can include each of these.

[0034] 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 practicable integer. It should be understood that not all compounds corresponding to the definitions necessarily exist.

[0035] 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 a maximum of Y carbon atoms, where Y is any practicable integer. It is understood that not all compounds corresponding to the definitions necessarily exist.

[0036] 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) single-branched i-paraffin, CXY-CXZ multi-branched i-paraffin, CXY-CXZ hydrocarbon, or CXY-CXZ fatty acid means a range of paraffin, n-paraffin, i-paraffin, single-branched i-paraffin, multi-branched i-paraffin, hydrocarbon, or fatty acid, respectively, where XY and XZ are executable 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, for paraffin, n-paraffin, i-paraffin, single-branched i-paraffin, multi-branched i-paraffin, hydrocarbon, or fatty acid, in some cases, not all of the carbon atoms within said range, especially the carbon atoms at the end-points or in the vicinity thereof, necessarily exist 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.

[0037] Typically, as defined each time, it means the total amount as weight or volume of paraffin, n-paraffin, i-paraffin, single-branched i-paraffin, multi-branched i-paraffin, hydrocarbon, or fatty acid of all carbon atoms included. For example, C15~C22 n-paraffin refers to n-paraffin within the range such as C15, C16, C17, C18, C19, C20, C21, C22 n-paraffin, even if the content of C15 n-paraffin is zero. In other words, the total amount is obtained by adding 0 (referring to non-existent C15 n-paraffin) to the total weight of all other C15~C22 n-paraffin present.

[0038] Isomerization converts at least a certain amount of n-paraffin into i-paraffin, particularly mono-branched i-paraffin. By (further) increasing the degree of isomerization, for example, by increasing the severity of hydroisomerization as described below, more n-paraffin can be converted into i-paraffin, and mono-branched i-paraffin can be converted into i-paraffin having multiple branches, such as di-branched and / or tri-branched i-paraffin, and even i-paraffin containing three or more branches.

[0039] As used herein and in the context, the degree of effective cracking refers to cracking that results in non-gaseous (NTP) cracking products, and particularly, as shown herein, cracking as the ratio of the C8-C14 hydrocarbon content in the hydrocracking effluent (Process I) or recycle stream (Process II) to the C8-C14 hydrocarbon content in the second reactor feed.

[0040] As used herein, 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. Those skilled in the art will understand that any "reactor" may actually be implemented as a reactor system composed of one or more reactors. Whether the reactor is actually arranged in a single reactor or in multiple 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.

[0041] Catalyst properties such as the total number of acidic sites, for example, refer to the catalyst properties at the start of the process, in an immediately usable state, in the context of the present disclosure.

[0042] As used herein, 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 decrease in the desired reaction product in the reactor effluent) of a catalyst at a given time point (t n ) as 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 thought to be due to poisoning and fouling phenomena and encompasses both reversible and irreversible deactivation

[0043] As used herein, the term "renewable" refers to a compound or composition that is available, derivable, or derived from plants and / or animals, including all or part of a compound or composition that is available, derivable, or derived from fungi and / or algae. As used herein, a renewable compound or composition may include a genetically engineered compound or composition. A renewable feed, ingredient, compound, or composition may also be referred to as a biological feed, ingredient, compound, or composition, or a bio-based feed, ingredient, compound, or composition

[0044] As used herein, the term "fossil" refers to a compound or composition that is 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 that are available from subterranean / underground sources

[0045] 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. Therefore, they may be treated differently 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.

[0046] The renewable or fossil origin of any organic compound containing hydrocarbons can be chemically determined by appropriate methods for analyzing the carbon content of renewable origin, such as DIN 51637 (2014), ASTM D6866 (2020), and EN 16640 (2017). Such methods are based on the fact that renewable or biogenic carbon atoms have a higher number of unstable radiocarbon ( 14 C) atoms compared to fossil-derived carbon atoms. Therefore, 12 C and 14By 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. Thus, 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)). As used herein, 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, even more preferably about 100 wt-%, based on the total weight of the carbon in the material (EN 16640 (2017)).

[0047] In a first exemplary aspect, provided herein is a process for producing at least one liquid transportation fuel component, the process comprising: 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 in a first reactor in the presence of a hydroisomerization catalyst to obtain a hydroisomerization effluent; i) subjecting the hydroisomerization effluent to fractional distillation to separate at least a recycle stream having a T5 temperature (5 vol% recovery, EN ISO 3405-2019) of 270 °C or higher from the fractionation extract; ii) 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 to obtain a recycled effluent; iii) a step of feeding the recycled 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; and a step of monitoring a parameter indicating deactivation of the hydroisomerization catalyst A to receive a value; a step of comparing the received value with a predetermined value; and when the received value reaches the predetermined value, from steps i), ii), iii) to the following: I) a step of subjecting a second reactor B feed containing the hydroisomerization effluent to hydrocracking in a second reactor B in the presence of a hydrocracking catalyst B to obtain a hydrocracking effluent; II) a step of subjecting the hydrocracking effluent to fractionation, and recovering at least one or more liquid transportation fuel components from the fractionation are included.

[0048] Preferably, this process is a continuous process.

[0049] The process operated according to steps i), ii), iii) may be referred to as the initial / first mode of the process / operation, and the process operated according to steps I), II) may be referred to as the switched / second mode of the process / operation.

[0050] The first exemplary embodiment provides a process for producing at least one liquid transportation fuel component, in which, in a first run mode, a paraffinic hydrocarbon feed is converted to a hydroisomerization effluent, fractionated, and the fractions are recycled to the fractionation via a second hydrocracking reactor, from which a liquid transportation fuel component, preferably an aviation fuel component, can be recovered. In this process, parameters indicating deactivation of the hydroisomerization catalyst are monitored, and when these reach a predetermined value, the process is switched to a second operating mode in which the hydroisomerization effluent is subjected to hydrocracking and the resulting hydrocracked effluent is fractionated to obtain a liquid transportation fuel component, preferably an aviation fuel component.

[0051] At least one or more liquid transportation fuel components recovered from the fractionation can be one or more of an aviation fuel component, a diesel fuel component, a gasoline fuel component, and / or a marine fuel component. Preferably, at least an aviation fuel component is recovered, more preferably at least an aviation fuel component and a diesel fuel component, or at least an aviation fuel component and a gasoline fuel component, are recovered.

[0052] By the process of the present invention, it is possible to obtain a higher yield of an aviation fuel component throughout the life of the hydroisomerization (HI) catalyst without reducing the ability of HI in the first reactor and / or without improving the quality of the aviation fuel component, as compared to conventional processes for producing fuel components by hydrodeoxygenation (HDO) and hydroisomerization (HI) of renewable oils and fats, for example.

[0053] By the process of the present invention, it is possible to produce an aviation fuel component that has excellent low-temperature properties even near the end of operation and can thus be used as an aviation fuel at a high mixing ratio or as it is without mixing, i.e., when appropriately additives are added. Further, the process of the present invention makes it possible to extend the life of the HI catalyst and enables the use of a wider range of feedstocks that are heavier and contain more impurities, as compared to conventional processes for producing fuel components by HDO and HI of renewable oils and fats.

[0054] 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, for example based on market dynamics.

[0055] The present manufacturing method proposes subjecting the HI effluent or a portion thereof to hydrocracking (HC), which cracks longer paraffin chains into paraffins boiling in the aviation fuel range, and further isomerizes the n-paraffins in the HC feed and the n-paraffins formed during the cracking reaction, and further isomerizes the isoparaffins by increasing the number of branches in the isoparaffin molecules to produce, for example, multi-branched isoparaffins. The hydrocracking can not only increase the yield of the aviation fuel component, but also improve its quality, such as low-temperature properties, especially the freezing point and / or viscosity at sub-zero temperatures such as -20°C.

[0056] During the continuous operation of the hydrogen isomerization of the catalyst, the HI catalyst gradually deactivates, for example, due to impurities or coking in the process stream. This process is very flexible and has various possibilities for adjusting the yield and / or quality of the recovered liquid transport fuel components and, in particular, for extending the life of the HI catalyst. 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 for adjusting the yield and / or quality of the recovered liquid transport fuel components and for coping with catalyst deactivation and / or changes in market needs. In addition, for example, 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 the various possibilities of the process of the present invention, in particular for compensating for the deactivation of the HI catalyst, it is possible to use paraffinic hydrocarbon raw materials with a higher impurity content compared to conventional processes for the production of liquid fuel components by HDO and HI of renewable oils and fats. Also, the hydrocracking step allows 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 transport fuel components such as aviation fuel components and / or gasoline fuel components with good yields and quality.

[0057] This process includes a step of monitoring a parameter indicating the deactivation of the HI catalyst to receive a value, a step of comparing the received value with a predetermined value, and a step of switching from i), ii), iii) to I), II) when the received value reaches or equals the predetermined value, that is, a step of switching from the first mode to the second mode. Preferably, the received value is compared with the corresponding predetermined value. The switching from i), ii), iii) to I), II) makes it possible to compensate for the deactivation of the HI catalyst and enables a good yield and quality of at least one recovered liquid transport fuel component for a longer period before the need to replace or regenerate the HI catalyst in the first reactor.

[0058] Initially, at the beginning of the process operation, typically, the activity of the HI catalyst is good or sufficient, and the received value from the monitoring is not equal to the (corresponding) predetermined value. However, at a certain point during the process execution, the deactivation of the HI catalyst typically reaches the point when the received value from the monitoring reaches the (corresponding) predetermined value, and this predetermined value is specified to indicate that the performance of the HI catalyst is insufficient or close to an insufficient state, for example, with respect to the volume (yield), and / or composition, and / or physicochemical properties of the recovered liquid transportation fuel component. At the point when the value received from the monitoring reaches the (corresponding) predetermined value, typically, a switch from i), ii), iii) to I), II) can be executed in order to recover and preferably exceed the target minimum value of the process performance. By switching from i), ii), iii) to I), II), the process can be operated to produce the desired liquid transportation fuel component with the desired quantity and quality for a longer time.

[0059] In certain embodiments, in addition to switching from the first mode to the second mode, the process may include adjusting one or more operating conditions of the first reactor and / or the second reactor to reach, maintain, or even exceed a target minimum value of process performance. In such embodiments, switching from the first mode to the second mode may be performed one or more times at some point after the operating conditions of the first reactor and / or the second reactor have been adjusted. The operating conditions may be adjusted to achievable limits and then the switch may be performed, alternatively, the operating conditions may be adjusted to some extent and the switch may already be performed before reaching the limits. Adjusting said one or more operating conditions may be based on the same parameters as the switch from i), ii), iii) to I), II), III) or on different parameters. Preferably, one or more operating conditions of the first reactor and / or the second reactor, particularly of the first reactor, are first adjusted to compensate for catalyst deactivation, particularly for deactivation of the HI catalyst, and when compensation for catalyst deactivation by simply adjusting the operating conditions of the first reactor and / or the second reactor is no longer feasible (or no longer desired), the switch from i), ii), iii) to I), II) is performed. In certain embodiments, after the switch from i), ii), iii) to I), II), when the HI effluent is fed substantially completely to the second reactor for hydrocracking, the operating conditions of the first reactor may be relaxed, and thus, the target yield and / or quality of the recovered fuel components may be achieved in the first reactor at a lower temperature and / or a higher WHSV, for example, than just before the switch. In these embodiments, it may be beneficial to increase the temperature of the second reactor to compensate for the typically increased WHSV after the switch. During the course of the second operating mode, one or more operating conditions of the first reactor and / or the second reactor may be (again) adjusted to compensate for further catalyst deactivation, particularly for deactivation of the HI catalyst in the first reactor.

[0060] If the process is operated in the switching mode, I), II) for a sufficiently long time and the operating conditions of the first reactor and / or the second reactor are optionally adjusted to their feasible limits, for example, with respect to the yield, and / or composition, and / or physicochemical properties of the recovered liquid transport fuel component, the target performance of the process can no longer be achieved due to the degree of catalyst deactivation. Thereafter, typically, before optionally starting the operation of the process in the first mode, i.e., executing the sequence i), ii), iii), the catalyst is either replaced with a new one or regenerated.

[0061] In certain embodiments, the process does not include adjustment of operating conditions to compensate for catalyst deactivation, i.e., is carried out without compensating for catalyst deactivation, and the deactivation of the HI catalyst in the first reactor is compensated by the switch from i), ii), iii) to I), II). In such embodiments, the total feasible operating time of the process may be shorter than in embodiments where, in addition to the switch from i), ii), iii) to I), II), at least the operating conditions of the first reactor are also adjusted.

[0062] A further variation of the process may include switching from I), II), III) to i), ii), iii) and then adjusting the operating conditions at least to compensate for the deactivation of the HI catalyst. Again, the operating conditions may be adjusted to their feasible limits and then switched from i), ii), iii) to I), II), or the operating conditions may be adjusted to some extent and switched from i), ii), iii) to I), II) already before reaching the limits.

[0063] An exemplary sequence for applying these variations involves operating the process in a first mode and adjusting the operating conditions up to the maximum practicable limit, then switching to a second mode and adjusting the operating conditions up to the maximum practicable limit, then switching again, i.e., from i), ii), iii) to i), ii), iii) and operating while adjusting the operating conditions until the target is no longer met, then switching from i), ii), iii) to I), II) and operating while adjusting the operating conditions until the target is no longer met (this leads to catalyst regeneration or replacement).

[0064] The first and second operating modes, in combination with appropriate temperatures and other operating conditions in the first and second reactions, provide the possibility of flexibly adjusting the process to meet and even optimize the target yields and / or qualities of the various recovered components.

[0065] In certain preferred embodiments of the present process, in step ii), a portion of the hydroisomerization effluent is fed as co-feed (as part of the second reactor feed) with the recycle stream to hydrocracking in the second reactor; and / or in step II), a portion of the hydroisomerization effluent is fed as co-feed with the hydrocracking effluent to fractionation. In these embodiments, the portion can be obtained, for example, by simply splitting all or the degassed HI effluent between the second reactor and fractionation using a fixed or preferably stepwise adjusted ratio. These embodiments provide additional flexibility in operating the process of the present invention and offer the possibility to more precisely tune the process in order to meet the target yields and qualities of multiple recovered components at once. By doing so, it may be possible to avoid situations where the target yield and quality of one recovered fuel component are met at the expense of an over-quality of another recovered fuel component (e.g., producing a diesel fuel component with an unnecessarily low cloud point). Splitting the HI effluent is also beneficial when switching the process from i), ii), iii) to I), II), providing a smooth transition between modes. For example, the switch from i), ii), iii) to I), II) starts from i), ii), iii), feeds a gradually decreasing portion of the HI effluent to fractionation, and simultaneously feeds a gradually increasing portion of the HI effluent as co-feed with the recycle stream (as part of the second reactor feed) to hydrocracking until essentially all (degassed) HI effluent is fed there, i.e., until the process is operated according to I), II).

[0066] In embodiments where a portion of the hydroisomerization effluent is fed as co-feed with the hydrocracking effluent to fractionation in step II), the amount of such portion of the HI effluent in step II) can vary, but generally is only a small portion (outside of the switch). Optionally for example, the portion of the HI effluent fed as co-feed with the hydrocracking effluent to fractionation in step II) can be less than 50 wt-%, preferably less than 30 wt-%, more preferably less than 10 wt-% of the HI effluent.

[0067] In this process, a parameter indicating the deactivation of HI catalyst A is monitored to receive a value, and in addition to the initiation of any switching, a comparison of that value with a predetermined value thereof can be used to select an appropriate adjustment for operating conditions in the first reactor and optionally further process units.

[0068] The parameter indicating the deactivation of HI catalyst A can be freely selected. Preferably, at least two of the parameters to be monitored belong to one or more of the following items a, b, c, d, e, f, g, h, and / or i. For example, two of the parameters can be selected from one of the items, and a further parameter can be selected from other items, or one of the parameters can be selected from one of the items, and at least two or more parameters can be selected from other items. Thus, in a preferred embodiment, the parameter indicating the deactivation of HI catalyst A includes at least two or more of the following: a. 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, especially deactivators of non-sulfided bifunctional HI catalysts containing noble metals. Also, said species or impurities are generally present in varying amounts in feeds originating from vegetable oils, animal fats, microbial oils, thermally and / or enzymatically liquefied organic wastes and residues, and feeds from the Fischer-Tropsch process, and therefore, in certain embodiments, are carried over in varying amounts into the paraffinic hydrocarbon feed and can be present therein. Typically, elemental impurities do not exist as such in the paraffinic hydrocarbon feed, but their content indicates the presence of compounds containing said impurities. Elemental impurities and coke-forming compounds are measured by standard laboratory analysis. An increase in the content of any of these impurities can lead to increased catalyst deactivation. b. The content of NH3 or H2S in the gas phase of the hydrotreated effluent A; in some cases, an increased content of NH3 and / or H2S in the gas phase of the hydroisomerization effluent may indicate an increased exposure of the catalyst to said impurities, and an increased amount of any of these impurities may lead to an increase in catalyst deactivation. c. At least one or more of the physicochemical properties of the hydroisomerization effluent, preferably the cloud point, freezing point, pour point, clogging point, kinematic viscosity, density, and / or distillation characteristics; an increase in any of the cloud point, freezing point, pour point, clogging point, kinematic viscosity, and / or density may indicate an increase in catalyst deactivation. Distillation characteristics that may indicate catalyst deactivation include T5, T50, FBP, etc. As further distillation characteristics, a shift in the boiling point distribution towards higher-boiling compounds may indicate catalyst deactivation in some cases. d. Composition characteristics of the hydroisomerization effluent, preferably at least one or more of the content of isoparaffins, the content of C8 - C14 hydrocarbons, the content of multi-branched isoparaffins, and / or the content of C1 - C4 hydrocarbons in the hydroisomerization effluent; a decrease in the content of isoparaffins, multi-branched isoparaffins, and / or C8 - C14 hydrocarbons may indicate an increase in catalyst deactivation. The content of C1 - C4 hydrocarbons may decrease together as the catalyst deactivation increases. However, increasing the operating temperature to compensate for catalyst deactivation may lead to an increase in the content of C1 - C4 hydrocarbons. e. The yield of at least one or more of the recovered liquid transportation fuel components and / or the separated recycle streams, preferably the yield of the aviation fuel component; an increase in the yield of higher-boiling hydrocarbons and an increase in the amount of the recovered recycle stream may indicate an increase in catalyst deactivation. f. At least one or more physicochemical properties of the recovered liquid transport fuel component and / or the separated recycle stream, preferably at least one or more of 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, an increase in, for example, T5, T50, T95, FBP, etc. may indicate catalyst deactivation. As further distillation characteristics, a shift in the boiling point distribution to higher boiling compounds may suggest catalyst deactivation. The physicochemical properties may to some extent indicate or correlate with the content of isoparaffins or multi-branched isoparaffins in the recovered liquid transport fuel component and / or the separated recycle stream. g. At least one or more compositional properties of the recovered liquid transport fuel component and / or the recycle stream, preferably the content of isoparaffins and / or the content of multi-branched isoparaffins in one or more of the recovered liquid transport fuel components and / or the separated recycle streams; A decrease in the content of isoparaffins, multi-branched isoparaffins, and C8-C14 hydrocarbons may indicate an increase in catalyst deactivation. The content of isoparaffins or multi-branched isoparaffins may to some extent indicate or correlate with the physicochemical properties of the recovered liquid transport fuel component and / or the separated recycle stream. h. The temperature difference in the first reactor or in one or more catalyst beds therein; said temperature difference can be monitored relatively easily, and a decrease in the temperature difference may indicate an increase in catalyst deactivation. Or i. The operating conditions in the first reactor selected from temperature, pressure, weight hourly space velocity (WHSV), H2 ratio to p-paraffin feed, and / or H2 partial pressure at the inlet of the first reactor. For example, temperature and / or WHSV and / or pressure may already need to be adjusted during the continuous operation of the process to compensate for the deactivation of the HI catalyst, so an increase in temperature, a decrease in WHSV, and / or an increase in pressure may indicate an increase in catalyst deactivation. Conveniently, the temperature in the reactor is measured at the inlet of the reactor.

[0069] The active sites of the HI catalyst can be occupied by impurities and coke, and the catalyst pores can be blocked, so that the sites are no longer available as a catalyst. For example, coke is caused by coke-forming compounds such as olefins, aromatics, and naphthenes, and coke formation can be promoted by additional impurities if additional impurities are present in the paraffinic hydrocarbon feed. For impurities that cause reversible catalyst deactivation, it may be sufficient to monitor the total content of such impurities or a plurality of impurities in the feed, since they can exhibit the expected catalyst deactivation. For other impurities, especially those that cause irreversible catalyst deactivation, it may be necessary to monitor the content of one or more impurities in the paraffinic hydrocarbon feed and calculate the cumulative amount of impurities encountered by the HI catalyst at a given point in time since the start of the run as the received value, and then compare the received value to a pre-determined value based on, for example, past data or a model based on past data, in order to reflect a HI catalyst deactivation that is so high that the target yield and / or quality of the desired fuel component can no longer be predicted.

[0070] In certain preferred embodiments, the process involves monitoring at least two, or at least three, of the above-described parameters indicative of deactivation of the HI catalyst. For example, good low-temperature properties of the HI effluent (e.g., cloud point, pour point, sub-zero viscosity) may be achieved due to an increase in the amount of short-chain carbons caused by an increase in cracking occurring in the first reactor, instead of a sufficient degree of isomerization. Thus, it may be beneficial to monitor at least two or three, or more, parameters in order to gain a better understanding of the state of deactivation of the HI catalyst. For example, one or more operating conditions in the first reactor, and one or more physicochemical properties and / or yields of the recovered liquid transportation fuel components are conveniently monitored and provide an improved understanding of the deactivation state of the HI catalyst. In one exemplary embodiment, the monitored parameters that may indicate deactivation of the HI catalyst include the temperature in the first reactor, and optionally the WHSV, and for the recovered diesel fuel component yield, at least one or more distillation properties, and / or cloud point, and for the recovered jet fuel component yield, at least one or more distillation properties, and / or freezing point.

[0071] Monitoring of the parameters indicative of deactivation of the HI catalyst can be carried out continuously, repeatedly, continuously, periodically, intermittently, discontinuously, or as a one-time monitoring. Monitoring of the parameters indicative of deactivation of the HI catalyst can be performed online, for example, using one or more sensors provided in any of the process stream, feed tank, and / or product tank, including a slipstream arrangement, or offline based on a sample taken from any of the process stream, feed tank, and / or product tank. The frequency and method of monitoring one or more parameters can be carried out independently of other monitored parameters, i.e., one parameter can be monitored continuously online, for example, and other parameters can be monitored periodically offline, for example.

[0072] A method of selecting the HI and hydrotreating conditions, preferably within the ranges of the HI conditions and hydrocracking conditions defined below, 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 it is well known to those skilled in the art to consider the selected hydrocracking (HC) catalyst, the composition of the second reactor feed, and the targeted effective degree of cracking, as well as the targeted content of isoparaffins in the effluent of the second reactor, 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 and / or second reactors, to some extent, catalyst aging or catalyst deactivation can also be considered. During continuous operation, for example, due to impurities or coking in the process stream, the HI catalyst and the HC catalyst gradually deactivate. When the catalyst deactivates, the catalyst activity decreases and the selectivity is affected, and at some point, the desired properties of the HI effluent, recycle effluent, hydrocracking effluent, recovered liquid transportation fuel components, and / or separated recycle streams cannot be achieved. When such a situation occurs, 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, can be adjusted, preferably within the operating condition ranges defined below, to compensate for the catalyst deactivation so that the desired properties of the HI effluent, recycle effluent, hydrocracking stream, recovered liquid transportation fuel components, and / or separated recycle streams can be reached again. Typically, this means increasing the temperature and / or decreasing the WHSV and / or adjusting the ratio of H2 to the paraffinic hydrocarbon feed 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 thermal cracking side reactions increase, the production of gaseous hydrocarbons increases, and thus the yield of the liquid product decreases.Therefore, typically, at the initial stage of operation, it is beneficial to start operating the low-temperature HI reactor (the first reactor) using, for example, the lowest temperature feasible within a specific range to provide the widest window for increasing the temperature under stepwise catalyst deactivation. Also, the HC catalyst typically deactivates gradually during continuous operation, albeit at a slower pace compared to the HI catalyst, and similar considerations apply to adjusting the operating conditions of Reactor B.

[0073] In certain preferred embodiments, the process includes separating a recycle stream from the fractionation and feeding the recycle stream as a co-feed to the first reactor together with the paraffinic hydrocarbon feed; and / or separating a side cut from the fractionation and feeding the side cut as a co-feed to the first reactor together with the paraffinic hydrocarbon feed; and / or feeding a portion of the paraffinic hydrocarbon feed to the second reaction, where the portion is obtained by dividing the paraffinic hydrocarbons between the first reactor and the second reactor. In addition to being able to adjust the operating conditions in the first reactor and / or the second reactor, these embodiments provide further improved flexibility for operating the process, including being able to adjust the process, for example, in response to variations in the properties of the paraffinic hydrocarbon feed, in response to the demand and / or quality of one or more recovered liquid transportation fuel components, and / or in response to the activity and / or selectivity of the HI and / or HC catalysts that change over their lifetimes.

[0074] The desired properties of the HI effluent, recycle effluent, hydrocracked effluent, recovered liquid transportation fuel component, and / or separated recycle stream include compositional and / or physicochemical properties such as, for example, wt-% of isoparaffin, wt-% of multi-branched isoparaffin, wt-% of hydrocarbons within a specific carbon number range, cloud point, freezing point, pour point, clogging point, kinematic viscosity, density, and / or distillation properties, among at least one or more thereof. The properties of the HI effluent, recycle effluent, hydrocracked effluent, recovered liquid transportation fuel component, and / or separated recycle stream can change during the operation of the process due to reasons other than just the deactivation of the HI and / or HC catalyst, such as changes in the paraffinic hydrocarbon feed composition. Therefore, one or more parameters indicating the deactivation of the HI and / or HC catalyst, and / or one or more parameters indicating the properties of the paraffinic hydrocarbon feed can be monitored to receive one or more values, and the received values can be compared with predetermined adjustment values. The predetermined adjustment values are typically closer to the initial process settings than the predetermined values used to trigger the switch from the first mode to the second mode.

[0075] Thus, in an embodiment, the process further includes monitoring at least one or more parameters indicative of deactivation of the HI catalyst to receive at least one or more values; and / or monitoring at least one or more parameters indicative of deactivation of the HC catalyst to receive at least one or more values; and / or monitoring at least one or more parameters indicative of the properties of the paraffinic hydrocarbon feed to receive at least one or more values; comparing the received values with predetermined setpoints, and based on said comparison, adjusting at least one or more operating conditions in the first reactor and / or the second reactor, and / or adjusting the composition of the paraffinic hydrocarbon feed and / or the second reactor feed, preferably, the temperature, pressure, and / or weight hourly space velocity (WHSV) in the first reactor and / or the second reactor, the H2 ratio to the paraffinic hydrocarbon feed, and / or the H2 ratio to the second reactor feed, and / or the H2 partial pressure at the inlet of the first reactor and / or the second reactor, the weight ratio in the second reactor feed of the separated recycle stream or optional additional recycle stream fed to the second reactor, the split ratio of the HI effluent between the second reactor and the fractionation, and / or the weight ratio in the feed to the first reactor of the separated side cut recycled to the process (fed to the first reactor), more preferably, increasing the temperature and / or pressure in the first reactor, and / or more preferably, 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, and / or adjusting the weight ratio of the separated recycle feed fed to the second reactor, and / or any additional recycle feed, and / or adjusting the split ratio of the HI effluent between the second reactor and the fractionation.

[0076] Adjustment of operating conditions to obtain or maintain desired properties of the HI effluent, recycle effluent, hydrocracked effluent, recovered liquid transport fuel components, and / or separated recycle streams can be performed, for example, based on past process data, models such as theoretical models or models based on past process data, and / or one or more parameters related to or indicative of one or more properties of the HI effluent A, recycle effluent, hydrocracked effluent, recovered liquid transport fuel components, and / or separated recycle streams. For example, the adjustment can be performed using similar qualitative and quantitative predictions for similar supplied and recovered liquid transport fuel components, for example using models and / or operating condition profiles based on past process data from previous processes performed based on past process data.

[0077] In this process, the paraffinic hydrocarbons subjected to hydroisomerization in the first reactor contain at least 60 wt-% paraffin, based on the total weight of the paraffinic hydrocarbon feed, and of this paraffin, at most 30 wt-% is isoparaffin. This means that when the paraffinic hydrocarbon feed contains 60 wt-% paraffin, based on the total weight of the paraffinic hydrocarbon feed, at most 30 wt-% of the total weight of the paraffin in the paraffinic feed, i.e., at most 18 wt-% of the total weight of the paraffinic hydrocarbon feed, is isoparaffin. 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-% paraffin, based on the total weight of the paraffinic hydrocarbon feed. The paraffinic hydrocarbon feed of the present disclosure may contain at least 95 wt-% paraffin, based on the total weight of the paraffinic hydrocarbon feed, or may consist essentially of paraffin. 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 also contain small amounts of aromatics and / or naphthenes.

[0078] The advantage of using a highly paraffinic hydrocarbon feed in this process is 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.

[0079] Preferably, at most 25 wt-%, more preferably at most 20 wt-%, and still more preferably at most 15 wt-% of the paraffins in the paraffinic hydrocarbon feed of the present disclosure are isoparaffin. 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 may be isoparaffin.

[0080] A high weight ratio of n-paraffin to isoparaffin in a paraffinic hydrocarbon feed (wt-%:wt-%) can contribute to the suppression of cracking side reactions during HI in the first reactor because n-paraffin tends to be more resistant to cracking compared to isoparaffin with the same number of carbon atoms. However, the presence of a certain amount of isoparaffin in the paraffinic hydrocarbon feed is still beneficial. A hydrocarbon feed containing a certain amount of isoparaffin can result in an HI effluent containing more multi-branched isoparaffin compared to a similar feed without isoparaffin.

[0081] Preferably, the paraffinic hydrocarbon feed of the present disclosure contains 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-%, and even more preferably at least 95 wt-%, based on the total weight of the paraffinic hydrocarbon feed. In a particularly preferred embodiment, the paraffinic hydrocarbon feed contains 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-%, and even more preferably at least 95 wt-%, based on the total weight of the paraffinic hydrocarbon feed. A paraffinic hydrocarbon feed rich in C12 to C30 hydrocarbons is preferred because it enables good yields of various types of two or more liquid transportation fuel components. C14 to C22 hydrocarbons are particularly preferred for the same reason and also because they are readily available from conventional HDO of vegetable oils, animal fats, and / or microbial oils, for example, containing fatty acids.

[0082] 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. This type of composition can be achieved by appropriately selecting the heavier paraffinic hydrocarbon feeds from which they are produced, in particular by appropriately selecting feedstocks such as oxygen-containing hydrocarbons. Examples of suitable heavy oxygen-containing 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.

[0083] The paraffinic hydrocarbon feed can include any suitable paraffinic hydrocarbon composition or combinations thereof. Preferably, in this process, the step of providing the paraffinic hydrocarbon feed is the step of subjecting a hydrotreating feed to catalytic hydrotreating to obtain a paraffinic hydrotreated effluent, preferably the step of subjecting an oxygen-containing hydrocarbon feed to catalytic hydrodeoxygenation, wherein the hydrotreating feed preferably includes 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 syngas to Fischer-Tropsch conversion to obtain a paraffinic FT effluent; the step of subjecting the paraffinic hydrotreated effluent and / or the paraffinic FT effluent to gas-liquid separation, optionally paraffinic feed fractionation, to provide the paraffinic hydrocarbon feed. Gas-liquid separation means removing compounds that are gaseous at least at NTP.

[0084] 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.

[0085] In one embodiment, the paraffinic hydrocarbon feed comprises, consists essentially of, or consists of a de-aerated 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 mainly n-paraffins having a wide carbon chain length distribution, e.g., C2 - C100+, typically about C5 - about C50. The FT effluent is typically highly paraffinic, containing mainly 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.

[0086] 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 oils, animal fats, microbial oils, thermally liquefied organic wastes and residues, and / or enzymatically liquefied organic wastes and residues, more preferably at least one or more of vegetable, animal fats, and / or microbial oils, 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 de-aerated paraffinic hydrotreating effluent or a fraction thereof, and comprises, consists essentially of, or consists of a de-aerated paraffinic hydrotreating effluent or a fraction thereof.

[0087] The term "catalytic hydrotreatment" is often also referred to as "hydroprocessing", which means a catalytic process of 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 chlorine compounds as hydrochloric acid (HCl), hydrodechlorination (HDCl), and / or removes metals by hydrodemetallization, 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.

[0088] Preferably, the paraffinic hydrocarbon feed of the present disclosure is obtained by catalytic hydrodeoxygenation (HDO) of an oxygen-containing hydrocarbon feed containing at least one or more of vegetable oil, animal fat and / or microbial oil, in particular, 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 HDO effluent or a fraction thereof, and contains or consists essentially of a degassed HDO effluent or a fraction thereof. Nitrogen impurities are generally present in various amounts in the oxygen-containing hydrocarbon feed containing vegetable oil, animal fat and / or microbial oil, and are carried over and may be present in various amounts in the degassed HDO effluent or a fraction thereof.

[0089] 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 hydrodeoxygenation effluent, and subjecting the hydrodeoxygenation effluent to gas-liquid separation and optionally paraffinic feed fractionation to obtain a degassed hydrodeoxygenation effluent or a fraction thereof as the hydrocarbon feed, where 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 / 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. 129220.

[0090] 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.

[0091] 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 at least one or more of Ni and / or Co and Mo and / or W, such as at least one or more of NiMo, CoMo, NiCoMo, NiW, NiMoW, etc. 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 for hydrodeoxygenation as a hydrodeoxygenation catalyst or as a cocatalyst, an HDO effluent having a somewhat high isoparaffin content can be obtained.

[0092] In certain embodiments, the paraffinic hydrocarbon feed may include a side cut separated in the fractionation of this process. The side cut is preferably included in the paraffinic hydrocarbon feed as a minor component. The side cut is preferably a fraction rich in C14 - 18 hydrocarbons, more preferably a fraction rich in C15 - C17 hydrocarbons. The side cut is preferably a relatively narrow fraction to enable accurate correction of the boiling point distribution of the total feed to fractionation. Incorporating such a side cut into the paraffinic hydrocarbon feed may improve the quality of the recovered liquid transportation fuel component or at least a part of the recovered liquid transportation fuel component, particularly the quality of the aviation fuel component. Since the side cut is separated after HI and hydrocracking, it usually has a high isoparaffin content. Thus, when a side cut is included in the paraffinic hydrocarbon feed, the isoparaffin content of the paraffinic hydrocarbon feed may increase to some extent, preferably up to a maximum of 30 wt-% relative to the total weight of the paraffins in the paraffinic hydrocarbon feed. The HI in the first reactor, the hydrocracking in the second reactor, and the optionally performed HDO and / or hydrodearomatization (HDA) processes may have an impurity removal effect on the treated stream, especially when followed by gas-liquid separation. By adding even a small amount of a side cut containing at most a very small amount of impurities to the paraffinic hydrocarbon feed, the impurity content of the paraffinic hydrocarbon feed can be reduced or diluted, and the deactivation of the HI catalyst can be retarded.

[0093] In this process, the paraffinic hydrocarbon feed is subjected to hydroisomerization (HI) 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.

[0094] Preferably, the hydrogen isomerization 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 in the range of 0.1 to 10, preferably 0.2 to 8, more preferably 0.4 to 6 kg of paraffinic hydrocarbon feed / kg catalyst / hour, and a ratio of H2 to paraffinic hydrocarbon feed in the range of 10 to 2000, preferably 50 to 1000 normal liters of H2 / paraffin hydrocarbon feed.

[0095] 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 of paraffinic hydrocarbon feed / 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.

[0096] In a particularly preferred embodiment, the hydrogen isomerization in the first reactor is carried out at a temperature in the range of 230°C to 500°C, a pressure in the range of 2 to 8 MPa, an H2 partial pressure at the first reactor inlet in the range of 2 to 8 MPa, a weight hourly space velocity of paraffinic hydrocarbon feed in the range of 0.2 to 8 kg of paraffinic hydrocarbon feed / 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.

[0097] 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 lower pressures, and / or higher WHSV. As the life of the HI catalyst approaches its end, higher temperatures, and / or higher 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 wt-% to 95 wt-% and a multi-branched i-paraffin content in the range of 25 wt-% 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 low severity, or moderate severity, or high severity of HI, respectively, but these content ranges are only for illustrative purposes of the order of magnitude, may overlap to some extent, and may vary depending on the case.

[0098] 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 each HI effluent to the wt-% amount of isoparaffin based on the total weight of paraffins in the paraffinic hydrocarbon feed 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 branched isoparaffin based on the total weight of paraffins in each hydrotreated effluent to the wt-% amount of multi-branched isoparaffin based on the total weight of paraffins in the paraffinic hydrocarbon feed 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 (total) HI effluent 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 especially when operating the first reactor within the HI operating conditions and / or when using the HI catalyst and / or paraffinic hydrocarbon feed defined herein.

[0099] The HI effluent is preferably subjected to gas-liquid separation, i.e., removal of compounds that are gaseous at least at NTP. This can be done, for example, as an integral step within the first reactor or as part of a separation in step i) when operating the process in the first mode, before leading to step i) or I).

[0100] When operating this step in the second mode, there is no need to gas-liquid separate the HI effluent, and in certain embodiments, substantially the entire HI effluent can be fed to the second reactor. By omitting the gas-liquid separation of the HI effluent, the investment cost and operating cost can be reduced, and the energy efficiency can also be improved.

[0101] However, preferably, the HI effluent is subjected to gas-liquid separation as part of the fractional distillation in step i) or I), or when the process is operated in the first mode, before being led to step i) or I). More preferably, the HI effluent is subjected to gas-liquid separation at least before being led to step I). Degassing removes, for example, gaseous impurities from the HI effluent and increases the hydrogen partial pressure in the second reactor feed. Further, when the reactor feed is less non-uniform, it becomes easier to optimize the operating conditions in the second reactor.

[0102] 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-% paraffin, based on the total weight of the HI effluent. In certain embodiments, the HI effluent may consist essentially of paraffin.

[0103] Typically, based on the total weight of paraffin in the HI effluent, it may contain at least 50 wt-%, preferably at least 60 wt-%, more preferably at least 70 wt-%, even more preferably at least 80 wt-% isoparaffin, and optionally, based on the total weight of paraffin 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-% multi-branched isoparaffin. Typically, when the hydrotreating in reactor A and / or B is hydroisomerization, the HI effluent may contain 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-% multi-branched isoparaffin, based on the total weight of paraffin in the HI effluent. Typically, the HI liquid may have a cloud point (ASTM D5771-17) below 0 °C, preferably below -5 °C, more preferably below -8 °C, even more preferably below -10 °C, or below -15 °C.

[0104] The presence of multi-branched isoparaffins in the HI effluent is considered beneficial as it can beneficially contribute to the extent of effective 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 transport fuels, in particular the low-temperature properties of the aviation fuel components and / or diesel fuel components, and / or the RON of the gasoline fuel components. Without being bound by any theory, multi-branched isoparaffins are likely to form two branched paraffin molecules upon cracking in the hydrotreating in the subsequent reactor, instead of one branch and one n-paraffin, and thus are considered to increase the isoparaffin content of the second hydrotreating effluent obtained.

[0105] When operating in the first mode, the process involves subjecting the HI effluent to fractional distillation to separate a recycle stream having a T5 temperature (recovery rate 5 vol%, EN ISO 3405 - 2019) of at least 270 °C or higher from the HI effluent. The total feed subjected to fractional distillation in the first mode is initially the HI effluent, optionally after being integrally subjected to gas-liquid separation in the first reactor, and as the process continues to operate, the total feed subjected to fractional distillation includes the HI effluent and the recycle effluent, and the effluents can preferably be combined.

[0106] 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 to the fractional distillation, i.e., the recycle stream may contain the heavy bottoms of the total feed to the fractional distillation.

[0107] Preferably, the recycle stream has a T5 temperature of 275 °C or higher. In a preferred embodiment, 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 overall feed to the fractional distillation, i.e., the recycle stream may contain the heavy bottoms of the total feed to the fractional distillation.

[0108] The T5 temperature of the recycle stream is preferably, when present, selected such that at least a portion of the C16 n-paraffins present in the total feed to the fractional distillation, such as the C16 n-paraffins present in the HI effluent, are recovered in the recycle stream. Recovering C16 n-paraffins in the recycle stream can be achieved by appropriately selecting the T5 temperature and / or IBP of the recycle stream. The boiling point of C16 n-paraffin is 287 °C (at atmospheric pressure), but fractional distillation, such as distillation separation, is not completely sharp, so C16 n-paraffin can be recovered over a temperature range near its boiling point. Preferably, the recycle stream contains C16 n-paraffin.

[0109] 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 reaction for hydrocracking. Thus, for example, the presence of any significant amount of C16 n-paraffins in the recovered aviation fuel component results in poor low-temperature properties, particularly a poor pour point, and / or a poor kinematic viscosity below the freezing point, such as -20 °C or -40 °C, which may even prevent the aviation fuel component from being used in an aviation fuel composition. In any case, the C16 n-paraffins in the recovered aviation fuel component have impaired low-temperature properties compared to an aviation fuel component having a low or no C16 n-paraffin content, i.e., one or more of the cloud point, pour point, freezing point, low-temperature plugging point, and / or kinematic viscosity below the freezing point are increased. Preferably, the recycle stream contains at least 20 wt-% or at least 30 wt-% of the C16 n-paraffins in the total feed to the fractionation, more preferably at least 40 wt-% or at least 50 wt-%. The amount of n-paraffins containing C16 n-paraffins in the total feed to the fractionation can be increased by HI catalyst deactivation and can also be formed by cracking in the second reactor.

[0110] In a particularly preferred embodiment, the recycle stream contains at least 85 wt-%, preferably at least 90 wt-%, more preferably at least 95 wt-% of C16+ paraffins based on the total weight of the paraffins in the recycle stream. Subjecting C16+ paraffins to hydrocracking in the second reaction is beneficial in that it can increase the yield of the aviation fuel component and / or improve the quality. C16+ n-paraffins have poor low-temperature properties, and C18+ n-paraffins generally boil outside the aviation fuel boiling range.

[0111] Typically, the recycle stream 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, based on the total weight of the recycle stream, or the recycle stream can consist essentially of paraffin. In a particularly preferred embodiment, the recycle stream contains at least 50 wt-%, preferably at least 60 wt-%, more preferably at least 70 wt-%, or at least 80 wt-%, and / or up to 100 wt-% or up to 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-% multi-branched isoparaffin, based on the total weight of the paraffin in the recycle stream. Typically, the recycle stream contains up to 95 wt-%, or up to 90 wt-%, or up to 80 wt-%, or up to 70 wt-%, for example up to 60 wt-%, or up to 50 wt-%, or up to 40 wt-%, in some cases up to 30 wt-%, or even up to 20 wt-% multi-branched isoparaffin, based on the total weight of the paraffin in the recycle stream. Typically, the recycle stream contains multi-branched isoparaffin 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-%, based on the total weight of the paraffin in the recycle stream. Typically, the recycle stream has a cloud point of less than 0 °C, preferably less than -5 °C, more preferably less than -10 °C, even more preferably less than -20 °C, even more preferably less than -30 °C (ASTM D5771-17).

[0112] Generally, paraffins tend to be more easily cracked and isomerized than cyclic hydrocarbons, and longer-chain paraffins tend to crack more than shorter-chain paraffins and isoparaffins tend to crack more than n-paraffins, and since the relative uniformity of the recycle stream composition can make it easier to optimize the hydrocracking conditions in the second reactor, this type of recycle stream has a beneficial composition from the perspective of efficient cracking in hydrocracking and / or the degree of isomerization to form hydrocarbons boiling in the aviation fuel range and in the gasoline boiling range. Further, these embodiments facilitate easy separation by simple splitting of, for example, several examples of components that can be separated from the recycle stream, such as diesel fuel components, marine fuel components, base oil components, and / or transformer oil components.

[0113] The process can also include, in step II), recovering a further recycle stream from the fractionation having a T5 temperature (recovery rate 5 vol%, EN ISO 3405-2019) of 270 °C or higher, and feeding the recovered further recycle stream to the second reactor as a co-feed with the HI effluent, i.e., as part of the second reactor feed. In this case, the second reactor feed consists of the combination of the HI effluent and the recovered further recycle stream. The further recycle stream is preferably a recycle stream as defined above. Preferably, the further recycle stream consists of C16 n-paraffins.

[0114] In certain preferred embodiments, the second reactor feed consists essentially of at least a portion of the recycle stream and / or the hydrogen isomerization effluent and / or any optional additional recycle stream. For example, in step i), the second reactor feed may consist essentially of the recycle stream, or a portion of the recycle stream and the HI effluent, and / or in step II), the second reactor feed may consist essentially of the HI effluent and optionally an additional recycle stream, or at least a portion of the HI effluent and optionally an additional recycle stream.

[0115] In embodiments where the second reactor feed comprises a portion of the HI effluent in step i), the amount of such portion can vary but is generally a minor portion (outside of the switch). For example, in step i), the second reactor feed may optionally contain, preferably in a degassed state, less than 50 wt-%, preferably less than 30 wt-%, more preferably less than 10 wt-% of the HI effluent, based on the total weight of the second reactor feed. The process includes, in step ii), subjecting the second reactor feed comprising the recycle stream to hydrocracking in the second reactor in the presence of an HC catalyst to obtain a recycle effluent, and in step II), subjecting the second reactor feed comprising the HI effluent to hydrocracking in the second reactor in the presence of an HC catalyst to obtain a hydrocracking effluent.

[0116] 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.

[0117] In certain preferred embodiments, 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, 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 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 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 in the range of 0.1 kg to 10 kg / kg catalyst / hour, 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.

[0118] According to one 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 second reactor feed / kg 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 certain preferred embodiments, 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 to 7 MPa, a weight hourly space velocity in the range of 0.4 to 6 kg second reactor feed / kg 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. Operating the HC at a sufficiently low temperature and a sufficiently high pressure better suppresses the aromatization side reaction or promotes dearomatization.

[0119] Preferably, in the hydrocracking in the second reactor, the ratio of the wt-% amount of isoparaffin to the total weight of paraffin in the hydrocracked effluent (process I)) and / or the recycle effluent (process II)) 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 with respect 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 hydrocracked effluent (process I)) or the recycle effluent (process II)) 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.

[0120] 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 total hydrocarbon cracking effluent (step I)) in the second reactor to the wt-% amount 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 (step ii)) or (total) hydrocracking effluent (step I)) consists of C1-C4 hydrocarbons that are each less than 20 wt-%, or less than 10 wt-%, or less than 5 wt-% based on the total weight of the recycle effluent or hydrocracking effluent.

[0121] These can be achieved especially when using the second reactor feed defined above 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 Group VIII noble metal, more preferably Pt and / or Pd.

[0122] Typically, the hydrocracking effluent (step I)) and / or the recycle effluent (step ii)) each 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-% paraffin based on the total weight of the hydrocracking effluent or recycle effluent. The hydrocracking effluent (step I)) and / or the recycle effluent (step ii)) can even consist essentially of paraffin.

[0123] According to certain preferred embodiments, the hydrocracking effluent (Process I)) and / or the recycle effluent (Process 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, based on the total weight of paraffins in the hydrocracking effluent or recycle effluent, and / or contains at least 3 wt-%, or at least 5 wt-%, or at least 10 wt-%, or at least 15 wt-%, or at least 20 wt-% multi-branched isoparaffin, based on the total weight of paraffins in the hydrocracking effluent or recycle effluent, respectively. 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 given point in time including 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.

[0124] By operating the first reactor and the second reactor within the operating condition ranges defined above, in particular 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 cracking 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, it is possible to achieve the desired degree of effective cracking under milder operating conditions, in particular at low temperatures, thereby improving the yields of hydrocarbons in the aviation fuel and gasoline boiling ranges without excessive thermal cracking leading to gas formation.

[0125] 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 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. The bifunctional HI catalyst and the HC catalyst include a metal site for catalyzing a (de)hydrogenation reaction and an acid site for catalyzing an isomerization reaction and a cracking reaction. 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 provides a synergistic effect between the metal site and the acid site. The bifunctional HI and HC catalysts are also beneficial in that the molecular access and diffusion to the catalyst sites can be controlled by appropriately selecting the porous properties of the catalyst, particularly the pore size, pore dimension, and / or interconnectedness of the pores of the catalyst.

[0126] 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 Pt and / or Pd, and at least one or more acidic porous materials, and wherein the p-paraffin 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.

[0127] The sulfur content can be determined in accordance with ISO 20846-2019 for liquids and ASTM-D6667 for gaseous fractions.

[0128] 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 does not require the inefficient separation and recovery of H2S from various process streams, and is thus preferred. In particular, a non-sulfided bifunctional catalyst containing a noble metal can be active at a lower temperature and can exhibit higher selectivity for the isomerization reaction compared to a sulfided catalyst, but is susceptible to deactivation by H2S.

[0129] Preferably, each paraffinic hydrocarbon feed contains sulfur 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) as measured according to ISO 20846-2019.

[0130] 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 does not exist in the HI effluent. In such an embodiment, the gas-liquid separation of the HI effluent before feeding it to the second reactor for hydrocracking (step I)) is not necessary to protect the HC catalyst in the second reactor, but nevertheless, the gas-liquid separation of the HI effluent can be optionally carried out. Thus, the overall process is more simplified and a liquid transportation fuel component with an ultra-low sulfur content can be obtained. Furthermore, since there is less H2S present, less corrosion is expected in the long term, and for some of the equipment materials, even less stringent corrosion resistance requirements may apply. 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.

[0131] The bifunctional HC catalyst and the bifunctional HI catalyst are similar in that they include a metal site capable of catalyzing the (de)hydrogenation of the corresponding n / i-olefin from n / i-paraffin, and an acid site capable of catalyzing the protonation of n / i-olefin to n / i-carbenium ion, the isomerization of n-carbenium ion and further i-carbenium ion, and / or the decomposition of n / i-carbenium ion to lighter n / i-olefin and lighter n / i-carbenium ion, and the deprotonation of n / i-carbenium ion 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 influenced 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.

[0132] 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 is thus preferred. The high activity at a lower temperature provides a wider temperature range in 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.

[0133] Preferably, the bifunctional HI and HC catalysts each independently comprise at least one or more porous acidic materials having a microporous, mesoporous, or hierarchical (micro-mesoporous) structure. Various zeolite-type materials such as SAPO and zeolites are available, which provide the desired acidity and porous properties.

[0134] 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 being 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, comprising the foregoing.

[0135] 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 zeolites 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.

[0136] In particular, for the hydrocracking reaction in the second reactor of the present process, bifunctional HI catalysts are 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. At low temperatures, the thermodynamic equilibrium tends to shift towards dearomatization, thus reducing aromatic formation due to side reactions. By feeding a bifunctional HC catalyst to the second reactor, the isoparaffin content (weight ratio wt-% of isoparaffin to the total weight of paraffins) in the recycle effluent and / or the hydrocracked effluent does not necessarily have to be significantly lower than that of the HI effluent and can be the same or higher.

[0137] Therefore, in one embodiment, the hydrocracking catalyst is a bifunctional hydrocracking catalyst, preferably a non-sulfided bifunctional hydrocracking catalyst, as follows selected from Group VIII of the periodic table, preferably from Group VIII Mo, Co, and / or W, preferably from Ni, Mo, Co, W, Pt, and / or Pd, more preferably from 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 an acidic porous material such as 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 Selected from bifunctional hydroisomerization catalysts, preferably non-sulfided bifunctional hydroisomerization catalysts, containing the same. In one embodiment, the HI catalyst of the first reactor, the HI catalyst of 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, for example, adsorption-desorption methods such as the liberation of an adsorbed basic substance such as ammonia or pyridine at high temperature indicating 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 performed according to the procedure described therein 1 by the 1H-NMR method. In one embodiment, the bifunctional HC catalyst of the second reactor has a higher number of Bronsted acid sites compared to the bifunctional HI catalyst of the first reactor, as determined by NH3-TPD. In one embodiment, the bifunctional HC catalyst has a higher total number of acid sites compared to the bifunctional HI catalyst, as determined by NH3-TPD.

[0138] 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 even 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 metals as compared to the bifunctional HI catalyst.

[0139] If one of the HI catalyst of the first reactor and the HC catalyst of the second reactor deactivates earlier than the other, the need to replace the catalyst with a new one or to regenerate the catalyst can be determined based on the catalyst that deactivates earlier.

[0140] In this process, a paraffinic hydrocarbon feed is subjected to HI in the presence of an HI catalyst, and the recycle stream and the hydroisomerization effluent are 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 differ 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 or the HI effluent is contacted with the HC catalyst under hydrocracking conditions, more cracking is expected as compared to when the paraffinic hydrocarbon feed is contacted with the HI catalyst under HI conditions, even if the catalysts are 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 cracking, and when the recycle stream or the HI effluent is contacted with the HC catalyst under hydrocracking conditions, cracking of this feed is more dominant than isomerization.

[0141] Acid site Acid site 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 performed before or during startup to adjust properties such as selectivity and / or activity, and they may be treated by any conventional method. In this specification, a hydrotreated HI catalyst, an HC catalyst, a fresh catalyst, and a regenerated catalyst generally mean catalysts in a usable state.

[0142] In certain embodiments, following hydrocracking, further hydroisomerization is carried out in the presence of an additional HI catalyst. The additional HI can be achieved, for example, by placing an additional HI catalyst in at least one separate bed in a second reactor. 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 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.

[0143] The process may include hydrodearomatization (HDA) of one or more process streams or products. In certain embodiments, the process includes feeding at least one or more of the HI effluent, the hydrocracking effluent, the recycle effluent, the recycle stream, the recovered liquid transportation fuel component, and / or any fraction thereof to an HDA reactor, and performing hydrodearomatization in the HDA reactor in the presence of an HDA catalyst to reduce the level of aromatic hydrocarbons to, for example, less than 5000 w-ppm, or less than 300 w-ppm, preferably less than 100 w-ppm, or less than 50 w-ppm (preferably as determined according to UOP 495-03).

[0144] The HDA step may be beneficial particularly when the paraffinic hydrocarbon feed supplied to the first reactor contains a high concentration of aromatics and / or when the HI in the first reactor and / or the hydrocracking in the second reactor is operated using a catalyst and / or conditions that promote the formation of aromatics as a side reaction, or when an ultra-low aromatic content is desired for all or part of the recovered liquid transportation fuel component or for other product fractions that may be recovered from the process. Examples of such other product fractions include product fractions intended for use in cosmetics, pharmaceuticals, and / or other applications involving close contact with humans.

[0145] HDA is preferably carried out at a temperature in the range of 80°C to 350°C, a pressure in the range of 3 MPa to 16 MPa, a liquid hourly space velocity in the range of 0.2 to 8 hr-1, and a normal liter ratio of H(2) to the HDA reactor feed in the range of 50 to 2000 per liter of HDA reactor feed.

[0146] HDA can be carried out using any catalyst conventionally used for hydrodearomatization. Preferably, a non-sulfided catalyst composed of a noble metal is used. A catalyst composed of a noble metal is already active in HDA at low temperatures, which is beneficial because the thermodynamic equilibrium tends to shift towards dearomatization at low temperatures. Further, in embodiments where the first reactor and the second reactor are also operated using a non-sulfided noble metal catalyst, there is no need to add sulfur to maintain the activity of the catalyst, and little or no effort is required to separate sulfur-containing compounds, particularly H2S, from the gas fraction of the effluent of the first reactor, the second reactor, and / or the had reactor. The recovered liquid transport fuel component(s) and any optional other product fraction are obtained with both ultra-low aromatic and sulfur contents. The process includes fractionation in which at least one or more liquid transport fuel components are recovered and recycle streams (and optionally additional recycle streams) can be separated. The amount of recycle stream separated, the amount of separated recycle stream, and the amount of recycle stream fed to the second reactor can vary within a wide range. For example, additional liquid streams or cuts such as sidecuts can optionally be separated and / or recovered from the fractionation and optionally recycled to the process.

[0147] Preferably, in step iii), the weight ratio of the recycle effluent to the HI effluent, which is subjected to fractionation in step iii), is 1:10 to 10:1, for example 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 is preferably a ratio towards the lower limit when treating a paraffinic hydrocarbon feed that boils at a low temperature, and a ratio towards the upper limit when treating a paraffinic hydrocarbon feed that boils at a high temperature, for example a feed containing paraffins heavier than C18.

[0148] The fractionation of the process can be constituted by any fractionation technique conventionally used. Preferably, the fractionation includes distillation such as atmospheric distillation or vacuum distillation, and optionally. Before fractionation, gas-liquid separation may be carried out, for example, as described below.

[0149] 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 transportation 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.

[0150] As described above, in the first mode, the recycle effluent and / or the HI effluent can be subjected to gas-liquid separation, either combined or independently of each other. Similarly, in the second mode, the hydrocracking effluent and / or the HI effluent can be subjected to gas-liquid separation. The gas-liquid separation can be carried out, for example, as an integral step 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.

[0151] According to certain embodiments of the present process, different products can be recovered from the fractionation as liquid transportation 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.

[0152] Liquid transport fuel components and any further products separated and / or recovered from the fractionation may include, for example, gasoline fuel components boiling in the range of about 25°C to about 200°C, aviation fuel components boiling in the range of about 100°C to about 300°C, such as in the range of about 150°C to about 300°C, a recycle stream having a T5 temperature of at least 270°C, diesel fuel components boiling in the range of about 160°C to about 380°C, and / or marine fuel components boiling 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 boiling in the range of about 25°C to about 200°C, aviation fuel components boiling 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 a recycle stream having a T5 temperature of at least 270°C are first recovered and / or separated from the fractionation, and then diesel fuel components boiling in the range of about 160°C to about 380°C, and / or marine fuel components boiling 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. Further products may be split or further separated from the fractionation, for example from the recycle stream, and recovered. Examples of such further products include solvents, electro-technical fluids, and components of base oils.

[0153] The present process enables the production of a low-viscosity aviation fuel component 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 the present process, and having similar IBP and FBP.

[0154] Thus, in a preferred embodiment of the present process, in steps iii) and III), at least one of the liquid transport fuel components recovered from the 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), which 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 into 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.

[0155] 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 certain preferred embodiments 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 thought to be due to the high content of C8 - C14 hydrocarbons and isoparaffins in the separately provided feed, a significant proportion of which are multi-branched isoparaffins. In certain preferred embodiments, the aviation fuel components have a difference between the T90 temperature and the T10 temperature determined in accordance with 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 for 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 a high degree of isomerization, particularly a high multi-branched i-paraffin content, and the amount of carbon atoms can be more evenly distributed, particularly in the range of C6 - C18.

[0156] Typically, in this process, in steps iii) and III), 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, or at least the aviation fuel component and the gasoline fuel component, 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.

[0157] In a preferred embodiment, the recovered liquid transport fuel components have a bio-based 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 bio-based carbon content in the recovered liquid transport fuel components is mainly affected by the bio-based carbon content in the paraffinic hydrocarbon feed and, in a preferred embodiment, by the oxygen-containing hydrocarbon feed subjected to HDO. However, the amount of a fossil hydrocarbon diluent, etc., supplied to the HDO reactor may affect the bio-based carbon content of the recovered liquid transport fuel components.

[0158] 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-%, even 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-%, even 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-%, even 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.

[0159] In this process, even if each of the gasoline fuel component, the aviation fuel component, and the diesel fuel component can be recovered simultaneously, they are recovered as moderately wide fractions. When optimizing the yield of the aviation fuel component, the diesel fuel component may be recovered as a narrower cut or not recovered at all.

[0160] The products recovered from this manufacturing method have excellent properties. The recovered liquid transportation fuel component is suitable for use as a blend component in a fuel composition and, when appropriately added, can be used as fuel as is, i.e., as an unblended component. The recovered liquid transportation fuel component, 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 operating oil, gear oil, transmission oil, degreasing composition, penetrating oil, rust preventive composition, multi-purpose oil, metalworking oil, rolling oil, especially for aluminum, cutting oil, drilling oil, in 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, hydrophobizing compositions, in agriculture, crop protection liquids, in construction, concrete release agents, in electronic devices, in medical devices, in 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 in a wide range of applications, especially those involving spraying, injection, and / or miscibility with other components.

[0161] Schematic of the process Figure 1 schematically shows a process according to an exemplary embodiment of a mode that is executed according to the exemplary embodiments of i), ii), iii) before switching from i), ii), iii) to I), II), III). In Figure 1, the oxygen-containing hydrocarbon feed 110 is supplied to the HDO reactor 120, where it is hydrodeoxygenated in the presence of the HDO catalyst 130 to obtain a hydrodeoxygenation 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 the 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 the first reactor 180, where the degassed HDO effluent 170 is subjected to hydroisomerization in the presence of the 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 the 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 the 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 the second reactor 290 in Figure 1, where hydrocracking is performed in the presence of the 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 the 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 fractional distillation together with the degassed HI effluent 230.In one embodiment, a portion of the HI effluents 200, 230 can be supplied as a co-feed 500 together with the recycle stream 280 for hydrocracking in the second reactor 290.

[0162] 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, when operated in the first mode, the monitored parameters indicating deactivation of the HI catalyst include two or more of the following: 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 one or more distillation characteristics of the aviation fuel component 260, and the corresponding received values of these are compared to predetermined values. When the monitored parameter is, for example, the temperature monitored at the inlet of the first reactor 180, the predetermined value is, for example, up to 450 °C; the predetermined value for the WHSV of the first reactor 180 is, for example, 6 kg of hydrocarbon feed / kg catalyst / hour; 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 D5771-2017); 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). When the received value of the monitored parameter reaches the corresponding predetermined value, the process switches to the second mode and is executed. After the switch, the monitored parameter and the predetermined value may be the same as in the first mode, or 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.

[0163] Figure 2 schematically shows a process according to an exemplary embodiment, after switching from i), ii), iii) to I), II), i.e., during execution according to the exemplary embodiments of I), II). In Figure 2, the oxygenated hydrocarbon feed 110 is supplied to the HDO reactor 120, where it is hydrodeoxygenated in the presence of the HDO catalyst 130 to obtain a hydrodeoxygenation effluent (HDO effluent) 140. The obtained HDO effluent 140 is subjected to gas-liquid separation 150 to separate at least the compounds that are gaseous at NTP 160 from the HDO effluent, obtaining 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 in Figure 2 to the first reactor 180, where the degassed HDO effluent 170 is subjected to hydroisomerization in the presence of the HI catalyst 190 to obtain an HI effluent 200. The obtained HI effluent 200 is subjected to gas-liquid separation 210 to separate at least the compounds that are gaseous at NTP 220 from the HI effluent 200, obtaining a degassed HI effluent 230. In Figure 2, the degassed HI effluent 230 is supplied to the second reactor 290, where it is subjected to hydrocracking in the presence of the HC catalyst 300 to obtain a hydrocracking effluent 350. The hydrocracking effluent 350 is subjected to gas-liquid separation 360 to separate at least the compounds that are gaseous at NTP 370 from the hydrocracking effluent 350, obtaining a degassed hydrocracking effluent 380. In Figure 2, the degassed hydrocracking effluent 380 is supplied to the 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, and a plurality of streams or cuts may be obtained therefrom. From the distillation in Figure 2, a gasoline fuel component 390, an aviation fuel component 400, and a diesel fuel component 410 are recovered. Further, a further recycle stream 420 with a T5 boiling point of 270 °C or higher may preferably be separated, in which case the diesel fuel component 410 may be partially separated and recovered therefrom. In Figure 2, the further recycle stream 420 may be supplied as a co-feed with the degassed HI effluent 230 to the second reactor 290 for hydrocracking.In certain embodiments, a portion of the HI effluents 200, 230 may be fed to the fractionation 240 as a co-feed 500 together with the hydrocracking effluents 350, 380.

[0164] The processes described herein can be controlled by means in the art, particularly computer-implemented means. In one exemplary embodiment, the process further includes causing a control device to compare a received value(s) to a predetermined value(s); and to switch from i), ii), iii) to I), II). In a particular exemplary embodiment, when the process is executed by a processor of a control device in a system for manufacturing at least one liquid transportation fuel component, as defined in a third exemplary aspect, the control device is caused to at least compare a received value to a predetermined value and, when the received value reaches the predetermined value, to switch from i), ii), iii) to I), II) in the process defined as a first exemplary aspect. The control device that executes the instructions of the computer program product may be, for example, a general-purpose computer or other electronic data processing device comprising a processor and a (non-transitory) memory. The instructions of the computer program product can be stored in the memory to be executed by the processor to cause the operation of the control device.

[0165] 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.

[0166] 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 without departing from the features of the invention, using equivalent means.

[0167] 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; i) subjecting the hydroisomerization effluent to fractional distillation to separate from the fraction at least a recycle stream having a T5 temperature of 270°C or higher (5 vol% recovery, EN ISO 3405-2019); ii) 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; iii) feeding the recycled effluent as a co-feed with the hydroisomerized effluent to the fractionation and recovering at least one or more liquid transportation fuel components from the fractionation; and monitoring a parameter indicative of deactivation of the hydroisomerization catalyst to receive a value; comparing the received value with a predetermined value; and If the received value reaches the predetermined value, steps i), ii) and iii) are changed to the following steps: I) subjecting the second reactor feed comprising the hydroisomerized effluent to hydrocracking in a second reactor in the presence of the hydrocracking catalyst to obtain a hydrocracking effluent; II) subjecting said hydrocracking effluent to fractional distillation and recovering at least one or more liquid transportation fuel components from said fractional distillation. The process of switching to A process involving:

2. The parameter indicative of deactivation of the hydroisomerization catalyst is a. 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; b. NH in the vapor phase of the hydroisomerization effluent 3 and / or H 2 S content c) the physicochemical properties of the hydroisomerization effluent, preferably at least one or more of cloud point, freezing point, pour point, plugging point, kinematic viscosity, density, and / or distillation properties; d. a compositional characteristic of the hydroisomerized effluent, preferably at least one or more of the isoparaffin content, the C8 to C14 hydrocarbon content, the multi-branched isoparaffin content, and / or the C1 to C4 hydrocarbon content in the hydroisomerized effluent; e. at least one or more yields of the recovered liquid transportation fuel components and / or the separated recycle stream, preferably a yield of an aviation fuel component; f) measuring 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, plugging point, kinematic viscosity, density, research octane number (RON), cetane number, and / or distillation properties; g. 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 one or more of the recovered liquid transportation fuel components and / or the separated recycle stream; h. the temperature differential in the first reactor or in one or more catalyst beds therein; i. Temperature, pressure, weight hourly space velocity (WHSV), H for paraffinic feed 2 ratio, and / or H at the inlet of the first reactor 2 and the operating conditions in said first reactor are selected from the partial pressure.

2. The process of claim 1, comprising at least two or more of:

3. 2. The process of claim 1, comprising step II) recovering a further recycle stream from said fractionation having a T5 temperature of 270°C or higher (5 vol% recovery, EN ISO 3405-2019) and feeding said further recycle stream to said second reactor as part of said second reactor feed.

4. 10. The process of claim 1, wherein said recycle stream and any said further recycle stream comprise C16 n-paraffins.

5. 2. The process of claim 1, further comprising step ii) subjecting a portion of the hydroisomerization effluent to hydrocracking in the second reactor as part of the second reactor feed, and / or step II) feeding a portion of the hydroisomerization effluent to fractionation as a co-feed with the hydrocracking effluent.

6. The process of claim 1, wherein the switching comprises feeding a decreasing portion of the hydroisomerization effluent to fractionation in step i) and simultaneously feeding an increasing portion of the hydroisomerization effluent to hydrocracking as part of the second reactor feed in step ii) until the process is operated in accordance with steps I) and II).

7. 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 partial pressure, 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 H 2 normal liters per liter of paraffinic hydrocarbon feed in the range of 10 to 2000, preferably 50 to 1000, normal liters of H 2 normal liters per liter of paraffinic hydrocarbon feed. 2 2. The process of claim 1, wherein the ratio of

8. 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 2. The process of claim 1 carried out at a partial pressure, a weight hourly space velocity of second reactor feed / kg catalyst / hr 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, and a ratio of H2 to second reactor feed in the range of 10 to 2000, preferably 50 to 1000 normal liters of H2 per liter of second reactor feed.

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

10. 2. The process of claim 1, wherein the hydroisomerization effluent 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 weight of total paraffins in the hydroisomerization effluent, and / or comprises at least 5 wt-%, preferably at least 10 wt-%, more preferably at least 15 wt-%, or at least 20 wt-% multiply-branched isoparaffins, based on the weight of total paraffins in the hydroisomerization effluent, and / or the hydroisomerization effluent 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, or less than -15°C (ASTM D 5771-17).

11. 2. The process of claim 1, wherein the hydroisomerization catalyst is a non-sulfided bifunctional hydroisomerization catalyst, and the hydrocracking catalyst is a non-sulfided bifunctional hydrocracking catalyst, and the non-sulfided bifunctional catalyst comprises at least one or more metals selected from the noble metals of Group VIII of the Periodic Table, preferably 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, of the total sulfur in each feed, measured according to ISO 20846-2019 (ppm by weight, calculated as elemental S).

12. the hydrocracking catalyst is a bifunctional hydrocracking catalyst, preferably a non-sulfided bifunctional hydrocracking catalyst, containing 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:

13. The method of claim 1, wherein the hydroisomerization catalyst is a bifunctional hydroisomerization catalyst, preferably a non-sulfided bifunctional hydroisomerization catalyst; at least one metal selected from Group VIII of the Periodic Table, preferably from the noble metals of Group VIII, more preferably from Pt and / or Pd; and 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 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 of alumina, silica, amorphous silica-alumina, 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 process of claim 1, wherein the paraffinic hydrocarbon feed comprises at least 70 wt-%, preferably at least 80 wt-%, more preferably at least 90 wt-% of paraffins based on 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-% of isoparaffins based on 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-% of 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-% of C14 to C22 hydrocarbons based on the total weight of the paraffinic hydrocarbon feed.

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 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.

19. 2. The process of claim 1, wherein in steps iii) and II) at least one or more of an aviation fuel component, a diesel fuel component, a gasoline fuel component, and / or a marine fuel component is recovered from the fractionation, preferably at least an aviation fuel component, more preferably at least an aviation fuel component and a diesel fuel component, or at least an aviation fuel component and a gasoline fuel component.

20. In steps iii) and II), 730 to 772 kg / m 3 2. The process of claim 1, wherein aviation fuel components having a density at 15°C in the range of (EN ISO 12185-1996), a T10 temperature (EN ISO 3405-2019) of at most 205°C, a final boiling point (EN ISO 3405-2019) of at most 300°C, a flash point (IP 170-2013, Avel close-cup method) of at least 38°C, and a freezing point (IP 529-2016) of at most -40°C are recovered from at least the fractional distillation.

21. The process of claim 18, wherein the aviation fuel component is recovered in a yield of at least 30 wt %, preferably in the range of 30 wt % to 90 wt %, based on the total weight of the paraffinic hydrocarbon feed.

22. 1. A system for producing at least one liquid transportation fuel component, the system being configured to carry out a process using i), ii), iii) or i), II), III), the system comprising: means configured to supply a paraffinic hydrocarbon feed comprising at least 60 wt. % paraffins based on a total weight of the paraffinic hydrocarbon feed, wherein up to 30 wt. % of the paraffins are isoparaffins; a first reactor configured to subject the paraffinic hydrocarbon feed to hydroisomerization in the first reactor in the presence of a hydroisomerization catalyst to obtain a hydroisomerized effluent; a fractionation system configured to: i) subject the hydroisomerization effluent to fractionation and to subject the recycle effluent to fractionation in order to separate from the fractionation at least a recycle stream having a T5 temperature of 270°C or greater (5 vol% recovery, EN ISO 3405-2019) (ii) and iii) below; and II) subject the hydrocracking effluent to fractionation; ii) subjecting a second reactor feed comprising said recycle stream to hydrocracking in a second reactor in the presence of a hydrocracking catalyst to obtain a recycle effluent; and I) a second reactor configured to subject a second reactor feed comprising said hydroisomerization effluent to hydrocracking in said second reactor in the presence of said hydrocracking catalyst to obtain a hydrocracked effluent; iii) conduits configured to supply the recycle effluent and the hydroisomerized effluent to the fractionation system, and III) conduits configured to supply the hydrocracked effluent to the fractionation system; means configured to recover at least one or more liquid transportation fuel components from the fractionation system; and a controller configured to monitor a parameter indicative of deactivation of the hydroisomerization catalyst to receive a value; to compare the received value with a predetermined value; and to switch the system from i), ii), or iii) to I), II), or III) when the received value reaches the predetermined value. A system including:

23. 21. A computer program product comprising instructions that, when executed by a processor of a controller in a system for producing at least one liquid transportation fuel component, cause the controller to compare the received value with a predetermined value and switch from i), ii), or iii) to I) or II) in the process of any one of claims 1 to 20 when the received value reaches the predetermined value.

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