Process for producing liquid transport fuel component

Abstract

A process for producing at least one liquid transport fuel component is provided. In the process, a paraffin feed is provided and hydroisomerized to obtain a hydroisomerized effluent; a recycle stream is separated from the hydroisomerized effluent and hydrocracked to obtain a recycle effluent, the hydroisomerized effluent and the recycle effluent are fed to fractionation, from which at least one liquid transport fuel component is recovered.

Description

Technical Field

[0001] The present disclosure generally relates to methods for producing renewable fuel components. The present disclosure particularly, but not exclusively, relates to methods for producing at least one or more liquid transportation fuel components, preferably at least an aviation fuel component. Background Art

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

[0003] Currently, there is a need to reduce greenhouse gas emissions and / or carbon footprint in transportation, especially aviation. Therefore, interest in renewable aviation fuels and aviation fuel components is and has been increasing.

[0004] Methods for producing aviation fuel components from renewable raw materials have been proposed. However, in the described methods, the yield of aviation fuel components (compared to other fuel components) is relatively low. In addition, there is a need to improve the quality of renewable aviation fuel components. In particular, there is still interest in the production of aviation fuel components that can be used in higher amounts in aviation fuels, or, when appropriately added, even used as aviation fuels themselves. Summary of the invention

[0005] The object is to solve or mitigate at least some of the problems associated with the prior art. The object is to improve the quality of aviation fuel components obtainable from renewable sources. Another object is to be able to increase the yield of aviation fuel components. Another object is to reduce the formation of C1-C4 hydrocarbons, especially C1-C2 hydrocarbons, in a process for producing a renewable liquid transportation fuel component. In addition, the object is to extend the life of a hydroisomerization catalyst in a process for producing a renewable liquid transportation fuel component.

[0006] The accompanying claims define the scope of protection. Any examples and technical descriptions of devices, systems, products and / or methods in the specification and / or drawings that are not covered by the claims are provided as examples useful for understanding the present invention.

[0007] According to a first example aspect, there is provided a method of producing at least one liquid transportation fuel component, the method comprising:

[0008] providing a paraffin feed comprising at least 60 wt-% paraffins based on the total weight of the paraffin feed, at most 30 wt-% of the paraffins being isoparaffins;

[0009] subjecting the paraffin feed in the first reactor to hydroisomerization (HI) in the presence of a hydroisomerization catalyst to obtain a hydroisomerization effluent;

[0010] subjecting the hydroisomerization effluent to fractionation to separate from the fractionation a recycle stream comprising at least C16 normal paraffins and having a T5 temperature (recovery 5 vol-%, EN ISO 3405-2019) of above 270°C;

[0011] 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;

[0012] feeding the recycle effluent to fractionation as a co-feed with the hydroisomerization effluent; and

[0013] At least one or more liquid transportation fuel components are recovered from the fractionation.

[0014] The process of the invention enables to obtain an improved yield and / or quality of recovered fuel components, and in particular preferably recovered aviation fuel components, while the amount of low-profit products (combustible gases) can be kept at a low level. In the process of the invention, as indicated, the recovery and recycling of the heavy fraction of the hydroisomerization (HI) effluent to hydrocracking has proven to be successful in converting said heavy hydrocarbons into valuable fuel components, in particular fuel components in the aviation fuel range. It has proven to be extremely beneficial to subject the highly isomerized recycle stream to hydrocracking, in particular to hydrocracking in the presence of a hydrocracking catalyst capable of both cracking and isomerization.

[0015] The inventor has found that the obtainable fuel component by the inventive method has extremely useful characteristics.With from the hydrodeoxygenation comprising fat raw materials, then the obtainable liquid fuel component of the conventional method of hydroisomerization is compared, the obtainable fuel component by the inventive method can especially have higher isoparaffin content, particularly multi-branched isoparaffin content, lower normal paraffin content and the carbon number and / or boiling point distribution of change.Usually, the low temperature properties of these enhancements of the obtainable fuel component by the inventive method and even the fluidity / compatibility at lower temperatures make the obtainable fuel component by the inventive method not only for the use in the fuel composition, but also in a wide range of other uses, be desired and useful.

[0016] Different non-combined example aspects and implementations have been described above. The above implementations are only used to explain selected aspects or steps that can be used in different implementations. Some implementations are only provided for certain example aspects. It should be understood that the corresponding implementations can also be applied to other example aspects. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Some example embodiments will be described with reference to the accompanying drawings, in which:

[0018] Figure 1 Example embodiments of the process of the present invention for producing at least one or more liquid transportation fuel components comprising hydrocracking are schematically illustrated.

[0019] Figure 2 Comparative processes involving hydrocracking for producing at least one or more liquid transportation fuel components are illustratively shown. DETAILED DESCRIPTION

[0020] In the following description, like reference symbols denote like elements or steps.

[0021] Unless otherwise stated, all standards referred to herein are to the most recent revision available on the date of submission.

[0022] Unless otherwise stated, 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, reference is made to EN ISO 3405-2019. IBP is the temperature at which the first drop of condensate falls from the lower end of the condenser tube, and FBP is the maximum thermometer reading obtained during the test, which usually occurs after all the liquid at the bottom of the flask has evaporated. For boiling point distribution, reference may also be made to the GC-based method (simdis) ASTM D2887-19e1, or, for gasoline range hydrocarbons, to ASTM D7096-19.

[0023] As used in the context of the present disclosure, aviation fuel components refer to hydrocarbon compositions suitable for use in fuel compositions that meet standard specifications for aviation fuels, such as the specifications specified in ASTM D7566-21. Typically, the boiling points of these aviation fuel components, i.e., IBP and FBP, are in the range of about 100°C to about 300°C, such as in the range of about 150°C to about 300°C, as determined according to EN ISO 3405-2019.

[0024] 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 a standard specification for diesel fuel, such as the specifications specified in EN 590:2022 or EN 15940:2016+A1:2018+AC:2019. Typically, the boiling points, i.e., IBP and FBP, of these diesel fuel components are in the range of about 160°C to about 380°C, as determined according to EN ISO 3405-2019.

[0025] As used in the context of the present disclosure, gasoline fuel components or naphtha refers to hydrocarbon components suitable for use in fuel compositions that meet standard specifications for gasoline fuels, such as the specifications specified in EN 228-2012+A1-2017. Typically, the boiling points of these gasoline fuel components, i.e., IBP and FBP, are in the range of about 25°C to about 210°C, as determined according to EN ISO 3405-2019.

[0026] As used in the context of this disclosure, a bunker fuel component refers to a hydrocarbon component suitable for use in a fuel composition that meets a standard specification for bunker fuels, such as the specification specified in ISO 8217-2017. Typically, the boiling points of these bunker fuel components, i.e., IBP and FBP, are in the range of about 180°C to about 600°C, such as in the range of about 180°C to about 400°C, as determined according to EN ISO 3405-2019.

[0027] As used herein, hydrocarbon refers to a compound consisting of carbon and hydrogen. Hydrocarbons of particular interest in the context of this article include paraffins, normal paraffins, isoparaffins, monobranched isoparaffins, multibranched isoparaffins, olefins, naphthalene and aromatics. Oxygenated hydrocarbons refer to hydrocarbons containing covalently bound oxygen in this article.

[0028] As used herein, paraffin refers to non-cyclic paraffins, i.e., non-cyclic, open-chain saturated hydrocarbons that are straight (normal paraffins) or branched (isoparaffins). In other words, paraffins herein refer to normal paraffins and / or isoparaffins.

[0029] In the context of the present disclosure, isoparaffin refers to branched open chain alkanes, i.e., non-cyclic, open chain saturated hydrocarbons with one or more alkyl side chains. In this article, isoparaffins with one alkyl side chain or branch are referred to as monobranched isoparaffins, and isoparaffins with two or more alkyl side chains or branches are referred to as multi-branched isoparaffins in this article. In other words, isoparaffin refers to monobranched isoparaffins and / or multi-branched isoparaffins in this article. For example, the alkyl side chain of isoparaffin can be a C1-C9 alkyl side chain, preferably a methyl side chain. The amount of monobranched and multi-branched isoparaffins can be given separately. The term "isoparaffin" refers to the total amount of any monobranched isoparaffin and any multi-branched isoparaffin (if present), which represents the total amount of any isoparaffin present without considering the number of branches. Accordingly, "paraffin" refers to the total amount of any normal paraffin, any monobranched and any multi-branched isoparaffin (if present).

[0030] In the context of the present disclosure, olefin refers to an unsaturated, linear, branched or cyclic hydrocarbon, excluding aromatic hydrocarbons. In other words, olefin refers to a hydrocarbon having at least one unsaturated bond, excluding unsaturated bonds in aromatic rings.

[0031] As used herein, cycloalkanes refer to all hydrocarbons containing ring structures, including cycloolefins, naphthalene and aromatic hydrocarbons.Naphthalene refers to cycloalkanes in this article, i.e., saturated hydrocarbons containing at least one ring structure with or without side chains.Since naphthalene is a saturated compound, they are compounds without aromatic ring structures.Aromatic hydrocarbons refer to hydrocarbons containing at least one aromatic ring structure in this article, i.e., a ring structure with delocalized alternating π bonds around the ring structure.

[0032] In the context of the present disclosure, for gasoline fuel components, the content of n-paraffins, iso-paraffins, mono-branched iso-paraffins, multi-branched iso-paraffins, olefins, naphthalenes and aromatics is expressed as weight % (wt-%) relative to the weight of the feed, stream, effluent, product, component or sample in question, or, when so defined, as weight % (wt-%) relative to the (total) weight of paraffins or the (total) weight of iso-paraffins of the feed, stream, effluent, product, component or sample in question. The content can be determined by GC-FID / GC-MS method, which is preferably implemented as follows: run GC-FID as disclosed in ASTM D6839 using the following parameters: column ZB-1 60m, ID 0.25mm, df 1.0 micron or similar column; column oven 0°C (2min)-1.5°C / min-300°C (5min); injector and detector 300°C; carrier gas: helium, 1.0ml / min; detector gas: H 2 , 35 ml / min, and air, 350 ml / min; makeup gas flow: helium, 30 ml / min; split: 165:1 (165 ml / min). Individual compounds were identified using GC-MS (operating parameters: ion source: 230 °C; interface: 280 °C; scan: 25-280 m / z; scan speed: 303; scan event time: 0.88). The detected compounds or hydrocarbon radicals were identified using commercial tools (Shimadzu LabSolutions / GCMSSolutions and Agilent OpenLab) and their mass concentrations were determined by applying the response factor relative to n-heptane to the area of ​​the detected peaks and then normalizing to 100 wt-% (for liquid volume concentrations: by applying the density factor to the calculated mass concentration of the detected peaks and then normalizing to 100 vol-%). The olefin naphthalene is reported under naphthalene. The limit of quantification of the individual compounds of this method is 0.1 wt-%.

[0033] In the context of the present disclosure, for other compositions boiling at 36°C or above (at standard atmospheric pressure), the content of n-paraffins, iso-paraffins, mono-branched iso-paraffins, various multi-branched iso-paraffins, naphthalenes and aromatics is 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 iso-paraffins of the feed, stream, effluent, product, component or sample in question. The content can be determined by the GC×GC-FID / GC×GC-MS method, preferably performed as follows: The GC×GC (2D GC) method is performed as generally disclosed in UOP 990-2011 and Nousiainen M. in his master's thesis Comprehensive two-dimensional gas chromatography with mass spectrometric and flame ionization detectors in petroleum chemistry, University of Helsinki, August 2017, with the following modifications. The GC×GC was operated in reverse mode, first using a semipolar column (Rxi17Sil) and then a nonpolar column (Rxi5Sil), followed by an FID detector, using the following operating parameters: carrier gas: helium 31.7 cm / sec (column flow 1.60 ml / min at 40°C); 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), run time: 52 min; modulation period: 10 s; detector: 300°C, using H 2 40 ml / min and air 400 ml / min; makeup gas flow: helium 30 ml / min; sampling rate: 250 Hz, and injection volume: 0.2 microliters. Individual compounds were identified using GC×GC-MS, MS parameters: ion source: 230°C; interface: 300°C; scan range: 25-500 amu; event time (seconds): 0.05; scan speed: 20000. Data processing was performed using commercial tools (Shimadzu's LabSolutions, Zoex's GC Image), including identification of the detected compounds or hydrocarbon groups and determination of their mass concentrations by applying a response factor relative to n-heptane to the volume of the detected peaks and then normalizing to 100 wt-%. Unless reported separately, olefins are grouped with naphthalene and heteroatom species are grouped with aromatics. The quantification limit for individual compounds of this method is 0.1 wt-%.

[0034] In the context of the present disclosure, various characteristics of a feed, stream, effluent, product, component or sample are determined according to appropriately prepared standard methods mentioned or disclosed herein. For example, the cloud point is determined from a degassed feed, stream, effluent, product, component or sample according to ASTM D 5771-17.

[0035] Typically, the various paraffinic feeds, streams, effluents and fuel components referred to herein as recovered products or fractions thereof may contain, in addition to hydrocarbons, varying trace amounts of, for example, heteroatom-containing hydrocarbons and inorganic compounds as impurities, and the oxygenated hydrocarbon feeds contain varying amounts of, for example, other heteroatom-containing hydrocarbons and inorganic compounds as impurities. Typically, the impurity levels in the main process streams are highest in the first part of the process and subsequently decrease to negligible or even below the detection limit of the recovered liquid transportation fuel components.

[0036] In the context of the present disclosure, unless otherwise stated, the feed to a reactor, in particular the first reactor and / or the second reactor, is defined such that the H that may be fed to the respective reactor is 2 , for example, H fed to the hydroisomerization 2 and H fed to the hydrocracking 2 Not included in the definition of feed.

[0037] As used herein, hydroisomerization (HI) effluent refers to total HI effluent, degassed HI effluent, or degassed and stabilized HI effluent, as appropriate, and the term HI effluent may encompass each of these.

[0038] In the context of the present disclosure, CX+ paraffins, CX+ normal paraffins, CX+ isoparaffins, CX+ monobranched isoparaffins, CX+ multibranched isoparaffins, CX+ hydrocarbons or CX+ fatty acids refer to paraffins, normal paraffins, isoparaffins, monobranched isoparaffins, multibranched isoparaffins, hydrocarbons or fatty acids having a carbon number of at least X, respectively, wherein X is any feasible integer. It should be understood that every compound falling within the scope of this definition does not necessarily have to be present.

[0039] In the context of the present disclosure, CY-alkane, CY-n-alkane, CY-iso-alkane, CY-mono-branched iso-alkane, CY-multi-branched iso-alkane, CY-hydrocarbon or CY-fatty acid refers to an alkane, n-alkane, iso-alkane, mono-branched iso-alkane, multi-branched iso-alkane, hydrocarbon or fatty acid having a carbon number up to Y, respectively, wherein Y is any feasible integer. It should be understood that every compound falling within the scope of this definition does not necessarily have to be present.

[0040] In the context of this disclosure, CX Y -CX Z (or CXY To CX Z ) Alkanes, CX Y -CX Z Normal paraffin, CX Y -CX Z Isoparaffin, CX Y -CX Z Monobranched isoparaffins, CX Y -CX Z Multi-branched isoparaffins, CX Y -CX Z Hydrocarbon or CX Y -CX Z Fatty acids refer to a certain range of paraffins, normal paraffins, isoparaffins, monobranched isoparaffins, multibranched isoparaffins, hydrocarbons or fatty acids, wherein X Y and X Z Is a feasible end value integer, wherein the carbon number within the range is indicated by any integer between the end value integer and the end value (if any). However, unless explicitly stated, all of the carbon numbers are within the range, and paraffins, normal paraffins, isoparaffins, monobranched isoparaffins, multi-branched isoparaffins, hydrocarbons or fatty acids at or near the endpoints are not necessarily present, as the case may be. On the other hand, according to the definition, isomers can include several compounds with the same carbon number, such as C15 isomers can include methyl tetradecane (different positions of methyl branches), dimethyl tridecane (different positions of two methyl branches), etc., wherein "C15 isomers" include the sum of all these variants.

[0041] Generally, the sum of the weight or volume of paraffins, normal paraffins, isoparaffins, monobranched isoparaffins, multibranched isoparaffins, hydrocarbons or fatty acids, as defined in each case, means including all carbon numbers. For example, C15 to C22 normal paraffins refers to any normal paraffin within the stated range, such as C15, C16, C17, C18, C19, C20, C21 and C22 normal paraffins, even if the content of C15 normal paraffin is zero. In other words, the total amount is obtainable by adding 0 (referring to the absence of C15 normal paraffin) to the total weight of all other C15 to C22 normal paraffins present.

[0042] Isomerization converts at least a certain amount of n-paraffins into iso-paraffins, in particular into mono-branched iso-paraffins. By (further) increasing the degree of isomerization, for example by increasing the severity of the hydroisomerization as described below, more n-paraffins can be converted into iso-paraffins, and mono-branched iso-paraffins can be converted into multi-branched iso-paraffins, such as doubly and / or triply branched iso-paraffins, or even iso-paraffins containing more than three branches.

[0043] As used herein and in the context of the second reactor, the extent of effective cracking refers to cracking that produces non-gaseous (NTP) cracked products, and particularly as expressed as the ratio of the C8 to C14 hydrocarbon content in the recycle effluent to the C8 to C14 hydrocarbon content in the second reactor feed.

[0044] As used herein, as long as the reaction step is defined as occurring in a "reactor", such as a first reactor and a second reactor, the expression is primarily for illustrative purposes. Those skilled in the art recognize that any "reactor" is implemented in practice as a reactor system that can be composed of one or more reactors. Whether the reactor is actually arranged in a single reactor or in several reactors is an engineering problem and may be affected by practical issues such as the maximum height of the field facility, the reactor diameter, the management and maintenance issues on site, the wind conditions on site and / or the available equipment. Similarly, "fractionation" can be carried out in a fractionation system, which typically includes (for example) separation and distillation units, which can be arranged according to conventional engineering practices in the art.

[0045] In the context of the present disclosure, catalyst characteristics, such as the total number of acid sites, refer to the characteristics of the catalyst in its ready-to-use state at the beginning of the process of the present invention.

[0046] As used herein, the term catalyst deactivation refers to the time at which the catalyst is deactivated relative to the start of the process of the present invention (t 0 ) compared to the activity and / or selectivity of the catalyst at a given time point (t n The term catalyst deactivation is defined as a decrease in catalyst activity (reflected by the amount of unconverted feed in the reactor effluent) and / or a decrease in catalyst selectivity (reflected by a decrease in the amount of desired reaction product in the reactor effluent). As used herein, the term catalyst deactivation is not limited to any particular type or mechanism of deactivation, although catalyst deactivation observed in the process of the present invention is generally believed to be due to poisoning and fouling phenomena, and encompasses both reversible and irreversible deactivation.

[0047] As used herein, the term renewable refers to a compound or composition that is obtainable, derivable or sourced from plants and / or animals in whole or in part, including a compound or composition that is obtainable, derivable or sourced from fungi and / or algae. As used herein, renewable compounds or compositions may include genetically manipulated compounds or compositions. Renewable feed, component, compound or composition may also be referred to as biofeed, component, compound or composition, or as biogenic feed, component, compound or composition.

[0048] As used herein, the term fossil refers to a compound or composition obtainable, derivable or sourced from a naturally occurring non-renewable composition, such as crude oil, petroleum / petroleum gas, shale oil / shale gas, natural gas or coal deposits, and the like, and combinations thereof, including any hydrocarbon-rich deposits that can be utilized from above-ground / underground sources.

[0049] The term "recycled" refers to recycled materials that are usually derived from non-renewable energy sources. For example, the term "recycled" may refer to recycled materials derived from waste plastics. Based on their sources and impact on environmental issues, the renewable, recycled and fossil compounds or compositions are considered to be different from each other. Therefore, they may be treated differently under regulations and regulatory frameworks. Typically, renewable, recycled and fossil compounds or compositions are distinguished based on their sources and information provided by the producers.

[0050] Chemically, the carbon content of any organic compound, including hydrocarbons of renewable or fossil origin, can be determined by appropriate methods for analyzing the carbon content of renewable origin, for example, DIN 51637 (2014), ASTM D6866 (2020) or EN 16640 (2017). The methods are based on the fact that carbon atoms of renewable or biological origin contain a higher number of unstable radiocarbons ( 14 C) atoms. Therefore, it is possible to analyze 12 C and 14 C isotope ratios are used to distinguish carbon compounds derived from renewable or biological sources or raw materials from carbon compounds derived from non-renewable or fossil sources or raw materials. Therefore, the specific ratio of the 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 chemical reaction. Therefore, the isotope ratio can be used to identify renewable compounds, components and compositions and distinguish them from non-renewable, fossil materials in reactor feeds, reactor effluents, separated product fractions and various blends thereof. Numerically, the biochar content can be expressed as the amount of biochar in the material as a weight percentage of the total carbon (TC) in the material (according to ASTM D6866 (2020) or EN 16640 (2017)). In the context of the present invention, the term renewable preferably refers to a material having a biocarbon content of more than 50 wt-%, in particular more than 60 wt-% or more than 70 wt-%, preferably more than 80 wt-%, more preferably more than 90 wt-% or more than 95 wt-%, even more preferably about 100 wt-%, based on the total weight of carbon in the material (EN 16640 (2017)).

[0051] The present disclosure provides a method for producing at least one liquid transportation fuel component, the method comprising: providing a paraffinic feed comprising at least 60 wt-% paraffins of the total weight of the paraffinic feed, of which at most 30 wt-% are isoparaffins; subjecting the paraffinic feed in a first reactor to hydroisomerization (HI) in the presence of a hydroisomerization catalyst to obtain a hydroisomerization effluent; subjecting the hydroisomerization effluent to fractionation to separate from the fractionation a recycle stream comprising at least C16 normal paraffins and having a T5 temperature (recovery 5 vol-%, EN ISO 3405-2019) of above 270°C; subjecting a second reactor feed comprising the recycle stream to hydrocracking (HC) in the presence of a hydrocracking catalyst in a second reactor to obtain a recycle effluent; feeding the recycle effluent to fractionation as a co-feed with the hydroisomerization effluent; and recovering at least one or more liquid transportation fuel components from the fractionation.

[0052] Preferably, the process of the present invention is a continuous process.

[0053] Typically, in the inventive method, at least one or more of aviation fuel components, diesel fuel components, gasoline fuel components and / or marine fuel components are recovered from fractionation, preferably at least aviation fuel components are recovered. Compared with the conventional method of producing fuel components by hydrodeoxygenation (HDO) and hydroisomerization (HI) of renewable fats and oils, using the inventive method, it is possible to obtain higher aviation fuel component yields during the entire HI catalyst life without reducing the capacity of HI in the first reactor, and / or improve the quality of aviation fuel components. Experimentally, the test run implemented according to the inventive method has shown that up to 64wt-% of the recycle stream can still be converted into a renewable aviation fuel component. It is believed that the heavy molecules of the recycle stream contribute to the increase in yield to the cracking of the C8-C14 range in particular, while the degree of isomerization will not be significantly reduced.

[0054] Using the process of the present invention, it is possible to produce aviation fuel components that have excellent low temperature properties and are therefore usable in aviation fuel at high blending ratios or even by themselves (i.e., unblended) when appropriately added, even near the end of the HI catalyst life. In addition, compared to conventional methods of producing fuel components from HDO and HI of renewable fats and oils, the process of the present invention can extend the HI catalyst life and can utilize a wider range of feeds, including heavier and more impure feeds. In addition, even at the end of the HI catalyst life, the process of the present invention can flexibly adjust product selectivity for a variety of liquid transportation fuel components, such as gasoline fuel components, aviation fuel components, diesel fuel components, and / or marine fuel components based on (for example) market dynamics.

[0055] The method of the present invention proposes to subject the heavy fraction (i.e., recycle stream) of the HI effluent to hydrocracking, which cracks the longer paraffin chains into paraffins boiling in the range of, for example, aviation fuel, and can even isomerize the normal paraffins in the second reactor feed and the normal paraffins formed during the cracking reaction, and further isomerize the isoparaffins by increasing the number of branches in the isoparaffin molecules, for example, producing multi-branched isoparaffins. Typically, the recycle stream subjected to hydrocracking contains compounds boiling above the target aviation fuel boiling range, and / or normal paraffins, particularly C16+ normal paraffins, thereby affecting low temperature properties. By operating the method of the present disclosure, a high degree of isomerization can be achieved in the first reactor. This is beneficial for achieving the desired effective cracking degree in the second reactor under milder operating conditions (compared to the less isomerized second reactor feed). Preferably, in the second reactor, by operating the method of the present invention, the content of multi-branched isoparaffins in the HI effluent is also effectively increased compared to their content in the paraffin feed, which has a beneficial contribution to the effective cracking degree, especially for C8-C14 hydrocarbons, but also to the effective cracking degree of lighter non-gaseous hydrocarbons. It is also believed that multi-branched isoparaffins increase the isoparaffin content of the recycle effluent (compared with the second reactor feed with a lower or no multi-branched isoparaffin content). For both the yield and quality of the recovered transportation fuel components, especially for the yield and quality of the aviation fuel components preferably recovered, the effective cracking degree increased in the second reactor without forming excessive gaseous hydrocarbons and the isoparaffin content of the recycle effluent can be beneficial. Hydrocracking can increase the yield of the aviation fuel component and improve its quality, such as its low temperature properties, especially reduce its freezing point and / or viscosity at sub-zero temperatures (such as -20 ° C).

[0056] During the continuous operation of catalytic hydroisomerization and hydrocracking, the catalyst (for example) gradually deactivates due to impurities and coking in the process stream. The method of the present invention is highly flexible and involves multiple possibilities for adjusting the yield and / or quality of the recovered liquid transportation fuel components and extending the life of the HI and HC catalysts. Adjusting the amount of the recycle stream subjected to hydrocracking and / or the amount of heavy materials removed from the method 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 transportation fuel components and responding to catalyst deactivation or changing market demands. In addition, when only the recycle stream (i.e., only the heavy fraction of the HI effluent) is hydrocracking, the gaseous impurities that are usually present in the gas phase of the HI effluent do not contact the hydrocracking (HC) catalyst. Compared with the conventional method of producing liquid fuel components by HDO and HI of renewable fats and oils, the multiple possibilities of compensating for the deactivation of the HI catalyst, in particular, enable the use of paraffin feeds with higher impurity contents. Additionally, the hydrocracking step enables the use of feedstocks containing heavier and longer chain molecules than described conventional processes for producing liquid fuel components (typically diesel components), while enabling the production of lower boiling liquid transportation fuel components, such as aviation fuel components and / or gasoline fuel components, in good yield and quality.

[0057] In certain preferred embodiments of the process of the present invention, the second reactor feed also comprises a portion of the HI effluent (except the recycle stream). In these embodiments, for example, the portion can be obtained by simply diverting the total HI effluent or preferably degassed HI effluent between the fractionation and the second reactor using, for example, a fixed or preferably gradually adjusted ratio. These embodiments provide further flexibility for the operation of the process of the present invention, and provide the possibility of even more accurately adjusting the process to simultaneously meet the target yield and quality of more than one recovered fuel component. In this way, it may be possible to avoid a situation in which the target yield and quality of a recovered fuel component are met, but at the expense of producing an excessively high quality of another recovered fuel component (e.g., producing a diesel fuel component with an unnecessarily low cloud point).

[0058] In the method of the present invention, the paraffin feed that carries out hydroisomerization in the first reactor comprises at least 60wt-% paraffins of the gross weight of paraffin feed, and the paraffins are isoparaffins at most 30wt-%. This means that when the paraffin feed comprises 60wt-% paraffins of the gross weight of paraffin feed, at most 30wt-% of the total weight of paraffins in the paraffin feed, i.e. at most 18wt-% of the gross weight of paraffin feed is isoparaffins. Preferably, the paraffin feed comprises at least 70wt-% of the gross weight of the paraffin feed, more preferably at least 80wt-%, even more preferably at least 90wt-% paraffins. The paraffin feed of the present disclosure can comprise even at least 95wt-% paraffins of the gross weight of paraffin feed, or is substantially composed of paraffins. The paraffinic feedstock of the present disclosure may contain small amounts of olefins, preferably less than 5 wt-%, more preferably less than 1 wt-% olefins, based on the total weight of the paraffinic feedstock, and small amounts of aromatics and / or naphthalene.

[0059] An advantage of using a highly paraffinic feed in the process of the present invention is that paraffins are relatively easy to isomerize and are isomerized under milder conditions when subjected to HI than, for example, cyclic hydrocarbons. In addition, paraffins are relatively easy to crack and are cracked under milder conditions when subjected to hydrocracking.

[0060] Of the paraffins in the paraffin feed of the present disclosure, preferably at most 25 wt-%, more preferably at most 20 wt-%, and even more preferably at most 15 wt-% are isoparaffins. For example, 1 wt-% to 30 wt-%, or 1 wt-% to 20 wt-%, or 2 wt-% to 30 wt-% or 2 wt-% to 20 wt-% of the paraffins in the paraffin feed may be isoparaffins.

[0061] A high weight ratio (wt-%:wt-%) of normal paraffins to isoparaffins in the paraffin feed can help limit cracking side reactions during HI in the first reactor, since normal paraffins are less susceptible to cracking than isoparaffins of the same carbon number. However, the presence of a certain amount of isoparaffins in the paraffin feed may still be beneficial. A paraffin feed containing a certain amount of isoparaffins may produce a HI effluent having a higher content of multi-branched isoparaffins than an otherwise similar feed that does not contain isoparaffins.

[0062] Preferably, the paraffinic feed of the present disclosure comprises at least 70wt-%, preferably at least 80wt-%, more preferably at least 90wt-%, even more preferably at least 95wt-% of hydrocarbons with carbon numbers in the range of C12 to C30 of the total weight of the paraffinic feed. In certain particularly preferred embodiments, the paraffinic feed comprises at least 70wt-%, preferably at least 80wt-%, more preferably at least 90wt-%, even more preferably at least 95wt-% of hydrocarbons with carbon numbers in the range of C14 to C22 of the total weight of the paraffinic feed. Paraffinic feeds with high C12 to C30 hydrocarbon content are preferred because they allow good yields of two or more different types of liquid transportation fuel components. For the same reason, C14 to C22 hydrocarbons are particularly preferred, and also because they are easily (for example) obtained from conventional hydrodeoxygenation (HDO) processes of vegetable oils, animal fats and / or microbial oils containing fatty acids.

[0063] In order to improve the yield of aviation fuel components and / or diesel fuel components, it is particularly preferred that the paraffin feed comprises at least 50wt-%, preferably at least 60wt-%, more preferably at least 70wt-%, even more preferably at least 80wt-% or at least 90wt-% of the total weight of paraffins in the paraffin feed. In certain embodiments, the paraffin feed comprises at least 50wt-% of the total weight of paraffins in the paraffin feed C17+ paraffins. By appropriately selecting a heavy paraffin feed, in particular by appropriately selecting the raw materials used to produce them, such as oxygenated hydrocarbons, such compositions are obtainable. Examples of suitable heavy oxygenated hydrocarbon feeds include oils from energy crops, such as Brassica species, algae oils, crude tall oil (CTO), tall oil fatty acids (TOFA), tall oil pitch (TOP) and / or feeds derived from lignocellulose. C17+ paraffins are also obtainable by Fischer-Tropsch conversion of synthesis gas.

[0064] The paraffin feed may comprise any suitable paraffin composition or combination thereof. Preferably, in the process of the present invention, the step of providing the paraffin feed comprises catalytic hydrotreating of a hydrotreated feed, preferably catalytic hydrodeoxygenation of an oxidized hydrocarbon feed, wherein the hydrotreated feed preferably comprises at least one or more of vegetable oil, animal fat, microbial oil, thermally liquefied organic waste and residue and / or enzymatically liquefied organic waste and residue, more preferably, the oxidized hydrocarbon feed comprises at least one or more of vegetable oil, animal fat and / or microbial oil, and / or subjecting the synthesis gas to Fischer-Tropsch conversion to obtain a paraffin FT effluent; subjecting the paraffin hydrotreating effluent and / or the paraffin FT effluent to gas-liquid separation and / or paraffin feed fractionation to provide the paraffin feed. Gas-liquid separation refers to the removal of compounds that are gaseous at least at NTP.

[0065] Although (for example) fossil-derived paraffinic FT effluents are readily available (in addition to FT effluents of renewable origin), it is preferred that the paraffinic feedstock of the present disclosure is at least partially renewable, i.e. comprises biogenic components. In certain preferred embodiments, the biogenic carbon content of the paraffinic feedstock 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 carbon weight (TC) of the paraffinic feedstock, preferably as determined according to EN 16640 (2017).

[0066] In certain embodiments, the paraffin feed comprises a degassed paraffin Fischer-Tropsch effluent or a fraction thereof or consists essentially of it. The Fischer-Tropsch process comprises a synthesis gas comprising carbon monoxide and hydrogen, which is generally catalytically converted into a substantially Gaussian distributed hydrocarbon chain, mainly normal paraffins, having a wide carbon chain length distribution, such as from C2 to C100+, generally from about C5 to about C50. The FT effluent is generally highly paraffinic, comprising mainly normal paraffins. The catalytic FT conversion of the synthesis gas can result in a lesser degree of isomerization, and the FT effluent generally comprises about 10wt-% or less of the total weight of the FT effluent of isoparaffins. The synthesis gas used in the FT process can be produced by renewable materials, natural gas, coal or a combination thereof.

[0067] Preferably, the paraffinic feed of the present disclosure comprises or consists essentially of a degassed paraffinic hydroprocessing effluent or a fraction thereof, in particular as obtained by catalytic hydroprocessing of a hydroprocessing 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 oils, animal fats and / or microbial oils, to obtain a paraffinic hydroprocessing effluent, followed by subjecting the paraffinic hydroprocessing effluent to gas-liquid separation and optionally to fractionation of the paraffinic feed to provide a degassed hydroprocessing effluent or a fraction thereof.

[0068] The term "catalytic hydroprocessing", sometimes also referred to as hydrotreating, refers to a catalytic process for treating organic materials with molecular hydrogen. Preferably, catalytic hydroprocessing removes oxygen from organic oxygen compounds in the form of water, i.e., hydrodeoxygenation (HDO), and from organic sulfur compounds in the form of dihydrosulfide (H 2 S) in the form of hydrodesulfurization (HDS), which removes sulfur from organic nitrogen compounds in the form of ammonia (NH 3), i.e., hydrodenitrogenation (HDN), removal of halogens, e.g., removal of chlorine from organic chlorine compounds in the form of hydrochloric acid (HCl), i.e., hydrodechlorination (HDCl), and / or removal of metals by hydrodemetallization, and / or hydrogenation of olefinic bonds, if present in the hydroprocessing feed. Depending on the composition of the hydroprocessing feed, different reactions may occur and / or proceed.

[0069] Preferably, the paraffinic feed of the present disclosure comprises or consists essentially of a degassed hydrodeoxygenation (HDO) effluent or a fraction thereof, in particular as obtained by catalytic hydrodeoxygenation (HDO) of an oxidized hydrocarbon feed comprising at least one or more of vegetable oil, animal fat and / or microbial oil, thereby obtaining a paraffinic HDO effluent, followed by gas-liquid separation of the paraffinic HDO effluent and optionally fractionation of the paraffinic feed to provide a degassed HDO effluent or a fraction thereof.

[0070] In certain embodiments, providing the paraffin feed comprises subjecting the oxygenated hydrocarbon feed to hydrodeoxygenation, preferably in a hydrodeoxygenation (HDO) reactor in the presence of a hydrodeoxygenation catalyst to obtain a hydrodeoxygenation effluent, and subjecting the hydrodeoxygenation effluent to gas-liquid separation and optionally to paraffin feed fractionation to obtain a degassed hydrodeoxygenation effluent or a fraction thereof as the paraffin feed, wherein the hydrodeoxygenation is preferably carried out under the following conditions: a temperature in the range of 200° C. to 500° C., a pressure in the range of 1 MPa to 20 MPa, an HDO at the reactor inlet in the range of 1 MPa to 20 MPa, and a pressure in the range of 1 MPa to 20 MPa. 2 partial pressure, a weight hourly space velocity in the range of 0.1 to 10 kg oxygenated hydrocarbon feed / kg catalyst / hour, and a catalyst selected from 50 to 2000 standard liters H 2 / L oxygenated hydrocarbon feed in the range of H 2 The ratio of the oxygenated hydrocarbon feed to the oxygenated hydrocarbon feed is preferably 1: 1. The oxygenated hydrocarbon feed comprises at least one or more of a vegetable oil, an animal fat and / or a microbial oil. The hydrodeoxygenation is preferably carried out as described in prior art publications such as FI100248B, EP1741768A1, EP2155838B1 or FI129220 B1.

[0071] The optional paraffinic feed fractionation is usually carried out in a fractionation unit different from the fractionation unit used to recover liquid transportation fuel components and / or separate recycle streams. The optional paraffinic feed fractionation can be considered separate from the fractionation of the process of the present invention, which includes fractionation to recover liquid transportation fuel components and / or separate recycle streams.

[0072] Preferably, the HDO catalyst is a sulphurized catalyst comprising 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, even more preferably at least one or more of Ni, and / or Co and Mo, and / or W, such as NiMo, CoMo, NiCoMo, NiW and / or NiMoW. These catalysts are effective, readily available and well tolerate typical impurities of fatty feedstocks. If a catalyst having hydrodewaxing properties, such as a catalyst containing NiW, is used in the hydrodeoxygenation as a hydrodeoxygenation catalyst or as a co-catalyst, an HDO effluent with a slightly increased isoparaffin content can be obtained.

[0073] In the process of the present invention, the paraffin feed is hydroisomerized in the presence of a HI catalyst in the first reactor to obtain a HI effluent. Generally, in the context of the present disclosure, the HI of the paraffin feed in the first reactor is operated so that the isomerization reaction is dominant while the cracking reaction is controlled or suppressed.

[0074] Preferably, the hydroisomerization in the first reactor is carried out at a temperature 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, at a pressure of 1 MPa to 10 MPa, preferably 2 MPa to 8 MPa or 3 MPa to 10 MPa, at a pressure of 1 MPa to 10 MPa, preferably 2 MPa to 8 MPa or 3 MPa to 10 MPa, at a pressure of 1 MPa to 10 MPa, preferably 2 MPa to 8 MPa at the inlet of the first reactor. 2 partial pressure, a weight hourly space velocity of 0.1 to 10, preferably 0.2 to 8, more preferably 0.4 to 6 kg paraffin feed / kg catalyst / hour, and a standard liter H 2 / L H of paraffin feed 2 The feed ratio is carried out at the same time as the paraffin feed.

[0075] According to certain embodiments, the hydroisomerization in the first reactor is carried out under the following conditions: a temperature in the range of 200°C to 500°C, a pressure in the range of 1 MPa to 10 MPa, and a H 2 The partial pressure is in the range of 1 MPa to 10 MPa, the weight hourly space velocity is in the range of 0.1 to 10 kg paraffin feed / kg catalyst / hour, and H 2 The feed ratio of paraffin is between 10 and 2000 Nl H 2 / L paraffin feed range.

[0076] According to certain particularly preferred embodiments, the hydroisomerization in the first reactor is carried out under the following conditions: the temperature is in the range of 230°C to 500°C, the pressure is in the range of 2MPa to 8MPa, and the H at the inlet of the first reactor is 2 The partial pressure is in the range of 2 MPa to 8 MPa, the weight hourly space velocity is in the range of 0.2 to 8 kg paraffin feed / kg catalyst / hour, and H 2 The feed ratio of paraffin is between 50 and 1000 Nl H 2 / L paraffin feed range.

[0077] Preferably, the HI effluent is subjected to a gas-liquid separation, i.e., to remove compounds that are gaseous at least at the NTP, including, for example, NH 3 and / or H 2 S. This can be done before directing the HI effluent to fractionation, for example, as an integrated step within the first reactor or as part of the fractionation.

[0078] The degree of isomerization of the HI effluent can be improved by increasing the severity of the HI, for example by at least one or more of: reducing the WHSV, increasing the temperature, and / or increasing the pressure. When using a fresh HI catalyst, high severity HI conditions can be achieved at lower temperatures and / or pressures and / or using higher WHSVs. Towards the end of the HI catalyst life, higher temperatures and / or pressures and / or lower WHSVs may be required to achieve even moderately severe HIs. In the context of the present invention, a liquid effluent produced from HI having, as wt-% of paraffins in the liquid effluent, a total isoparaffin content in the range of 50 wt-% to 85 wt-% and a multi-branched isoparaffin content of up to 25 wt-%, or a total isoparaffin content in the range of 85 wt-% to 95 wt-% and a multi-branched isoparaffin content in the range of 25 wt-% to 55 wt-%, or a total isoparaffin content of at least 95 wt-% and a multi-branched isoparaffin content of greater than 55 wt-%, is generally considered to be a low severity, medium severity or high severity HI, respectively, although these content ranges are merely for illustrative purposes and may overlap to some extent and vary depending on the circumstances.

[0079] Preferably, the hydroisomerization in the first reactor is operated such that the ratio of the amount of wt-% of isoparaffins based on the total weight of paraffins in the HI effluent to the amount of wt-% of isoparaffins based on the total weight of paraffins in the paraffin 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 such that the ratio of the amount of wt-% of multi-branched isoparaffins based on the total weight of paraffins in the HI effluent to the amount of wt-% of multi-branched isoparaffins based on the total weight of paraffins in the paraffin 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 such that the (total) HI effluent comprises less than 20 wt-%, or less than 10 wt-%, preferably less than 5 wt-%, more preferably less than 3 wt-% of C1 to C4 hydrocarbons, based on the total weight of the HI effluent. This may be achieved in particular when operating the first reactor within HI operating conditions and / or using a HI catalyst and / or a paraffin feed as defined herein.

[0080] Typically, the HI effluent comprises at least 60 wt-%, preferably at least 70 wt-%, more preferably at least 80 wt-%, even more preferably at least 90 wt-% or at least 95 wt-% paraffins based on the total weight of the HI effluent. In certain embodiments, the HI effluent may even consist essentially of paraffins.

[0081] Typically, the HI effluent comprises at least 50 wt-%, preferably at least 60 wt-%, more preferably at least 70 wt-%, even more preferably at least 80 wt-% of isoparaffins, and optionally at least 5 wt-%, more preferably at least 10 wt-%, even more preferably at least 15 wt-%, or at least 20 wt-% of multi-branched isoparaffins, based on the total weight of paraffins in the HI effluent. Typically, the HI effluent comprises up to 75 wt-%, or up to 70 wt-%, or up to 60 wt-%, such as up to 50 wt-%, or up to 40 wt-%, sometimes up to 30 wt-%, or even up to 20 wt-% of multi-branched isoparaffins, based on the total weight of paraffins in the HI effluent. Typically, the HI 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).

[0082] The presence of multi-branched isoparaffins in the HI effluent can be considered to be beneficial because it can be beneficial to the effective cracking degree in the second reactor. When the desired degree of effective cracking is achieved in the second reactor under milder operating conditions, particularly for C8-C14 hydrocarbons and for the effective cracking of lighter non-gaseous hydrocarbons, overcracking can be avoided and the formation of gaseous hydrocarbons can be reduced. In addition, the increased content of multi-branched isoparaffins in the HI effluent can be considered to be beneficial because it can improve the low temperature properties of the recovered liquid transportation fuel components, especially the low temperature properties of the aviation fuel component and / or the diesel fuel component and / or the RON of the gasoline fuel component. Without being bound by any theory, it is believed that multi-branched isoparaffins are more likely to form two branched paraffin molecules rather than one branched paraffin and one normal paraffin when cracking in the second reactor, which therefore increases the isoparaffin content of the recycled effluent.

[0083] The process of the present invention comprises subjecting a second reactor feed comprising a recycle stream to hydrocracking in the second reactor in the presence of a hydrocracking (HC) catalyst to obtain a recycle effluent. The hydrocracking isomerized heavy paraffins in the recycle stream increase the yield of aviation fuel components and provide flexibility for the use of different paraffin feeds, especially for the use of oxygenated hydrocarbon feeds converted thereto. Typically, the hydrocracking is carried out in the second reactor so that the cracking reactions, predominantly those that increase the effective degree of cracking, are more abundant than the hydroisomerization reactions in the first reactor. Preferably, the cracking reactions, especially those that increase the effective degree of cracking, predominate in the hydrocracking of the second reactor, but typically without overcracking and excess fuel gas formation.

[0084] The second reactor feed may also (in addition to the recycle stream) comprise a portion of the HI effluent, preferably as a degassed HI effluent, i.e. after the HI effluent is subjected to a gas-liquid separation to remove compounds that are gaseous at least at the NTP. In these embodiments, for example, the portion may be obtained by simply diverting the total HI effluent or preferably degassed HI effluent between the fractionation and the second reactor using, for example, a fixed or preferably gradually adjusted ratio. These embodiments provide further flexibility for the operation of the method, including further possibilities of adjusting the ratio of the recovered fuel components and their quality, as explained above. The amount of this portion of the HI effluent fed to the second reactor may vary, but typically only a smaller portion. Therefore, in certain preferred embodiments of the process of the present invention, the second reactor feed also comprises less than 50 wt-%, preferably less than 30 wt-%, more preferably less than 10 wt-% of HI effluent, preferably as a degassed HI effluent, based on the total weight of the second reactor feed.

[0085] In certain preferred embodiments, the second reactor feed consists essentially of the recycle stream and optionally (in addition to the recycle stream) a portion of the hydroisomerization effluent.

[0086] In the process of the present invention, the hydrocracking in the second reactor may be carried out at a temperature of 200°C to 450°C, preferably 220°C to 430°C, more preferably 280°C to 350°C, a pressure of 0.4MPa to 8MPa, preferably 1MPa to 7MPa, more preferably 2.5MPa to 7MPa, a H2O2 at the inlet of the second reactor of 0.4MPa to 8MPa, preferably 1MPa to 7MPa, more preferably 2.5MPa to 7MPa. 2 partial pressure, 0.1 to 10, preferably 0.2 to 8, more preferably 0.4 to 6, even more preferably 0.5 to 1.5 kg second reactor feed / kg catalyst / hour weight hourly space velocity, and 10 to 2000, preferably 50 to 1000 standard liters H 2 / L H of the second reactor feed 2 Typically, in the process of the present invention, the hydrocracking in the second reactor is carried out under the following conditions: a temperature in the range of 200°C to 450°C, a pressure in the range of 0.4MPa to 8MPa, and a ratio of H at the inlet of the second reactor to the feed of the second reactor. 2 The partial pressure is in the range of 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa, the weight hourly space velocity is in the range of 0.1 to 10 kg second reactor feed / kg catalyst / hour, and H 2 The ratio of the feed to the second reactor is between 10 and 2000, preferably between 50 and 1000 standard liters of H 2 / L of second reactor feed.

[0087] According to certain preferred embodiments, the hydrocracking in the second reactor is carried out under the following conditions: temperature in the range of 220°C to 430°C, pressure in the range of 1MPa to 7MPa, weight hourly space velocity in the range of 0.2 to 8kg second reactor feed / kg catalyst / hour, and H 2 The ratio of the feed to the second reactor is between 50 and 1000 standard liters of H 2 In other preferred embodiments, the hydrocracking in the second reactor is carried out under the following conditions: the temperature is in the range of 280°C to 350°C, the pressure is in the range of 2.5MPa to 7MPa, and the H at the inlet of the second reactor is 2 The partial pressure is in the range of 2.5 MPa to 7 MPa, the weight hourly space velocity is in the range of 0.4 to 6 kg second reactor feed / kg catalyst / hour, and H 2The ratio of the feed to the second reactor is between 50 and 1000 standard liters of H 2 When the HC is operated at a lower temperature and a sufficiently high pressure, the aromatization side reaction can be better suppressed or even dearomatization can be enhanced.

[0088] Preferably, the hydrocracking in the second reactor is operated so that the ratio of the wt-% amount of isoparaffins based on the total weight of paraffins in the recycle effluent to the wt-% amount of isoparaffins based on the total weight of paraffins in the feed to the second reactor 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; and / or so that the ratio of the C8-C14 hydrocarbon content in the recycle effluent to the C8-C14 hydrocarbon content in the feed to the second reactor is at least 1.1, preferably at least 1.3, more preferably at least 1.5, even more preferably at least 1.8 or at least 2.0.

[0089] In certain preferred embodiments, the hydrocracking in the second reactor is operated such that the ratio of the content of C1-C4 hydrocarbons formed during the hydrocracking in the (total) recycle effluent to the content of C1-C4 hydrocarbons in the (total) HI effluent is in the range of 1.1 to 5.0, preferably 1.1 to 4.0, more preferably 1.2 to 3.0; and / or such that the (total) recycle effluent contains less than 20 wt-%, or less than 10 wt-%, or less than 5 wt-% of C1-C4 hydrocarbons, based on the total weight of the recycle effluent.

[0090] This can be achieved in particular when using a second reactor feed as described above, and / or operating the second reactor under the hydrocracking operating conditions as described above, and / or in the presence of a HC catalyst as defined below, in particular in the presence of a non-sulphided bifunctional HC catalyst, preferably in the presence of a non-sulphided bifunctional HC catalyst comprising at least one or more Group VIII noble metals, more preferably Pt and / or Pd.

[0091] Typically, the recycle effluent comprises at least 60 wt-%, preferably at least 70 wt-%, more preferably at least 80 wt-%, even more preferably at least 90 wt-% or at least 95 wt-% paraffins based on the total weight of the recycle effluent. The recycle effluent may even consist essentially of paraffins.

[0092] According to certain preferred embodiments, the recycle effluent comprises at least 50 wt-%, preferably at least 60 wt-%, more preferably at least 70 wt-%, even more preferably at least 80 wt-% of isoparaffins, based on the total weight of the paraffins in the recycle effluent, and / or comprises at least 3 wt-%, or at least 5 wt-%, preferably at least 10 wt-%, more preferably at least 15 wt-%, even more preferably at least 20 wt-% of multi-branched isoparaffins, based on the total weight of the paraffins in the recycle effluent.

[0093] Preferably, when comparing the temperatures at the reactor inlets, the first reactor is operated at a higher temperature than the second reactor. The temperatures compared are the temperatures at the first reactor inlet and at the second reactor inlet, respectively, at a given point in time, including short time intervals. In other words, in this context, no comparison is made between the highest temperatures during the entire run from the start of the process to the termination of the process.

[0094] By operating the first reactor and the second reactor within the operating condition range as described above, and especially when the first reactor is operated at a higher temperature than the second reactor, a high degree of isomerization can be achieved in the first reactor while controlling, reducing or minimizing thermal cracking in the second reactor, and the content of multi-branched isoparaffins in the HI effluent can be increased. At the same time, under milder operating conditions, especially at lower temperatures, the desired effective cracking degree can be achieved in the second reactor, which improves the yield of hydrocarbons in the boiling range of aviation fuel and gasoline without causing excessive thermal cracking that leads to gas formation.

[0095] The process of the invention comprises subjecting the HI effluent to fractionation to separate from the fractionation a recycle stream comprising at least C16 n-paraffins and having a T5 temperature above 270°C (recovery 5 vol-%, EN ISO 3405-2019). The HI effluent may be fractionated as such, or as a degassed HI effluent, i.e. after subjecting the HI effluent to a gas-liquid separation to remove compounds that are gaseous at least at NTP, or the HI effluent, preferably as a degassed HI effluent, may be fractionated between the fractionation and the second reactor, typically a major portion thereof, as discussed above.

[0096] Preferably, the recycle stream has a T5 temperature of 275°C or more. In certain preferred embodiments, the T5 temperature of the recycle stream is in the range of 270°C to less than 300°C, preferably in the range of 270°C to less than 295°C, more preferably in the range of 270°C to less than 290°C; and / or the initial boiling point (IBP, EN ISO 3405-2019) is 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 be fractionated, i.e., the recycle stream may comprise the bottom heavy product of the total feed to be fractionated.

[0097] Preferably, the T5 temperature of the recycle stream is selected so that at least a portion of the C16 normal paraffins present in the total feed to be fractionated, such as the C16 normal paraffins present in the HI effluent (if any), are recovered in the recycle stream. Recovery of the C16 normal 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 normal paraffins is 287°C (at atmospheric pressure), but since fractionation (such as distillation separation) is not very precise, it is possible to recover C16 normal paraffins within a temperature range near this boiling point.

[0098] At least some C16 normal paraffins are recycled to the second reactor to carry out hydrocracking is beneficial, because C16 normal paraffins have a relatively high melting point. Therefore, C16 normal paraffins (for example) in the aviation fuel component of recovery may even make it unavailable in the aviation fuel composition with any large amount of existence, this is due to poor low temperature properties, especially freezing point difference, and / or at sub-zero temperatures, such as -20 ° C or -40 ° C The kinematic viscosity difference, i.e. high caused. In any case, the C16 normal paraffins in the aviation fuel component of recovery damage its low temperature properties, i.e. compared with the aviation fuel component with less or no C16 normal paraffin content, improve one or more in cloud point, freezing point, pour point and / or cold filter plugging point and / or sub-zero kinematic viscosity. Preferably, the recycle stream comprises at least 20wt-% or at least 30wt-%, more preferably at least 40wt-% or at least 50wt-% of the C16 normal paraffins in the total feed for fractionation. In the total feed to fractionation, the amount of normal paraffins, including C16 normal paraffins, may increase upon deactivation of the HI catalyst and may also be formed by cracking in the second reactor.

[0099] In certain particularly preferred embodiments, the recycle stream comprises at least 85 wt-%, preferably at least 90 wt-%, more preferably at least 95 wt-% C16+ paraffins of the total weight of paraffins in the recycle stream. Hydrocracking the C16+ paraffins in the second reactor is beneficial because it can increase the yield and / or improve the quality of aviation fuel components. C16+ normal paraffins have poor low temperature properties, while C18+ normal paraffins typically boil outside the aviation fuel boiling range.

[0100] Typically, the recycle stream comprises at least 60 wt-%, preferably at least 70 wt-%, more preferably at least 80 wt-%, even more preferably at least 90 wt-% or at least 95 wt-% of paraffins, based on the total weight of the recycle stream, or the recycle stream may even consist essentially of paraffins. In a particularly preferred embodiment, the recycle stream comprises at least 50 wt-%, preferably at least 60 wt-%, more preferably at least 70 wt-% or at least 80 wt-%, based on the total weight of paraffins in the recycle stream, and / or up to about 100 wt-%, or up to 98 wt-% of isoparaffins, and / or at least 5 wt-%, or at least 10 wt-%, preferably at least 15 wt-% or at least 20 wt-% of multi-branched isoparaffins, based on the total weight of paraffins in the recycle stream. Typically, the recycle stream comprises up to 95 wt-%, or up to 90 wt-%, or up to 80 wt-%, or up to 70 wt-%, such as up to 60 wt-%, or up to 50 wt-%, or up to 40 wt-%, sometimes up to 30 wt-%, or even up to 20 wt-% of multi-branched isoparaffins, based on the total weight of paraffins in the recycle stream, typically in the range of 5 wt-% to 95 wt-%, preferably 5 wt-% to 80 wt-%, or 5 wt-% to 70 wt-%, such as 10 wt-% to 70 wt-%, or 15 wt-% to 65 wt-% of multi-branched isoparaffins, based on the total weight of paraffins in the recycle stream. Typically, the cloud point of the recycle stream is less than 0°C, preferably less than -5°C, more preferably less than -8°C, even more preferably less than -10°C, further preferably less than -20°C, further preferably less than -30°C (ASTM D 5771-17). Typically, the recycle stream has a higher isoparaffin content and / or more multi-branched isoparaffin content than the HI effluent (total HI effluent or degassed HI effluent), preferably expressed as wt-% of isoparaffins or multi-branched isoparaffins, respectively, based on the total weight of paraffins in the corresponding stream or effluent.

[0101] Such a recycle stream has a particularly beneficial composition in view of the extent of effective cracking in the hydrocracking, thereby forming hydrocarbons boiling in the aviation fuel range and also in the gasoline boiling range, because paraffins are generally more easily cracked than cyclic hydrocarbons, longer paraffins are more easily cracked than shorter paraffins, and iso-paraffins are expected to be more easily cracked than normal paraffins, and the relative uniformity of the composition of the recycle stream can make it easier to optimize the hydrocracking conditions in the second reactor. In addition, these embodiments facilitate the easy separation of (for example) diesel fuel components, bunker fuel components, base oil components, and / or transformer oil components by diverting only from the recycle stream, to name only the components that can be separated from such a recycle stream.

[0102] Both the hydroisomerization (HI) and hydrocracking (HC) catalysts may be arranged in one or more catalyst beds within the respective reactors. The HI catalyst and the HC catalyst may be arranged in at least one or more fixed beds, respectively. The HI catalyst may be any conventionally used HI catalyst, and the HC catalyst may be any conventionally used HC catalyst. Preferably, the HI catalyst in the first reactor is a bifunctional HI catalyst, more preferably a non-sulfided bifunctional HI catalyst. More preferably, the HI catalyst in the first reactor and the HC catalyst in the second reactor are bifunctional HI and HC catalysts, respectively, more preferably non-sulfided bifunctional HI and HC catalysts, respectively.

[0103] Bifunctional HI and HC catalysts contain metal sites for catalyzing (de)hydrogenation reactions and acid sites for catalyzing isomerization and cracking reactions. Bifunctional HI catalysts and bifunctional HC catalysts are well known in the field of oil refining and renewable fuel production. Bifunctional HI and HC catalysts are preferred because they have excellent catalytic performance, thereby providing a synergistic effect between the metal sites and the acid sites. Bifunctional HI and HC catalysts are also beneficial because the entry and diffusion of molecules to the catalytic sites can be controlled by appropriately selecting the pore characteristics of the catalyst, especially the pore size, pore size and / or pore connectivity in the catalyst.

[0104] 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 noble metals selected from Group VIII of the Periodic Table of the Elements, more preferably metals selected from Pt and / or Pd, and at least one or more acidic porous materials, and wherein the paraffin feed and the second reactor feed each comprise less than 50 wt-ppm, preferably less than 30 wt-ppm, more preferably less than 10 wt-ppm sulfur (ppm by weight, calculated as elemental S) of the respective total feed as determined according to ISO 20846-2019.

[0105] Sulfur content can be determined from liquids according to ISO 20846-2019 or from gas fractions according to ASTM D6667.

[0106] Non-sulfided bifunctional catalysts are preferred because they do not require sulfidation to maintain their activity during operation and therefore the sulfur content of the process streams can be kept lower and less efficient H2 from the process streams is required. 2 In particular, the non-sulfided bifunctional catalyst containing a noble metal can be active at lower temperatures and show higher selectivity for isomerization reactions than the sulfided catalyst, but has a negative impact on the isomerization reaction by H 2 Sensitive to the inactivation of S.

[0107] Preferably, the paraffinic feed comprises less than 50 wt-ppm, preferably less than 30 wt-ppm, more preferably less than 10 wt-ppm (ppm by weight, calculated as elemental S) sulfur as determined according to ISO 20846-2019. A very low sulfur content in the stream entering the first reactor is beneficial because only very low amounts of H are formed in the HI in the first reactor. 2 S or almost no H 2 S, and therefore very low amounts of H in the HI effluent 2 S or almost no H 2 S. In these embodiments, the HI effluent is subjected to gas-liquid separation before feeding the portion to the second reactor, i.e., a portion thereof is introduced into the second reactor feed, and it is not necessary to protect the HC catalyst in the second reactor, but nonetheless, the gas-liquid separation of the HI effluent may be optionally performed. Thus, the entire process may be simpler, and a liquid transportation fuel component having an ultra-low sulfur content is obtainable. In addition, due to the presence of less H 2 S, in the long term, also foresee less corrosion and potentially for some equipment materials even less stringent corrosion resistance requirements may apply.

[0108] A variety of different kinds of bifunctional HI and HC catalysts are commercially available, for example with different metals or metal combinations, different metal loadings, different acid strengths and / or total acidities, and / or different porosities.

[0109] Bifunctional HC catalysts and bifunctional HI catalysts are similar in that both contain metal sites capable of catalyzing the hydrogenation (dehydrogenation) of normal (n) / iso (i)-alkanes to the corresponding n / i-olefins, and acid sites capable of catalyzing the protonation of n / i-olefins to n / i-carbenium ions, further isomerization of n-carbenium ions or i-carbenium ions, and / or cracking of n / i-carbenium ions to lighter n / i-olefins and lighter n / i-carbenium ions, as well as deprotonation of n / i-carbenium ions to n / i-olefins. The hydrogenation of various n / i-olefins to form n / i-alkanes is again catalyzed by the metal sites of these bifunctional catalysts. Under given operating conditions and given feed composition, which isomerization reaction or cracking reaction is dominant can be affected, among other things, by the characteristics of the bifunctional catalyst in contact with the feed. These characteristics of the bifunctional catalyst include, for example, the overall acidity of the catalyst, the number of Bronsted acid sites, the strength and / or density of the acid sites, and the metal content of the catalyst.

[0110] Preferably, the bifunctional HI and HC catalysts independently of each other comprise at least one or more metals selected from Group VIII of the Periodic Table of Elements, preferably noble metals selected from Group VIII, more preferably metals selected from Pt and / or Pd. Noble metals, especially noble metals in the bifunctional HI catalyst are preferred because they can provide higher selectivity for the isomerization reaction under the conditions of the first reactor compared to catalysts comprising only non-noble metals, and have high activity at lower operating temperatures. High activity at lower temperatures provides a wider temperature range within which the temperature can be adjusted during operation, typically increasing the temperature. The gradual deactivation of the catalyst that occurs when the process is operated for a longer period of time can be compensated to a certain extent by increasing the temperature in the reactor.

[0111] Preferably, the bifunctional HI and HC catalysts independently of each other comprise at least one or more porous acidic materials having a microporous, mesoporous or hierarchical (microporous-mesoporous) structure. A variety of zeolite-type materials, such as SAPO and zeolites are available to provide the desired acidity and pore characteristics.

[0112] According to certain embodiments, the HI catalyst is a bifunctional HI catalyst, preferably a non-sulfided bifunctional HI catalyst, comprising

[0113] at least one or more metals selected from Group VIII of the Periodic Table of Elements, preferably selected from noble metals of Group VIII, more preferably selected from metals of Pt and / or Pd; and

[0114] at least one or more acidic porous materials selected from zeolites and / or zeolite-type materials, wherein preferably at least one or more zeolites and / or zeolite-type materials have a framework type selected from the group consisting of 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

[0115] Optionally at least one or more of alumina, silica, amorphous silica-alumina, titania, titania and / or zirconia.

[0116] It has been found that this catalyst selection provides a higher isomerization selectivity in the first reactor, which further helps to achieve even higher amounts of isoparaffins, especially multi-branched isoparaffins, which can then be hydrocracked at lower temperatures in the second reactor. The SAPOs and zeolites mentioned are commercially available and have acidity and pore characteristics that allow isomerization of n-paraffins, even long chain n-paraffins, such as C16+ paraffins, including multi-branching.

[0117] In particular, for the hydrocracking reaction in the second reactor of the process of the present invention, bifunctional HC catalysts are beneficial because they have some isomerization activity in addition to cracking activity and may be particularly effective in efficient cracking. As a further advantage, it has been found that bifunctional HC catalysts comprising at least one or more metals selected from Group VIII noble metals, preferably selected from Pt and / or Pd, provide high activity at relatively low temperatures and thus even better control of thermal cracking compared to HC catalysts comprising non-noble metals. At low temperatures, the thermodynamic equilibrium tends to shift in the direction of dearomatization, thus reducing the formation of aromatics by side reactions. Providing a bifunctional HC catalyst to the second reactor makes it possible to achieve that the isoparaffin content (wt-% of isoparaffins on the total weight of paraffins) in the recycle effluent does not have to be significantly lower than that in the HI effluent, or can be the same or even higher.

[0118] Thus, according to certain embodiments, the hydrocracking catalyst is a bifunctional hydrocracking catalyst, preferably a non-sulfided bifunctional hydrocracking catalyst, comprising

[0119] At least one or more metals selected from Group VIII of the Periodic Table of Elements, Mo, Co and / or W, preferably selected from Ni, Mo, Co, W, Pt and / or Pd, more preferably selected from Pt and / or Pd; and

[0120] at least one or more acidic porous materials selected from zeolites, zeolite-type materials and / or amorphous silica-alumina, wherein preferably at least one or more zeolites or zeolite-type materials have a framework type selected from MFI, BEA, FAU, MOR, FER, AEL, AFI, ATO, AFO, MRE, MTT, MTW, TON and / or MRT, preferably at least one or more acidic porous materials selected from SAPO-5, SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, JSM-43, JSM-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, SAOP-11, ZSM-23, β-zeolite, Y-type zeolite and / or amorphous silica-alumina; and

[0121] Optionally, at least one or more of alumina, silica, titanium alumina, titania and / or zirconium oxide.

[0122] In certain embodiments, the HI catalyst in the first reactor and the HC catalyst in the second reactor have different acidity-related characteristics. The acidity-related characteristics of an acidic porous material, such as a zeolite, can include the nature, number and distribution of acid sites in terms of relative strength and can be determined by well-known methods, such as by adsorption-desorption methods, in which the release of adsorbed alkaline substances, such as ammonia or pyridine at higher temperatures indicates the presence of strong acid sites. As an example of a useful adsorption-desorption method, the temperature-programmed desorption of ammonia can be mentioned, for example, according to the procedure described in Niwa et al. (Niwa, M., Katada, N. Measurements of acidic property of zeolites bytemperature programmed desorption of ammonia. Catalysis Surveys from Asia 1, 215-226 (1997)). Another well-known method for determining the acidity of a zeolite, including the strength of the acidity, is 1H-NMR method, for example, as described in Heeribout et al. (Heeribout L., Semmer V., Batamack P., Dorémieux-Morin C., Fraissard J. Brønsted acid strength of zeolites studied by 1 H NMR: scaling, influence of defects. Microporous and Mesoporous Materials, Vol. 21, No. 4-6, May 1998, pp. 565-570). In certain embodiments, such as by NH 3 The bifunctional HC catalyst of the second reactor has a higher number of Bronsted acid sites than the bifunctional HI catalyst of the first reactor, as determined by NH 3 The bifunctional HC catalyst has a higher total number of acidic sites compared to the bifunctional HI catalyst as determined by -TPD.

[0123] In certain preferred embodiments, the bifunctional HC catalyst of the second reactor has a higher content (wt-%) of Group VIII noble metals than the bifunctional HI catalyst of the first reactor. In these embodiments, good or better yields of aviation fuel components are achieved at lower temperatures than in otherwise similar processes but using a bifunctional HC catalyst that does not have a higher content of said noble metals than the bifunctional HI catalyst.

[0124] In the process of the present invention, a paraffin feed is subjected to HI in the presence of a HI catalyst, and a second reactor feed comprising a recycle stream and optionally a portion of the HI effluent is subjected to hydrocracking in the presence of a HC catalyst. The HI catalyst and the HC catalyst may 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 in, for example, the choice of at least one or more of the catalyst components, acidity and / or metal loading, to name just a few examples, but it is also possible to use the same catalyst as the HI catalyst in the first reactor and the HC catalyst in the second reactor. Not only the catalyst, but also the operating conditions and the feed composition play a role in which reaction is dominant. For example, when the recycle stream is contacted with the HC catalyst under hydrocracking conditions, more cracking can be expected compared to contacting the paraffin feed with the HI catalyst under HI conditions, even if the catalyst is the same. Preferably, the paraffinic feed isomerizes rather than cracks when it is contacted with the HI catalyst under HI conditions, and the recycle stream (second reactor feed) cracks rather than isomerizes when it is contacted with the HC catalyst under hydrocracking conditions.

[0125] The HI catalyst and the HC catalyst may be in a ready-to-use state as such, or they may be treated in any conventional manner to adjust their properties (such as selectivity and / or activity) before or during startup by subjecting them to reduction, sulfidation and / or passivation, for example, with nitrogen-containing compounds such as amines or ammonia, to obtain ready-to-use fresh or regenerated HI catalyst and / or HC catalyst. As used herein, HI catalyst, HC catalyst, fresh catalyst and regenerated catalyst generally refer to catalysts in a ready-to-use state.

[0126] In certain embodiments, the hydrocracking is followed by additional hydroisomerization in the presence of an additional hydroisomerization catalyst. The additional HI can be achieved, for example, by disposing the additional HI catalyst in at least one separate bed in the second reactor and / or the subsequent third reactor.

[0127] The additional HI catalyst may be a HI catalyst as previously described in conjunction with the HI catalyst in the first reactor. Preferably, the additional HI catalyst is a bifunctional HI catalyst, more preferably a non-sulfurized bifunctional HI catalyst. The HI catalyst in the first reactor and the optional additional HI catalyst in the second and / or third reactor may have different characteristics and / or composition, or may have the same characteristics and composition, i.e. they may be different catalysts or the same catalyst. For simplicity of the process, preferably the additional HI catalyst is the same catalyst as the HI catalyst. In those embodiments, it is preferred that the HC catalyst is different from the HI catalyst and the optional additional HI catalyst.

[0128] How to select HI and hydrocracking conditions, preferably within the range of HI and hydrocracking conditions specified above, is well known to the skilled person, taking into account the selected HI catalyst, the composition of the paraffin feed and the target degree of isomerization, and the target content of multi-branched isoparaffins in the HI effluent; and taking into account the selected hydrocracking (HC) catalyst, the composition of the second reactor feed, the target effective degree of cracking, the target degree of isomerization, and the target content of multi-branched isoparaffins in the effluent of the second reactor. To some extent, when selecting or adjusting the operating conditions of the first and / or second reactor, the catalyst life or catalyst deactivation may also be taken into account. During continuous operation, the HI catalyst and the HC catalyst gradually deactivate (for example) due to impurities and coking in the process stream. Due to catalyst deactivation, the catalyst activity decreases and affects the selectivity, and at some point, the desired properties of the HI effluent and / or the recycle effluent can no longer be achieved. In addition, changes in the composition of the paraffin feed during operation can lead to deviations from the desired properties. When this occurs, at least one or more operating conditions of the first reactor and / or the second reactor may be adjusted, including, for example, temperature, pressure, WHSV, and / or H at the inlet of the first reactor and / or the second reactor. 2 The partial pressure is preferably adjusted within the operating conditions specified above to compensate for catalyst deactivation so that the desired properties of the HI effluent and / or the recycle effluent can be achieved again. Typically, this means increasing the temperature and / or reducing the WHSV and / or adjusting the H 2to paraffin feed ratio and / or increase the pressure. However, there are limits beyond which, for example, the temperature cannot be increased and / or the WHSV cannot be reduced without impairing the yield and / or quality of the recovered liquid transportation fuel components. For example, when the operating temperature is increased to sufficiently high values, thermal cracking side reactions increase, which increases the formation of gaseous hydrocarbons and thus reduces the yield of liquid products. Therefore, it is generally advantageous to start operating the HI reactor (the first reactor) at low temperature (using, for example, the lowest feasible temperature within the range specified) at the beginning of the run, as this provides the widest window for increasing the temperature as the catalyst gradually deactivates. In addition, the HC catalyst gradually deactivates during continuous operation, although generally at a lower rate than the HI catalyst, so similar considerations apply to adjusting the operating conditions of the second reactor.

[0129] In the process stream, the active sites of the catalyst may be occupied and the catalyst pores may be blocked by impurities and coke, making these sites no longer available for catalysis. For example, coke is caused by coke-forming compounds such as olefins, aromatics and naphthalene, and when present in the paraffin feed, coke formation can be enhanced by other impurities. For impurities that cause reversible catalyst deactivation, it may be sufficient to monitor the total content of this impurity or such impurities in the feed, as this can give an indication of the expected catalyst deactivation. For some other impurities, especially those that cause irreversible catalyst deactivation, it may be necessary to monitor the content of one or more such impurities in the paraffin feed and calculate as a received value: the cumulative amount thereof that the HI catalyst has encountered at a given time point from the start of the run, and compare the received value with a value that has been predetermined, for example, based on historical data or a model based on historical data to reflect excessive catalyst deactivation, so that it is no longer possible to foresee that the target yield and / or quality of the desired fuel component can be met.

[0130] Preferably, the process of the present invention comprises monitoring at least one or more parameters, typically parameters indicative of HI and / or HC catalyst deactivation, to receive at least one or more values, comparing the received values ​​with predetermined values, and adjusting at least one or more operating conditions in the first reactor and / or the second reactor based on the comparison, preferably within the operating conditions specified above for hydroisomerization and for hydrocracking, respectively.

[0131] Therefore, according to certain preferred embodiments, the method further comprises monitoring to receive at least one or more values ​​of at least one or more of the following parameters:

[0132] -The content of impurities in the paraffin 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 paraffin feed; the substance or impurity is a known catalyst deactivator, specifically a deactivator of a non-sulfurized bifunctional HI catalyst containing a precious metal. In addition, the substance or impurity is usually present in different amounts in feeds derived from vegetable oils, animal fats, microbial oils, organic wastes and residues from thermal liquefaction and / or enzymatic liquefaction, as well as in feeds derived from the Fischer-Tropsch process, and therefore can be brought into and present in the paraffin feed in different amounts in certain embodiments. Typically, elemental impurities themselves are not present in the paraffin feed, but their content indicates the presence of compounds containing the impurities. Elemental impurities and coke-forming compounds are determined by standard laboratory analysis. An increase in the content of any of these impurities may lead to an increase in catalyst deactivation.

[0133] -NH in the gas phase of the hydroisomerization effluent 3 and / or H 2 The content of S and / or NH in the gas phase of the recycle effluent 3 and / or H 2 S content; in some cases, NH 3 and / or H 2 An increased level of S may indicate increased exposure of the catalyst to said impurities. An increase in the level of any of these impurities may lead to increased catalyst deactivation.

[0134] - Physicochemical characteristics of the hydroisomerization effluent and / or the recycle effluent, preferably at least one or more of cloud point, freezing point, pour point, cold filter plugging point, kinematic viscosity, density and / or distillation characteristics; an increase in any of cloud point, freezing point, pour point, cold filter plugging point, kinematic viscosity and / or density may indicate increased catalyst deactivation. Distillation characteristics, where increases may indicate catalyst deactivation, include T5, T50, FBP, etc. As for other distillation characteristics, a shift in the boiling point distribution toward higher boiling point compounds may indicate catalyst deactivation. To some extent, the physicochemical characteristics may be indicative of or correlated with the content of isoparaffins or multi-branched isoparaffins in the HI effluent and / or the recycle effluent.

[0135] - Compositional characteristics of the hydroisomerization effluent and / or the recycle effluent, preferably at least one or more of the isoparaffin content, the C8-C14 hydrocarbon content, the multi-branched isoparaffin content and / or the C1-C4 hydrocarbon content in the hydroisomerization effluent and / or the recycle effluent; a decrease in the isoparaffin, multi-branched isoparaffin and / or C8-C14 hydrocarbon content may indicate an increase in catalyst deactivation. To some extent, the content of isoparaffin or multi-branched isoparaffin may be indicative of or correlated with the physicochemical characteristics of the HI effluent and / or the recycle effluent. The C1-C4 hydrocarbon content decreases with increasing catalyst deactivation. However, increasing the operating temperature to compensate for catalyst deactivation may result in an increase in the C1-C4 hydrocarbon content.

[0136] - The yield of at least one or more of the recovered liquid transportation fuel components and / or the separated recycle stream, preferably the yield of the recovered aviation fuel components; an increase in the yield of high boiling hydrocarbons and an increase in the volume of the separated recycle stream may indicate an increase in catalyst deactivation.

[0137] - At least one or more physicochemical characteristics of the recovered liquid transportation fuel component and / or the separated recycle stream, preferably at least one or more of cloud point, freezing point, pour point, cold filter plugging point, kinematic viscosity, density, research octane number (RON), cetane number and / or distillation characteristics; a decrease in cetane number can indicate an increase in catalyst deactivation. In the distillation characteristics, for example, an increase in T5, T50, T95 and / or FBP or a shift in the boiling point distribution to higher boiling compounds can indicate catalyst deactivation. To some extent, the physicochemical characteristics can be indicative of or correlated with the content of isoparaffins or multi-branched isoparaffins in the recovered liquid transportation fuel component and / or the separated recycle stream.

[0138] - Compositional characteristics of at least one or more of the recovered liquid transportation fuel component and / or the separated recycle stream, preferably the isoparaffin content and / or the multi-branched isoparaffin content of the recovered fuel component and / or the separated recycle stream; a decrease in the content of isoparaffins, multi-branched isoparaffins and C8-C14 hydrocarbons may indicate an increase in catalyst deactivation. To some extent, the content of isoparaffins or multi-branched isoparaffins may be indicative of or correlated with the physicochemical characteristics of the recovered liquid transportation fuel component and / or the separated recycle stream.

[0139] - and / or a temperature difference across the first reactor or the catalyst bed therein and / or across the second reactor or the catalyst bed therein; said temperature difference is relatively easy to monitor and a reduction in the temperature difference may be a typical feature of catalyst deactivation.

[0140] The received value is compared with a predetermined value, and based on the comparison, at least one or more operating conditions in the first reactor and / or the second reactor are adjusted, preferably the temperature, pressure, weight hourly space velocity (WHSV), H 2 The ratio of H 2 The ratio of the feed to the second reactor and / or the H at the inlet of the first reactor and / or the second reactor 2 At least one or more of the partial pressures, 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.

[0141] Different parameters may be monitored and / or different predetermined values ​​selected during the method, for example based on changes in target product and quality.

[0142] In certain preferred embodiments, the method includes monitoring at least two or at least three of the above parameters that are generally indicative of HI and / or HC catalyst deactivation. For example, an increase in the amount of shorter carbon chains due to increased cracking occurring in the first reactor (e.g., caused by an increase in temperature), rather than a sufficient degree of isomerization, can achieve good low temperature properties (e.g., cloud point, pour point, and / or sub-zero viscosity) of the HI effluent. Therefore, in order to better understand the state of catalyst deactivation, it may be beneficial to monitor at least two or three or even more parameters.

[0143] Monitoring can be performed continuously, repeatedly, continuously, periodically, intermittently, discontinuously, or monitoring can be a one-time monitoring. Monitoring can be performed online, for example, using one or more sensors located in any of the process stream, feed tank and / or product tank, including slipstream arrangements, or can be performed offline based on samples collected from any of the process stream, feed tank and / or product tank. The frequency and manner of monitoring one or more parameters can be performed independently of other monitored parameters, i.e., certain parameters can be (for example) continuously monitored online, while other parameters can be (for example) regularly monitored offline.

[0144] Monitoring can be discontinuous or one-time monitoring, particularly in embodiments where one or more operating conditions of the first reactor and / or the second reactor are adjusted based on historical process data, such as a model based on historical process data. For example, the content of one or more known catalyst deactivation impurities can be determined based on samples from each of the fresh feed tanks to be used in the method, and a temperature rise spectrum program can be set for the first reactor based on the content of the determined one or more impurities based on historical process data. Thus, adjustments to operating conditions can be made to obtain or maintain desired properties and / or yields of HI effluent, recycle effluent, separated recycle stream and / or recovered liquid fuel components, for example, based on historical process data from earlier method runs using, for example, similar feeds and similar qualitative and quantitative expectations for recovered liquid transportation fuel components, and / or models, such as theoretical models or models based on historical process data, and received values ​​obtained for the monitoring parameters illustrated above.

[0145] Once the operating conditions in the first reactor and / or the second reactor have been adjusted to their feasible extremes, preferably at the extremes within the range of hydroisomerization or hydrocracking conditions, respectively, as specified above, the catalyst needs to be changed to fresh catalyst or regenerated in order to reach the target isomerization degree and / or effective cracking degree again. As mentioned above, the process of the invention enables an improvement in catalyst life, i.e., an extension of the catalyst replacement / regeneration interval, and / or the use of feedstocks with a heavy impurity load.

[0146] The inventive method comprises fractionation, wherein reclaims at least one or more liquid transportation fuel components and separates the recycle stream. The amount of the separated recycle stream and the amount of the recycle stream fed to the second reactor can be changed within a wide range. Other liquid streams or fractions, such as side streams, can optionally be separated and / or recovered in the fractionation and optionally recycled back into the process.

[0147] Preferably, the recycle effluent and the HI effluent are fed to the fractionation in a weight ratio of 1:10 to 10:1, preferably 1:5 to 5:1. Preferably, the ratio is recycle effluent to HI effluent. When processing paraffinic feeds boiling at lower temperatures, a ratio of recycle effluent to HI effluent near the lower limit may be preferred, while when processing paraffinic feeds boiling at higher temperatures, such as paraffinic feeds containing paraffins heavier than C18, a ratio near the upper limit may be preferred.

[0148] The fractionation of the inventive method may include any commonly used fractionation techniques. Preferably, the fractionation includes distillation, such as atmospheric distillation or vacuum distillation, optionally preceded by gas-liquid separation, for example, as described below. The fractionation may be carried out in a fractionation system comprising one or more fractionation units. For example, gas and light naphtha may be separated in a pre-fractionation unit, while liquid transportation fuel components and recycle streams may be recovered and separated from a main distillation unit downstream of the pre-fractionation unit. In an alternative embodiment, a single fractionation unit may be used.

[0149] As mentioned, gas-liquid separation can be carried out to the recycle effluent and / or HI effluent in combination or independently of each other. Gas-liquid separation can be carried out as an integrated step in (for example) each reactor or in a fractionation system. Usually, 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 reactor in the effluent source, gas-liquid separation is carried out. Usually, the pressure during gas-liquid separation can be in the range of 0.1 MPa to 20 MPa, preferably in the range of 1 MPa to 10 MPa, or in the range of 3 MPa to 7 MPa.

[0150] According to certain embodiments of the present process, different products may be recovered from the fractionation as liquid transportation fuel components, depending, for example, on the operating conditions selected, the composition of the paraffinic feed used, and / or market demand at a given time.

[0151] The liquid transportation fuel components and optional other products separated and / or recovered from the fractionation may, for example, include a gasoline fuel component boiling in the range of about 25°C to about 200°C, an aviation fuel component 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, a diesel fuel component boiling in the range of about 160°C to about 380°C and / or a marine fuel component boiling in the range of about 180°C to about 600°C, such as in the range of about 180°C to about 400°C (boiling in the range determined according to EN ISO 3405-2019). In certain embodiments, first recover and / or separate gasoline fuel components boiling in the range of about 25°C to about 200°C from fractionation, at about 100°C to about 300°C, such as aviation fuel components boiling in the range of about 150°C to about 300°C and T5 temperature is a recycle stream of at least 270°C, and recover 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 in the range as determined according to EN ISO 3405-2019) from the separated recycle stream. Other products can be recovered from fractionation, such as shunting or further separating other products from the recycle stream. Examples of these other products include components for solvents, electrical fluids and base oils.

[0152] Using the process of the present invention, it is possible to produce an extremely low viscosity aviation fuel component having a lower freezing point, especially a lower kinematic viscosity at -20°C, compared to an aviation fuel component having similar IBP and FBP but produced by conventional HDO of a fat feedstock followed by HI (i.e., without hydrocracking as in the process of the present invention).

[0153] Therefore, in a preferred embodiment of the process of the present invention, the at least one liquid transportation fuel component recovered from the fractionation is an aviation fuel component having a density at 15°C in the range of 730 to 772 kg / m 3In some embodiments, the recovered aviation fuel component has a T10 temperature of at most 205°C (EN ISO 3405-2019), a T10 temperature of at most 205°C (EN ISO 3405-2019), a final boiling point of at most 300°C (EN ISO 3405-2019), a flash point of at least 38°C (IP 170-2013, Abel closed cup method) and a freezing point of at most -40°C (IP 529-2016). In these embodiments, the recovered aviation fuel component has a high quality and can be blended in an aviation fuel composition in an elevated amount. Typically, the T10 and T90 temperatures of the recovered aviation fuel component are in the range of 120°C to 295°C, preferably in the range of 130°C to 295°C, as determined according to EN ISO 3405-2019.

[0154] The inventive method can recover at least aviation fuel components with unexpectedly high yields, even at the end of the life of the HI catalyst. In a preferred embodiment of the inventive method, at least 30wt-%, preferably at least 40wt-%, more preferably at least 50wt-%, such as 30wt-% to 90wt-% of the gross weight of the paraffin feed are used to recover aviation fuel components. It is believed that this can be caused by the high content of C8 to C14 hydrocarbons and isoparaffins in the feed for fractionation, wherein a significant part is multi-branched isoparaffins. In some preferred embodiments, as determined according to EN ISO 3405-2019, the difference between the aviation fuel component T90 and T10 temperatures is at least 70°C, preferably at least 75°C, more preferably at least 80°C, even more preferably at least 85°C, usually at most 180°C, such as in the range of 80°C to 150°C, preferably in the range of 80°C to 130°C. In these embodiments, aviation fuel components can be recovered with improved yields while achieving desired low temperature properties, density and flash point characteristics. The poor quality of the total feed fed to the fractionation would require severe restriction of the FBP to meet the low temperature property requirements, which would also limit the T90 temperature and narrow the T90-T10 differential. However, in this context, the process of the present invention provides excellent characteristics, including a high degree of isomerization, particularly an extremely high multi-branched isoparaffin content, and an altered distillation profile because the amount of carbon number is more evenly distributed, particularly in the range of C6-C18.

[0155] Typically, in the method of the present invention, at least one or more aviation fuel components, diesel fuel components, gasoline fuel components and / or marine fuel components are recovered from fractionation, preferably at least aviation fuel components are recovered from fractionation, more preferably at least aviation fuel components and diesel fuel components, even more preferably at least aviation fuel components, diesel fuel components and gasoline fuel components. Typically, preferably at least regularly recover at least one heavy product from fractionation, such as diesel fuel components, marine fuel components and / or base oil components. In this way, the heaviest components can be removed from the recirculation loop.

[0156] In certain preferred embodiments, the recovered liquid transportation fuel component has a biogenic carbon content of at least 50 wt-%, preferably at least 70 wt-%, more preferably at least 90 wt-%, further preferably at least 95 wt-%, or even about 100 wt-%, based on the total weight of carbon (TC) in the corresponding recovered liquid transportation fuel component (EN 16640 (2017)). The biogenic carbon content in the recovered liquid transportation fuel component is primarily influenced by the biogenic carbon content in the paraffinic hydrocarbon feed, and in preferred embodiments, primarily by the oxygenated hydrocarbon feed subjected to the HDO. However, for example, any amount of fossil hydrocarbon diluent fed to the HDO reactor may affect the biogenic carbon content of the recovered liquid transportation fuel component.

[0157] Typically, the recovered liquid transportation fuel component has an improved (increased) isoparaffin content, in particular a polybranched isoparaffin content, compared to the corresponding component obtained by conventional HDO of a fatty feedstock followed by HI (i.e. without hydrocracking as in the process of the present invention). A typical aviation fuel component recovered from the process of the present invention comprises 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 isoparaffins, based on the total weight of the aviation fuel component; and / or at least 58 wt-%, preferably at least 60 wt-%, more preferably at least 62 wt-% of C6-C18 polybranched isoparaffins, based on the total weight of the aviation fuel component. Typical diesel fuel components recovered from the process of the present invention contain at least 70 wt-%, preferably at least 75 wt-%, more preferably at least 80 wt-%, even more preferably at least 90 wt-% C15-C22 isoparaffins by weight of the diesel fuel component; and / or at least 60 wt-%, preferably at least 63 wt-%, more preferably at least 65 wt-% C15-C22 multi-branched isoparaffins by weight of the diesel fuel component. Typical gasoline fuel components recovered from the process of the present invention contain at least 50 wt-%, preferably at least 55 wt-%, more preferably at least 60 wt-%, even more preferably at least 65 wt-% C4-C9 isoparaffins by weight of the gasoline fuel component; 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-% C6-C9 multi-branched isoparaffins by weight of the gasoline fuel component.

[0158] Even if each of the gasoline fuel component, the aviation fuel component and the diesel fuel component are recovered simultaneously in the process of the present invention, they can be recovered as reasonably broad fractions. When the yield of the aviation fuel component is optimized, the diesel fuel component can be recovered as a narrower fraction, or not recovered at all.

[0159] As shown in the examples, the products recovered from the process have excellent characteristics.The recovered liquid transportation fuel component is suitable for use as a blending component in a fuel composition and, when appropriately added, can even be used as a fuel itself, ie as an unblended component. The recovered liquid transportation fuel components and optional other products are suitable for a wide variety of other uses, such as in feedstocks for industrial conversion processes, preferably in thermal cracking feedstocks, such as steam cracking feedstocks and / or catalytic cracking feedstocks, in transformer oils, heat transfer media, switchgear oils, shock absorber oils, insulating oils, hydraulic fluids, gear oils, transmission fluids, degreasing compositions, penetrating oils, anti-corrosion compositions, multi-purpose oils, metalworking fluids, rolling oils, especially for aluminum, cutting oils, drilling fluids, solvents, lubricants, extender oils, carriers, dispersant compositions, demulsifiers, extractants, paint compositions, coating fluids or pastes, adhesives, resins, varnishes, printing pastes or inks, detergents, cleaning agents, plasticizing oils, turbine oils, hydrophobic compositions, agriculture, crop protection fluids, construction, concrete release formulations, electronic equipment, medical devices, compositions for the automotive, electrical, textile, packaging, paper, cosmetic and / or pharmaceutical industries, and / or intermediates for their manufacture. It is foreseen that a relatively high degree of isomerization and an increase in the shorter carbon chain fraction improves the flowability, pumping and mixing characteristics and miscibility of the recovered components and / or products. These are generally desirable and beneficial properties for a wide range of uses, particularly those involving spraying, injection and / or mixing with other ingredients.

[0160] Process diagram

[0161] Figure 1 The process according to the example embodiment is shown schematically. Figure 1 In the embodiment, an oxygenated hydrocarbon feed 110 is fed into an HDO reactor 120, wherein it is hydrodeoxygenated in the presence of an HDO catalyst 130 to obtain a hydrodeoxygenated effluent (HDO effluent) 140, and the obtained HDO effluent 140 is subjected to a gas-liquid separation 150 to separate a compound 160 that is gaseous at least at NTP from the HDO effluent to obtain a degassed HDO effluent 170, which in this example embodiment is a paraffin feed as defined herein. Then, Figure 1 The degassed HDO effluent 170 in the first reactor 180 is fed to the first reactor 180, wherein the degassed HDO effluent 170 is subjected to hydroisomerization in the presence of the HI catalyst 190 to obtain the HI effluent 200, and the obtained HI effluent 200 is subjected to gas-liquid separation 210 to separate the gaseous compound 220 at least at NTP from the HI effluent 200 to obtain the degassed HI effluent 230. Figure 1In the embodiment of the present invention, the degassed HI effluent 230 is fed to a distillation unit 240, which may include a single column or a pre-fractionation column and a main distillation column, from which several streams or fractions may be obtained. Figure 1 In the distillation, a gasoline fuel component 250, an aviation fuel component 260 and / or a diesel fuel component 270 are recovered. In addition, a recycle stream 280 having a T5 boiling point of 270°C or more is separated. Figure 1 In the embodiment of the present invention, the recycle stream 280 is fed to the second reactor 290, wherein it is hydrocracked in the presence of an HC catalyst 300 to obtain a recycle effluent 310. Figure 1 In the embodiment, the recycle effluent 310 is subjected to gas-liquid separation 320 to separate at least the gaseous compound 330 at NTP from the recycle effluent 310 to obtain a degassed recycle effluent 340, and then the degassed recycle effluent 340 is fed to the distillation unit 240 for fractionation as a co-feed with the degassed HI effluent 230. In certain embodiments, a portion of the HI effluent 200, 230 may be fed to the second reactor 290 as a co-feed 500 with the recycle stream 280 for hydrocracking.

[0162] Not limited to Figure 1In certain preferred embodiments of the method of the present invention wherein at least an aviation fuel component is recovered from fractionation and includes monitoring parameters preferably indicative of HI catalyst deactivation, the monitored parameters include at least one or more of the following: a temperature difference across the first reactor 180 or HI catalyst 190 bed, a cloud point and / or pour point of the degassed HI effluent 230, a cloud point and / or pour point of the recycle stream 280 or the diesel fuel component 270, a freezing point of the aviation fuel component 260, and / or one or more distillation characteristics, the corresponding received values ​​of the above being compared to predetermined values. When the monitored parameter is the cloud point of the degassed HI effluent 230, the predetermined value may be, for example, a maximum of -5°C; for the cloud point of the recycle stream 280 or the diesel fuel component 270, the predetermined value may be, for example, a maximum of -15°C (ASTM D 5771-17); for the freezing point of the aviation fuel component 260, the predetermined value may be, for example, a maximum of -40°C (IP 529-2016); for the distillation characteristics of the aviation fuel component 260, the predetermined value for T10 may be, for example, a maximum of 205°C, or for the T90-T10 difference may be, for example, a minimum of 22°C (EN ISO 3405-2019); for the distillation characteristics of the diesel fuel component 270, the predetermined value for T95 may be, for example, a maximum of 360°C (EN ISO 3405-2019). Parameters indicative of HC catalyst deactivation may be similarly monitored with reference only to the second reactor 290 and the HC catalyst 300 bed therein and the degassed recycle effluent 340 obtained therefrom. The received values ​​may be compared to predetermined values, and at least one or more operating conditions in the first reactor and / or the second reactor, preferably temperature, pressure, weight hourly space velocity (WHSV), H 2 Ratio of feed to paraffin, H 2 The feed ratio to the second reactor and / or the H at the inlet of the first reactor and / or the second reactor 2 After adjustment, the monitored parameters and predetermined values ​​may remain unchanged, or different parameters may be monitored and / or different predetermined values ​​may be selected, for example, based on whether the same product and its quality are still targeted.

[0163] Figure 2 A comparative process further comprising a hydrocracking step is shown as an example. For the comparative example, the process was used in Example 1. Figure 2In the comparative example, an oxygenated hydrocarbon feed 110 is fed into an HDO reactor 120, wherein it is hydrodeoxygenated in the presence of an HDO catalyst 130 to obtain a hydrodeoxygenated effluent (HDO effluent) 140, and the obtained HDO effluent 140 is subjected to a gas-liquid separation 150 to separate a compound 160 that is gaseous at least at NTP from the HDO effluent to obtain a degassed HDO effluent 170, which in this comparative example is a paraffin feed as defined herein. Then, Figure 2 The degassed HDO effluent 170 in the first reactor 180 is fed to the first reactor 180, wherein the degassed HDO effluent 170 is subjected to hydroisomerization in the presence of the HI catalyst 190 to obtain the HI effluent 200, and the obtained HI effluent 200 is subjected to gas-liquid separation 210 to separate the gaseous compound 220 at least at NTP from the HI effluent 200 to obtain the degassed HI effluent 230. Figure 2 In the process, the degassed HI effluent 230 is fed to a second reactor 290, wherein it is hydrocracked in the presence of an HC catalyst 300 to obtain a hydrocracked effluent 350, and the hydrocracked effluent 350 is subjected to a gas-liquid separation 360 to separate a compound 370 that is gaseous at least at NTP from the hydrocracked effluent 350 to obtain a degassed hydrocracked effluent 380. Figure 2 In the embodiment of the present invention, the degassed hydrocracking effluent 380 is fed to a distillation unit 240, which may include a single column or a pre-fractionation column and a main distillation column, where it is fractionated into several streams or fractions. Figure 2 In the distillation, a gasoline fuel component 390, an aviation fuel component 400 and a diesel fuel component 410 are recovered.

[0164] Example

[0165] Example 1 - Simulation

[0166] Simulations were performed using Aspen Plus V10.0 software to illustrate the benefits of the process of the present invention compared to a conventional HVO process in which a fat feedstock is subjected to a hydrodeoxygenation (HDO) step and a subsequent hydroisomerization (HI) step, as disclosed in, for example, FI100248 and EP1396531, and then fractionated to recover at least the aviation fuel components.

[0167] The oxygenated hydrocarbon feed fed to HDO contained 100% animal fat, and the high paraffin feed (containing about 98 wt-% paraffins) fed to HI contained about 59 wt-% C17-18 normal paraffins, about 29 wt-% C15-16 normal paraffins, about 4 wt-% C17-18 isoparaffins, and about 2 wt-% C15-16 isoparaffins. About 97 wt-% of the paraffin feed fed to HI was C14-C22 hydrocarbons, and about 1 wt-% was cyclic hydrocarbons.

[0168] Reference 1 (Tables 1 and 2) shows a typical product distribution recovered from the fractionation of a conventional HVO process operated in a winter grade renewable diesel production mode (i.e. comprising an HDO step followed by a medium severity HI step). Reference 2 (Tables 1 and 2) shows a typical product distribution recovered from the fractionation of an HVO process operated with a HDO step similar to Reference 1 but followed by a high severity HI step using fresh catalyst.

[0169] For INV (Tables 1 and 2), use Figure 1 The process shown, wherein the HDO and HI steps are run similarly to Reference 1, followed by fractionation of the HI effluent and the recycle effluent from the hydrocracking reactor fed with the recycle stream (a portion of the diesel component recovered from the fractionation). For the comparative examples (Tables 1 and 2), the Figure 2 The process shown in , where the HDO and HI steps are operated similarly to Reference 1, followed by hydrocracking and fractionation of the HI effluent.

[0170] The components shown in Table 1 are recovered from the fractionation. Tables 1 and 2 show that the method of INV provides a significantly improved yield (71.6 wt-%) of high-quality sustainable / renewable aviation fuel (SAF) components compared to the methods of Reference 2 and the Comparative Examples without sacrificing the overall yield of liquid products or the properties of other liquid products. In addition, the method using INV achieves an almost 5-fold higher yield of gasoline components. As a significant benefit relative to the method of Reference 2, improvements in yield and product quality are achieved while avoiding the limitations of the method of Reference 2, i.e., the use of high severity HI, which typically involves elevated temperatures and / or lower WHSVs compared to medium severity HI conditions, and / or the use of fresh HI catalysts, is not required. The product properties achieved by the INV method are at a similarly high level to the product performance achieved by the Comparative Examples, and the aviation fuel component obtained by INV has a slightly better (lower) kinematic viscosity at -40°C.

[0171] Table 1. Simulation test results, yields based on raw material feed (oxygenated hydrocarbons).

[0172]

[0173] Table 2. Product properties. SAF stands for Sustainable / Renewable Aviation Fuel Component.

[0174]

[0175] Example 2 - Test Run

[0176] 2.1 Production of Liquid Transportation Fuel Components

[0177] First, an oxygenated hydrocarbon feedstock containing animal fats and vegetable oils is pretreated to remove impurities using conventional bleaching procedures. The bleached oxygenated hydrocarbon feedstock is hydrodeoxygenated using a sulfided NiMo catalyst supported on alumina at about 320°C, about 50 bar, using a WHSV between 0.3 and 1 1 / h and a hydrogen flow rate between 500 and 1000 Nl / l feed. Gas and water are separated from the liquid stream and discarded to obtain a paraffinic feed. A typical exemplary composition of such a paraffinic feed derived from a mixture of animal fats and vegetable oils is, based on the total weight of the paraffinic feed: about 99 wt-% paraffins, about 9 wt-% total isoparaffins, about 2 wt-% multi-branched isoparaffins, about 90 wt-% normal paraffins, about 1 wt-% total amount of hydrocarbons other than paraffins (e.g., cyclic hydrocarbons, olefins), about 99 wt-% total amount of C12-C30 hydrocarbons, and about 98 wt-% total amount of C14-C20 hydrocarbons.

[0178] In the presence of a non-sulfurized bifunctional hydroisomerization catalyst (Pt / SAPO), the obtained paraffin feed is hydroisomerized. The conditions in the HI reactor are low severity conditions for obtaining stream 1 and high severity conditions for obtaining stream 2. The HI effluent is subjected to gas-liquid separation (degassing) and stabilization, whereby the gas is removed and the light naphtha fraction (first pass gasoline fuel component) is recovered to obtain streams 1 and 2. Fractionation is continued by recovering the (first pass) aviation fuel component and the heavy bottom product as a recycle stream that can be used as the (first pass) diesel fuel component from the stabilized stream, stream 1 and stream 2, respectively. Table 3 provides the properties of various streams and products.

[0179] Table 3. HI conditions, yields and properties of streams 1 and 2 of the degassed and stabilized HI effluent and first pass gasoline fuel components, first pass aviation fuel components and recycle streams 1 and 2 (first pass diesel fuel components).

[0180]

[0181] The properties of recycle stream 1 will allow it to be used as a diesel fuel component, for example in a summer diesel, while the properties of recycle stream 2 will allow it to be used as a diesel fuel component, for example in a winter diesel grade.

[0182] A portion of recycle stream 1 and a portion of recycle stream 2 are subjected to hydrocracking using a non-sulfided bifunctional precious metal catalyst on an acidic material. The temperature in the hydrocracking step is varied so that it is lower than, similar to, or higher than the temperature in the hydroisomerization step. The hydrocracking conditions, the nature of the total liquid product collected from the hydrocracking (i.e., the degassed recycle effluent), and the yield of the total liquid product (as a second reactor feed (including H 2 The wt-% of ) is shown in Table 4. The composition characteristics of the hydrocracking products (degassed recycle effluent) are shown in Table 5.

[0183] Table 4. Liquid yield (including H 2 The cloud point and density of the degassed recycle effluent (total liquid product) from the test runs performed using different conditions also indicate whether the temperature at the hydrocracking is higher, lower or approximately equal to the temperature at the corresponding HI (T(HI)). In all experiments, H 2 The feed ratio to the second reactor was 300 nL / L.

[0184]

[0185] As can be seen from Table 4, the liquid yields in each of the test runs in Table 4 were high, with higher HC temperatures having a slightly lowering effect on the liquid yields. In addition, each of the recycle effluents recovered from the test runs had a significantly lower cloud point and lower density compared to the corresponding recycle stream. The reduction in cloud point was more significant in the recycle effluent derived from recycle stream 1, which initially had a higher cloud point (compared to recycle stream 2).

[0186] Table 5. Composition analysis of the degassed recycle effluent (of total liquid products) as determined by GC x GC-FID / GC x GC-MS.

[0187]

[0188] As can be seen from Table 5, each recycle effluent derived from recycle stream 1 has an effectively reduced C15-C18 hydrocarbon content, a reduced normal paraffin content, and a greatly increased multi-branched isoparaffin content compared to recycle stream 1. The aromatic content in these recycle effluents is at most the same (at the highest HC temperature) or lower than the aromatic content in recycle stream 1, which indicates dearomatization at lower HC temperatures. Compared to recycle stream 2, each recycle effluent derived from recycle stream 2 (for which the C15-C18 content was determined) has an effectively reduced C15-C18 content. Compared to recycle stream 2, each recycle effluent derived from recycle stream 2 (for which the normal paraffin content was determined) has a slightly increased normal paraffin content. Compared to recycle stream 2, most recycle effluents derived from recycle stream 2 have an increased multi-branched isoparaffin content. Only the recycle effluent of the test run using the highest HC temperature had a slightly reduced content of multi-branched isoparaffins compared to recycle stream 2. The aromatic content in the recycle effluent originating from recycle stream 2 decreased, indicating that effective dearomatization occurred during HC, except in test run 3 involving HC at the highest temperature (352°C), where the aromatic content increased slightly, most likely due to the combination of high temperature and low pressure. In summary, these results indicate that hydrocracking of recycle streams reduces the C15-C18 content from about 95 wt-% to less than 90%, even below 40 wt-%, under a variety of hydrocracking conditions, and that hydrocracking not only cracks monobranched iP molecules into one normal paraffin and one isoparaffin, but also effectively increases the degree of isomerization in terms of multi-branched isoparaffin content. This effect can also be inferred from the physicochemical characteristics of the recycle effluent reported in Table 4: the density and especially the cloud point of the recycle effluent are lower than those of the corresponding recycle streams.

[0189] The yields of recoverable C1-C4 gases, C5+ gases and gasoline, aviation and diesel fuel components were calculated from the SIMDIS analysis of the recycle effluent and are reported in Table 6.

[0190] Table 6. Product yields (including H) based on gas analysis and liquid product analysis (simulated distillation ASTM D2887-19e1). 2 wt-% of the second reactor feed). Liq. means liquid.

[0191]

[0192] It can be seen from Table 6 that lower hydrocracking temperatures provide slightly higher liquid yields than higher hydrocracking temperatures. In general, the 150-300°C fraction yield (i.e., the aviation fuel boiling range) is at a good level, especially when a lower WHSV is used. Increasing the WHSV seems to reduce the 150-300°C fraction yield, but only a little, while at IBP-150°C, a more significant reduction in fraction yield is observed, and at the same time the 300°C-FBP fraction yield increases. Unexpectedly, even when hydrocracking the highly isomerized and multi-branched recycle stream 2, the yields of C1-C4 remain low. Only in test run 3 involving HC at high temperature (352°C) combined with low pressure (20 bar) did the gas yield increase. Therefore, adjusting the hydrocracking operating conditions seems to provide a convenient way to adjust the yields of different liquid transportation fuel components (for example) based on market demand.

[0193] 2.2 Properties of the Multi-Recovered Liquid Transportation Fuel Components

[0194] The recycle effluent from the hydrocracking test run was fractionated to recover gasoline fuel components, aviation fuel components and diesel fuel components. In addition, for one of the recycle effluents, fractionation was performed in an optimized manner to increase the yield of the aviation fuel component (test run 8 with optimized fractionation, TR8o). Table 7 reports some product properties.

[0195] Table 7. Distillation characteristics of gasoline, aviation and diesel fuel components recovered from the recycle effluent of selected test runs. Yields are expressed as wt-% of the degassed recycle effluent.

[0196]

[0197] It can be seen from Table 7 that the distillation characteristics of the gasoline, aviation and diesel fuel components recovered from the recycle effluent of the selected test runs meet the corresponding specifications.

[0198] The properties of jet fuel components from TR15 and TR8 with optimized fractionation (TR8o) were analyzed. The physicochemical characteristics are reported in Table 8 and the composition details for each carbon number analyzed by GC×GC-FID / GC×GC-MS are reported in Table 9. Paraffinic renewable jet fuel components obtained by conventional HDO and high severity HI processes (i.e. without hydrocracking) of aliphatic feedstocks were used as references (RRJF).

[0199] Table 8. Physicochemical characteristics of aviation fuel components recovered from test runs TR15 and TR8o compared to the reference jet component RRJF.

[0200]

[0201] Table 9. Compositional characteristics per carbon number of the recovered jet fuel components from test runs TR15 (overall results) and TR8o (detailed results) compared to the reference jet component RRJF (overall results) as determined by GC×GC-FID / GC×GC-MS. Results are provided as wt-%.

[0202]

[0203] In Table 9, nP refers to normal paraffin, monobranched iP refers to monobranched isoparaffin, iP-dimer refers to isoparaffin with two (methyl) branches, iP-trimer refers to isoparaffin with three (methyl) branches, and iP-tetramer refers to isoparaffin with four (methyl) branches.

[0204] From the analysis of the aviation fuel components (Table 8), it can be seen that the aviation fuel components recovered from the test runs have excellent low temperature properties, especially the freezing point and kinematic viscosity at -20°C. The composition analysis reported in Table 9 shows that for the aviation fuel components recovered from the test runs, the wt-% amount is more evenly distributed over carbon numbers in the C6-C18 range: TR8o produced 52.8 wt-% and TR15 produced 41.9 wt-% C15-C18 paraffins compared to 71.9 wt-% for the reference RRJF. This contributes to (for example) a more balanced distillation curve and combustion behavior, as well as a lower density. Detailed composition analysis of the TR8o aviation fuel components reveals extremely low nP content and extremely high iP content, especially high multi-branched iP content, which is reflected in the excellent freezing point and sub-zero kinematic viscosity.

[0205] The characteristics of the diesel fuel components of TR8, TR8o, TR14, TR15 and TR16 were analyzed and reported in Table 10. A winter grade paraffinic renewable diesel fuel component obtained by conventional HDO and medium severity HI processes of fatty feedstocks (i.e. without hydrocracking) was used as a reference (Ref RDW). A fossil Arctic diesel fuel component as well as recycle stream 2 (before hydrocracking) were used as another reference.

[0206] Table 10. Physicochemical characteristics of diesel fuel components recovered from the test runs.

[0207]

[0208] *Assuming TR8 diesel fuel composition and Ref RDW has a calorific value of 44.0 MJ / kg.

[0209] From Table 10 it can be seen that the diesel fuel components recovered from the test runs have improved low temperature properties in terms of cloud point compared to the winter grade reference renewable diesel and recycle stream 2, while the measured cetane number is at a similar high level. Unexpectedly, each of the diesel fuel components recovered from the test runs had a significantly higher viscosity at 40°C, and also had a higher density, especially compared to the reference winter diesel. This means that the diesel fuel components recovered from the test runs can be blended into diesel fuel at higher proportions and still meet the density requirements at 15°C in Table 1 of EN590-2022 (820-845 kg / m 3 The obtained diesel fuel component is also beneficial in Arctic grade diesel fuel (EN 590-2022 Table 3), where it effectively improves the viscosity of the fuel (at 40°C) and the spray behavior in the fuel system, leading to better fuel economy. Composition analysis of the diesel fuel component recovered from the test run (results not reported) showed that the total isoparaffins and multi-branched isoparaffins content were elevated compared to the reference RDW, which contributes to the excellent cloud point and viscosity characteristics shown in Table 10.

[0210] The characteristics of gasoline fuel components from TR8, TR15 and TR8o were analyzed and reported in Table 11. Paraffinic renewable gasoline fuel components obtained by conventional HDO and medium severity HI processes (ie without hydrocracking) of fatty feedstocks were used as reference (Ref RG).

[0211] Table 11. Physicochemical and compositional characteristics of gasoline fuel components recovered from the test runs.

[0212]

[0213] *Calculated based on the amount of wt-% of n-paraffins, iso-paraffins and multi-branched iso-paraffins per carbon number as determined by GC-FID / GC-MS

[0214] **Blend RON (bRON) and blend MON (bMON) are determined from blends with commercial gasoline components with high isoparaffin content according to EN ISO 5164-2014 (corresponds to ASTM D2699-18) and EN ISO 5163-2014 (corresponds to ASTM D2700-19), respectively.

[0215] It can be seen from Table 11 that the bRON and bMON octanes determined for the gasoline fuel components recovered from the test run are highly improved compared to the reference renewable gasoline fuel component (Ref RG). In addition, each gasoline fuel component recovered from the test run has a significantly higher C4-C9 isoparaffin content compared to the reference renewable gasoline component. This shows that hydrocracking not only cracks the paraffin molecules, but also improves the degree of isomerization. The average carbon number in the C4-C9 range is reduced, especially for normal paraffins. Both the higher degree of isomerization and the shorter normal paraffins are believed to contribute to the improved octane number. Due to the improved properties, the gasoline fuel component can be blended into the gasoline fuel at a higher ratio than the reference renewable gasoline fuel component.

[0216] In summary, for use in fuel compositions, each of the liquid fuel components recovered from the test runs had improved characteristics, at least in terms of improved degree of isomerization, which generally enhanced low temperature properties and flowability / mixability even at lower temperatures. These and other improved characteristics of the liquid fuel components recovered from the test runs are desirable and are also beneficial in a wide range of other uses, particularly those involving spraying, injection, and / or mixing with other ingredients.

[0217] A number of implementations have been provided.It should be understood that in this document, the words include, comprise and contain are each used as open expressions without intended exclusivity.

[0218] The above description provides a complete and informative description of the best mode currently considered by the inventors for implementing the present invention by means of non-limiting examples of specific implementations and embodiments. However, it is clear to those skilled in the art that the present invention is not limited to the details of the embodiments present in the above description, but in other embodiments, it can be implemented in an equivalent manner or in a combination of different embodiments without departing from the characteristics of the present invention.

[0219] In addition, some features of the example embodiments disclosed above can be used to provide advantages without the corresponding use of other features. As such, the above description should be considered as merely an illustration of the principles of the present invention, rather than a limitation thereof. Therefore, the scope of the present invention is limited only by the attached patent claims.

Claims

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

2. The process according to claim 1, wherein the hydroisomerization in the first reactor is carried out at a temperature in the range of 200 to 500°C, preferably 230 to 500°C, more preferably 250 to 450°C, even more preferably 280 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 partial pressure at the inlet of the first reactor of 1 MPa to 10 MPa, preferably 2 MPa to 8 MPa, a weight hourly space velocity in the range of 0.1 to 10, preferably 0.2 to 8, more preferably 0.4 to 6 kg paraffin feed / kg catalyst / hour, and a H to paraffin feed ratio in the range of 10 to 2000, preferably 50 to 1000 standard liters of H / liter of paraffin feed.

3. The process according to claim 1 or 2, wherein the hydrocracking in the second reactor is carried out at a temperature in the range of 200 to 450°C, preferably 220 to 430°C, more preferably 280 to 350°C, a pressure in the range of 0.4 to 8 MPa, preferably 1 MPa to 7 MPa, more preferably 2.5 MPa to 7 MPa, a H partial pressure at the second reactor inlet in the range of 0.4 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, preferably 0.2 to 8, more preferably 0.4 to 6, even more preferably 0.5 to 1.5 kg second reactor feed / kg catalyst / hour, and a H to second reactor feed ratio in the range of 10 to 2000, preferably 50 to 1000 standard liters of H / liter of second reactor feed.

4. A process according to any one of the preceding claims, wherein the first reactor is operated at a higher temperature than the second reactor.

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

6. The process according to any one of the preceding claims, wherein the recycle stream has a cloud point (ASTM D 5771-17) of less than 0°C, preferably less than -5°C, more preferably less than -8°C, even more preferably less than -10°C.

7. The process according to any one of the preceding claims, wherein the recycle stream has a T5 temperature (EN ISO 3405-2019) in the range of 270°C to less than 300°C, preferably in the range of 270°C to less than 295°C, more preferably in the range of 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.

8. Process according to any one of the preceding claims, wherein the recycle effluent and the hydroisomerization effluent are fed to fractionation in a weight ratio of 1 :10 to 10:1 , preferably 1 :5 to 5:1 .

9. The process according to any one of the preceding claims, wherein the second reactor feed further comprises a portion of the hydroisomerization effluent.

10. The method according to any one of the preceding claims, comprising monitoring to receive at least one or more values ​​of at least one or more of the following parameters: - the content of impurities in the paraffinic 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 feed; - the NH3 and / or H2S content in the gas phase of the hydroisomerization effluent and / or the NH3 and / or H2S content in the gas phase of the recycle effluent; - physicochemical characteristics of the hydroisomerization effluent and / or the recycle effluent, preferably at least one or more of cloud point, freezing point, pour point, cold filter plugging point, kinematic viscosity, density and / or distillation characteristics; - compositional characteristics of the hydroisomerization effluent and / or the recycle effluent, preferably at least one or more of the isoparaffin content, C8-C14 hydrocarbon content, multi-branched isoparaffin content and / or C1-C4 hydrocarbon content in the hydroisomerization effluent and / or the recycle effluent; - the yield of at least one or more of the recovered liquid transportation fuel components and / or said separated recycle stream, preferably the yield of recovered aviation fuel components; - a physicochemical characteristic of at least one or more of the recovered liquid transportation fuel component and / or the separated recycle stream, preferably at least one or more of cloud point, freezing point, pour point, cold filter plugging point, kinematic viscosity, density, research octane number (RON), cetane number and / or distillation characteristics; - compositional characteristics of at least one or more of the recovered liquid transportation fuel component and / or the separated recycle stream, preferably the isoparaffin content and / or the multi-branched isoparaffin content of the recovered fuel component and / or the separated recycle stream; - a temperature difference in the first reactor or in the catalyst bed therein, and / or a temperature difference in the second reactor or in the catalyst bed therein; The received value is compared with a predetermined value, and based on the comparison, at least one or more operating conditions in the first reactor and / or the second reactor are adjusted, preferably at least one or more of the temperature, pressure, weight hourly space velocity (WHSV), the ratio of H2 to paraffin feed, the ratio of H2 to the second reactor feed and / or the H2 partial pressure at the inlet of the first reactor and / or the second reactor, respectively, more preferably the temperature and / or pressure in the first reactor and / or the second reactor are increased, and / or the WHSV in the first reactor and / or the second reactor is decreased, respectively.

11. The process according to any one of the preceding claims, wherein the hydrocracking is followed by a further hydroisomerization in the presence of a further hydroisomerization catalyst, wherein the further hydroisomerization is preferably carried out under the operating conditions defined in claim 2.

12. The process according to any one of the preceding claims, wherein the hydroisomerization catalyst and / or the further hydroisomerization catalyst is a bifunctional hydroisomerization catalyst, preferably a non-sulfided bifunctional hydroisomerization catalyst, comprising at least one or more metals selected from Group VIII of the Periodic Table of Elements, preferably selected from noble metals of Group VIII, more preferably selected from Pt and / or Pd; and at least one or more acidic porous materials selected from zeolites and / or zeolite-type materials, wherein preferably at least one or more zeolites and / or zeolite-type materials have a framework type selected from the group consisting of 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, titania, titania and / or zirconia.

13. The process according to any one of the preceding claims, wherein the hydrocracking catalyst is a bifunctional hydrocracking catalyst, preferably a non-sulfided bifunctional hydrocracking catalyst, comprising At least one or more metals selected from Group VIII of the Periodic Table of Elements, Mo, Co and / or W, preferably selected from Ni, Mo, Co, W, Pt and / or Pd, more preferably selected from Pt and / or Pd; and at least one or more acidic porous materials selected from zeolites, zeolite-type materials and / or amorphous silica-alumina, wherein preferably at least one or more zeolites or zeolite-type materials have a framework type selected from MFI, BEA, FAU, MOR, FER, AEL, AFI, ATO, AFO, MRE, MTT, MTW, TON and / or MRT, preferably at least one or more acidic porous materials selected from SAPO-5, SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, JSM-43, JSM-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, SAOP-11, ZSM-23, β-zeolite, Y-type zeolite and / or amorphous silica-alumina; and Optionally, at least one or more of alumina, silica, titanium alumina, titania and / or zirconium oxide.

14. The process according to any one of the preceding claims, wherein the hydroisomerization catalyst and the hydrocracking catalyst are different from each other.

15. A process according to any one of the preceding claims, wherein the paraffinic hydrocarbon feed comprises At least 70 wt-%, preferably at least 80 wt-%, more preferably at least 90 wt-%, even more preferably at least 95 wt-% of the total weight of the paraffin feed of paraffins, 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 paraffin 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 the total weight of the paraffinic hydrocarbon feed are C12-C30 hydrocarbons, and / or At least 70 wt-%, preferably at least 80 wt-%, more preferably at least 90 wt-%, even more preferably at least 95 wt-% C14-C22 hydrocarbons based on the total weight of the paraffinic hydrocarbon feed.

16. The method according to any one of the preceding claims, wherein providing the paraffinic feed comprises catalytically hydrotreating a hydrotreated feed, preferably catalytically hydrodeoxygenating an oxygenated hydrocarbon feed, to obtain a paraffin hydrotreated effluent, wherein the hydrotreated feed preferably comprises at least one or more of vegetable oils, animal fats, microbial oils, thermally liquefied organic wastes and residues and / or enzymatically liquefied organic wastes and residues, and / or subjecting the synthesis gas to a Fischer-Tropsch (FT) conversion to obtain a paraffinic FT effluent, The paraffin hydrotreating effluent and / or the paraffin FT effluent is subjected to gas-liquid separation and optionally to paraffin feed fractionation to provide a paraffin feed.

17. The process of claim 16, wherein providing the paraffinic hydrocarbon feed comprises subjecting an oxygenated hydrocarbon feed to catalytic hydrodeoxygenation, and wherein the hydrodeoxygenation is carried out in the presence of a hydrodeoxygenation catalyst and at a temperature in the range of 200°C to 500°C, at a pressure in the range of 1 MPa to 20 MPa, at a H2 partial pressure at the reactor inlet in the range of 1 MPa to 20 MPa, at a weight hourly space velocity in the range of 0.1 to 10 kg oxygenated hydrocarbon feed / kg catalyst / hour and at a H2 to oxygenated hydrocarbon feed ratio of 50 to 2000 standard liters H2 / liter oxygenated hydrocarbon feed.

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

19. The method according to any one of the preceding claims, wherein the biocarbon content (EN 16640 (2017)) of the paraffinic 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 feed.

20. The process according to any one of the preceding claims, wherein at least one or more aviation fuel components, diesel fuel components, gasoline fuel components and / or marine fuel components are recovered from the fractionation, preferably at least an aviation fuel component, more preferably at least an aviation fuel component and a diesel fuel component, even more preferably at least an aviation fuel component, a diesel fuel component and a gasoline fuel component.

21. A process according to any one of the preceding claims, wherein the at least one liquid transportation fuel component recovered from the fractionation is an aviation fuel component having a relative humidity of 730 to 772 kg / m at 15°C. 3 density within the range of 100 °C (EN ISO 12185-1996), a T10 temperature of up to 205 °C (EN ISO 3405-2019), a final boiling point of up to 300 °C (EN ISO 3405-2019), a flash point of at least 38 °C (IP 170-2013, Abel closed cup method) and a freezing point of up to -40 °C (IP 529-2016).

22. The process according to any one of the preceding claims, comprising recovering aviation fuel components from fractionation at least 30 wt-%, preferably at least 40 wt-%, more preferably at least 50 wt-%, such as 30 to 90 wt-% of the total weight of the paraffinic feed.

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