Process for producing liquid transport fuel component

Abstract

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

Description

Technical Field

[0001] The present disclosure generally relates to a process for producing a renewable fuel component. The present disclosure particularly, but not exclusively, relates to a process 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] In the transportation sector, and in particular in the aviation sector, there is a continuing need to reduce greenhouse gas emissions and / or carbon footprint. As a result, interest in renewable aviation fuels and aviation fuel components is and has been growing.

[0004] Methods for producing aviation fuel components from renewable raw materials have been proposed. However, in such 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 present invention aims to solve or alleviate at least some of the problems associated with the prior art. One 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. Yet another object is to reduce the formation of C1-C4 hydrocarbons, especially C1-C2 hydrocarbons, in a method for producing a renewable liquid transportation fuel component. In addition, it is an object to extend the life of a hydroisomerization catalyst in a method 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 exemplary aspect, there is provided a method of producing at least one liquid transportation fuel component, the method comprising:

[0008] providing a paraffinic feed comprising at least 60 wt% paraffinic hydrocarbons based on the total weight of the paraffinic feed, at most 30 wt% of the paraffinic hydrocarbons being isoparaffinic hydrocarbons;

[0009] subjecting a paraffinic hydrocarbon feed to hydroisomerization in the presence of a hydroisomerization catalyst in a first reactor to obtain a hydroisomerization effluent comprising at least 50 wt% isoparaffins based on the total weight of the paraffinic hydrocarbons;

[0010] subjecting a second reactor feed comprising the hydroisomerization effluent to hydrocracking in a second reactor in the presence of a hydrocracking catalyst to obtain a hydrocracked effluent;

[0011] The hydrocracking effluent is subjected to fractionation and at least one or more liquid transportation fuel components are recovered from the fractionation.

[0012] 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, it has been shown that hydrocracking of a hydroisomerization (HI) effluent with a high degree of isomerization is successful in converting highly isomerized paraffins into valuable fuel components, in particular valuable fuel components in the aviation fuel range, without forming excessive light gases. It has been shown that hydrocracking of a highly isomerized HI effluent, in particular in the presence of a hydrocracking catalyst capable of both cracking and isomerization, is extremely beneficial.

[0013] The inventor has found that the obtainable fuel component by the inventive method has extremely useful characteristics.Compare with the obtainable liquid fuel component of the conventional method of hydroisomerization from the hydrodeoxygenation comprising fat raw materials, 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, these enhanced low-temperature properties of the obtainable fuel component by the inventive method and even 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.

[0014] 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

[0015] Some example embodiments will be described with reference to the accompanying drawings, in which:

[0016] Figure 1 A comparative process for producing at least one or more liquid transportation fuel components including hydrocracking is schematically illustrated.

[0017] Figure 2An exemplary embodiment of the process of the present invention for producing at least one or more liquid transportation fuel components comprising hydrocracking is schematically illustrated. DETAILED DESCRIPTION

[0018] In the following description, like reference symbols denote like elements or steps.

[0019] Unless otherwise stated, all standards referred to herein are to the latest revision available on the date of submission.

[0020] Unless otherwise stated, for distillation characteristics such as initial boiling point (IBP), final boiling point (FBP), T5 temperature (recovery 5 vol%), T95 temperature (recovery 95 vol%) 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.

[0021] As used in the context of this 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] As used herein. Hydrocarbons of particular interest in the context of this document include paraffins, n-paraffins, isoparaffins, mono-branched isoparaffins, multi-branched isoparaffins, olefins, cycloalkanes, and aromatics. Oxygenated hydrocarbons herein refer to hydrocarbons containing covalently bound oxygen.

[0026] As used herein, paraffin refers to non-cyclic alkanes, i.e., non-cyclic, open-chain saturated hydrocarbons that are straight (normal paraffin) or branched (isoparaffin). In other words, paraffin refers to normal paraffin and / or isoparaffin in this article.

[0027] 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, isoparaffin with an alkyl side chain or branch is referred to as monobranched isoparaffin, and isoparaffin with two or more alkyl side chains or branches is referred to as multi-branched isoparaffin in this article. In other words, isoparaffin refers to monobranched isoparaffin and / or multi-branched isoparaffin 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 isoparaffin can be given respectively. The term "isoparaffin" refers to the total amount of any monobranched isoparaffin and any multi-branched isoparaffin (if present), and it represents the total amount of any isoparaffin not considering the number of branches. Accordingly, "paraffin" refers to the total amount of any normal paraffin, any monobranched isoparaffin and any multi-branched isoparaffin (if present).

[0028] 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.

[0029] As used herein, cyclic hydrocarbons refer to all hydrocarbons containing ring structures, including cycloolefins, cycloalkanes and aromatic hydrocarbons. Cycloalkanes refer to cyclic alkanes (cycloalkanes) in this article, i.e., saturated hydrocarbons containing at least one ring structure with or without side chains. Since cycloalkanes are saturated compounds, they are compounds without aromatic ring structures. Aromatic hydrocarbons refer to hydrocarbons containing at least one aromatic ring structure in this article, i.e., ring structures with delocalized alternating π bonds around the ring structure.

[0030] In the context of the present disclosure, for gasoline fuel components, the content of n-paraffins, isoparaffins, mono-branched isoparaffins, various multi-branched isoparaffins, olefins, cycloparaffins 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 isoparaffins 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-160m, 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; tail gas flow: helium, 30 ml / min; split: 165:1 (165 ml / min). GC-MS was used to identify individual compounds (operating parameters: ion source: 230°C; interface: 280°C; scan: 25-280 m / z; scan speed: 303; scan event time: 0.88). Commercial tools (Shimadzu LabSolutions / GCMSSolutions and Agilent OpenLab) were used to identify the detected compounds or hydrocarbon groups, and their mass concentrations were determined by applying the response factor relative to n-heptane to the area of ​​the detected peak and then normalizing to 100 wt% (for liquid volume concentration: by applying the density factor to the calculated mass concentration of the detected peak and then normalizing to 100 vol%). Olefin cycloalkanes are reported under cycloalkanes. The quantitative limit of a single compound of this method is 0.1 wt%.

[0031] In the context of the present disclosure, for compositions boiling at or above 36°C (at standard atmospheric pressure), the content of normal paraffins, isoparaffins, mono-branched isoparaffins, various multi-branched isoparaffins, cycloparaffins 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 isoparaffins 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: as generally disclosed in the experimental part of 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, and with the following modifications to perform the GC×GC (2D GC) method. The GC×GC was run in reverse mode, first using a semipolar column (Rxi17Sil), then a nonpolar column (Rxi5Sil), followed by a 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; tail 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; scanning range: 25-500 amu; event time (seconds): 0.05; scanning 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 their mass concentrations were determined by applying the response factor relative to n-heptane to the volume of the detected peaks and then normalizing to 100 wt%. Unless reported separately, olefins are classified as cycloalkanes and heteroatom-containing substances are classified as aromatics. The quantitative limit of a single compound of this method is 0.1 wt%.

[0032] 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.

[0033] Typically, the various paraffinic hydrocarbon 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.

[0034] In the context of the present disclosure, unless otherwise stated, the feed to a reactor, in particular to the first reactor and / or the second reactor, is defined as the amount of H that is possible to feed to the respective reactor. 2 , for example, H fed to the hydroisomerization 2 and H fed to the hydrocracking 2 Excluded from the definition of feed.

[0035] 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.

[0036] 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.

[0037] In the context of the present disclosure, CY-paraffin, CY-n-paraffin, CY-isoparaffin, CY-monobranched isoparaffin, CY-polybranched isoparaffin, CY-hydrocarbon or CY-fatty acid refers to a paraffin, n-paraffin, isoparaffin, monobranched isoparaffin, polybranched isoparaffin, hydrocarbon or fatty acid having a carbon number up to Y, respectively, wherein Y is any feasible integer.

[0038] It should be understood that not every compound falling within the scope of this definition must be present. In the context of this disclosure, CX Y -CX Z (or CX Y To CXZ ) Paraffin, CX Y -CX Z Paraffin, CX Y -CX Z Isoparaffin, CX Y -CX Z Monobranched isoparaffin, 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 It is a feasible terminal integer, wherein the carbon number within the scope is indicated by any integer (if present) between the terminal integer and the described terminal. However, unless clearly stated, otherwise as the case may be, all the carbon numbers described are within the scope, and paraffin, normal paraffin, isoparaffin, single branched isoparaffin, multi-branched isoparaffin, hydrocarbon or fatty acid at or near the endpoint do not necessarily exist. On the other hand, according to definition, isomers can include several compounds with the same carbon number, such as C15 isomers can include methyltetradecane (different positions of methyl side chains), dimethyltridecane (different positions of two methyl side chains) etc., and wherein " C15 isomers " include the summation of all these variants.

[0039] Usually, the summation of the weight or volume of paraffin, normal paraffin, isoparaffin, single branched isoparaffin, multi-branched isoparaffin, hydrocarbon or lipid acid, as defined each time, represents to include all carbon numbers.For example, C15 to C22 normal paraffin refers to any normal paraffin in the described scope, as C15, C16, C17, C18, C19, C20, C21 and C22 normal paraffin, even if the content of C15 normal paraffin is zero.In other words, by 0 (referring to non-existent C15 normal paraffin) being joined in the gross weight of all other C15 to C22 normal paraffins existing, total amount is obtainable.

[0040] Isomerization converts at least a certain amount of normal paraffins into isoparaffins, especially into monobranched isoparaffins. By (further) increasing the degree of isomerization, for example by increasing the severity of the hydroisomerization as described below, more normal paraffins can be converted into isoparaffins, and monobranched isoparaffins can be converted into multi-branched isoparaffins, such as di-branched and / or tri-branched isoparaffins, or even isoparaffins containing more than three branches.

[0041] 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 hydrocracking effluent to the C8 to C14 hydrocarbon content in the second reactor feed.

[0042] 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 will 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, a separation and distillation unit, which can be arranged according to conventional engineering practices in the art.

[0043] 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 start of the process of the present invention.

[0044] As used herein, the term catalyst deactivation refers to the amount of catalyst deactivation occurring at the start of the process of the present invention (t 0 ) catalyst activity and / or selectivity at a given time point (t n The term catalyst deactivation is used herein to deactivate the catalyst, which is 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 deactivation type or mechanism, 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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 method is 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 their various blends. In numbers, the biochar content can be expressed as the weight percentage of the amount of biochar in the material to 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 greater than 50 wt%, in particular greater than 60 wt% or greater than 70 wt%, preferably greater than 80 wt%, more preferably greater than 90 wt% or greater than 95 wt%, even more preferably about 100 wt%, based on the total weight of carbon in the material (EN 16640 (2017)).

[0049] The present disclosure provides a method for producing at least one liquid transportation fuel component, the method comprising: providing a paraffinic feed, the paraffinic feed comprising at least 60 wt% paraffinic hydrocarbons based on the total weight of the paraffinic feed, and at most 30 wt% of the paraffinic hydrocarbons are isoparaffinic hydrocarbons; subjecting the paraffinic feed to hydroisomerization in a first reactor in the presence of a hydroisomerization catalyst to obtain a hydroisomerization effluent, the hydroisomerization effluent comprising at least 50 wt% isoparaffinic hydrocarbons based on the total weight of the paraffinic hydrocarbons; subjecting a second reactor feed comprising the hydroisomerization effluent to hydrocracking in a second reactor in the presence of a hydrocracking catalyst to obtain a hydrocracking effluent; subjecting the hydrocracking effluent to fractionation; and recovering at least one or more liquid transportation fuel components from the fractionation.

[0050] Preferably, the process of the present invention is a continuous process.

[0051] Typically, in the process 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 the fractionation, preferably at least aviation fuel components, 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. Compared to conventional processes for producing fuel components, for example, by hydrodeoxygenation (HDO) and HI of renewable fats and oils, using the process of the present invention, it is possible to obtain a higher yield of aviation fuel components over the life of the hydroisomerization (HI) catalyst without reducing the capacity of HI in the first reactor, and / or improve the quality of aviation fuel components. Experimentally, test runs carried out according to the process of the present invention have shown that an HI effluent having a total isoparaffin content of 94 wt% produces aviation fuel components in high yield, and has a total isoparaffin content of 92.5 wt% and a freezing point as low as -76.4°C. It is believed that the highly isomerized paraffins by the HI effluent contribute high yields and improved quality to cracking, particularly in the C8 to C14 range, without significantly reducing the degree of isomerization.

[0052] 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 life of a hydroisomerization (HI) catalyst. 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 life of the HI catalyst, 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.

[0053] The process of the present invention proposes to subject the hydroisomerization (HI) effluent with a high degree of isomerization 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 feed to the second reactor 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.

[0054] The highly isomerized HI effluent subjected to hydrocracking contains at least 50 wt% of isoparaffins and generally 5 to 75 wt% of multi-branched isoparaffins of the total weight of paraffins in the hydroisomerization effluent. 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 second reactor feed with less isomerization). 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 is for the effective cracking degree, especially for C8-C14 hydrocarbons, but also for the effective cracking degree of lighter non-gaseous hydrocarbons. It is also believed that multi-branched isoparaffins increase the isoparaffin content of the hydrocracking effluent (compared to the second reactor feed with a lower or no multi-branched isoparaffin content). The increased effective cracking degree in the second reactor without forming excess gaseous hydrocarbons and the increased isoparaffin content of the hydrocracking effluent can be beneficial for both the yield and quality of the recovered transportation fuel components, especially for the yield and quality of the preferably recovered aviation fuel components. Hydrocracking can increase the yield of the aviation fuel component as well as improve its quality, such as its low temperature properties, especially reducing its freezing point and / or viscosity at sub-zero temperatures (such as -20°C).

[0055] During the continuous operation of catalytic hydroisomerization and hydrocracking, the catalyst is gradually deactivated, for example, 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 for extending the life of the HI and HC catalysts. Compared with conventional methods for producing liquid fuel components by HDO and HI from renewable fats and oils, the present method compensates for the multiple possibilities of HI catalyst deactivation, in particular, enabling the use of paraffinic feeds with higher impurity contents. In addition, the hydrocracking step enables the use of feeds containing heavier and longer chain molecules than the conventional methods for producing liquid fuel components (usually diesel components), while enabling the production of lower boiling liquid transportation fuel components, such as aviation fuel components and / or gasoline fuel components, with good yields and quality.

[0056] In some preferred embodiments of the inventive method, a portion of the hydroisomerization effluent is fed to fractionation as a co-feed with the hydrocracking effluent. In these embodiments, for example, the portion can be obtained by simply shunting the total HI effluent or preferably degassed HI effluent between the second reactor and fractionation using a ratio that is, for example, fixed or preferably gradually adjusted. These embodiments provide further flexibility for the operation of the inventive method, and provide the possibility of even more accurately adjusting the method to simultaneously meet the target yield and quality of more than one recovered fuel component. In this way, it is possible to avoid the situation where 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 (for example, producing a diesel fuel component with an unnecessary low cloud point).

[0057] In the method of the present invention, the paraffin feed being hydroisomerized in the first reactor comprises at least 60wt% of the paraffin of the total weight of the paraffin feed, and the paraffin is at most 30wt% is isoparaffin. This means that when the paraffin feed comprises 60wt% of the paraffin of the total weight of the paraffin feed, at most 30wt% of the total weight of the paraffin in the paraffin feed, i.e. at most 18wt% of the total weight of the paraffin feed is isoparaffin. Preferably, the paraffin feed comprises at least 70wt% of the total weight of the paraffin feed, more preferably at least 80wt%, even more preferably at least 90wt% of the paraffin. The paraffin feed of the present disclosure may comprise even at least 95wt% of the paraffin of the total weight of the paraffin feed, or may consist essentially of paraffin. 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, and small amounts of aromatics and / or cycloalkanes based on the total weight of the paraffinic feedstock.

[0058] The advantage of using a highly paraffinic feed in the process of the present invention is that paraffins are relatively easy to isomerize and isomerize under milder conditions when subjected to HI than, for example, cyclic hydrocarbons. In addition, paraffins are relatively easy to crack and crack under milder conditions when subjected to hydrocracking.

[0059] Of the paraffins in the paraffin feed of the present disclosure, preferably up to 25 wt%, more preferably up to 20 wt%, and even more preferably up to 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.

[0060] 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 because 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 can produce a HI effluent with a higher content of multi-branched isoparaffins compared to an otherwise similar feed that does not contain isoparaffins.

[0061] Preferably, the paraffinic hydrocarbon feed of the present disclosure comprises at least 70wt% of the total weight of the paraffinic hydrocarbon feed, preferably at least 80wt%, more preferably at least 90wt%, even more preferably at least 95wt% of hydrocarbons having a carbon number in the range of C12 to C30. In certain particularly preferred embodiments, the paraffinic hydrocarbon feed comprises at least 70wt% of the total weight of the paraffinic hydrocarbon feed, preferably at least 80wt%, more preferably at least 90wt%, even more preferably at least 95wt% of hydrocarbons having a carbon number in the range of C14 to C22. Paraffinic hydrocarbon feeds having a 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 obtained (for example) from conventional hydrodeoxygenation (HDO) processes of vegetable oils, animal fats and / or microbial oils containing fatty acids.

[0062] 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% of the total weight of paraffins in the paraffin feed, preferably at least 60wt%, more preferably at least 70wt%, even more preferably at least 80wt% or at least 90wt% of the C16+ paraffins. 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.

[0063] 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 catalytically hydrotreating the hydroprocessed feed, preferably catalytically hydrodeoxygenating the oxidized hydrocarbon feed, to obtain a paraffin hydroprocessing effluent, wherein the hydroprocessing 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 hydroprocessing effluent and / or the paraffin FT effluent to gas-liquid separation, and optionally subjecting the paraffin feed to fractionation to provide the paraffin feed. Gas-liquid separation refers to the removal of compounds that are gaseous at least at NTP.

[0064] Although (for example) paraffinic FT effluents of fossil origin 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).

[0065] In certain embodiments, the paraffinic feed comprises or consists essentially of a degassed paraffinic Fischer-Tropsch effluent or a fraction thereof. The Fischer-Tropsch process comprises catalytically converting a synthesis gas comprising carbon monoxide and hydrogen, typically into substantially Gaussian distributed hydrocarbon chains, primarily normal paraffins, having a broad carbon chain length distribution, such as from C2 to C100+, typically from about C5 to about C50. The FT effluent is typically highly paraffinic, comprising primarily normal paraffins. Catalytic FT conversion of the synthesis gas may result in a lesser degree of isomerization, the FT effluent typically comprising about 10 wt% or less of isoparaffins based on the total weight of the FT effluent. The synthesis gas used in the FT process may be produced from renewable materials, natural gas, coal, or a combination thereof.

[0066] 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 gas-liquid separation of the paraffinic hydroprocessing effluent and optionally fractionation of the paraffinic feed to provide a degassed hydroprocessing effluent or a fraction thereof.

[0067] 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 removes organic sulfur compounds in the form of dihydrosulfide (H 2 S) in the form of hydrodesulfurization (HDS), from organic nitrogen compounds to ammonia (NH 3 ), i.e., hydrodenitrogenation (HDN), removal of halogens, e.g., removal of chlorine from organochlorine 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.

[0068] 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 to obtain 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.

[0069] In certain embodiments, providing a paraffinic hydrocarbon feed comprises subjecting an oxygenated hydrocarbon feed, preferably to hydrodeoxygenation 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 fractionation of the paraffinic hydrocarbon feed to obtain a degassed hydrodeoxygenation effluent or a fraction thereof as a paraffinic hydrocarbon 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. 2partial pressure, a weight hourly space velocity in the range of 0.1 to 10 kg oxygenated hydrocarbon feed / kg catalyst / hour, and a temperature in the range of 50 to 2000 Nl H 2 / L oxygenated hydrocarbon feed in the range of 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 vegetable oil, animal fat and / or microbial oil. Preferably, the hydrodeoxygenation is carried out as described in prior art publications such as FI100248B, EP1741768A1, EP2155838B1 or FI129220B1.

[0070] The optional paraffinic feed fractionation is usually carried out in a fractionation unit different from the fractionation unit used to recover the liquid transportation fuel components and / or separate the optional recycle stream. The optional paraffinic feed fractionation can be considered separate from the fractionation of the process of the present invention, which includes fractionation to recover the liquid transportation fuel components and / or to separate the optional recycle stream.

[0071] 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 tolerated by 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 having a slightly increased isoparaffin content can be obtained.

[0072] 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.

[0073] 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 ... 2partial 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 paraffin feed H 2 Carried out at a ratio with paraffin feed.

[0074] According to certain embodiments, the hydroisomerization in the first reactor is carried out under the following conditions: the temperature is in the range of 200° C. to 500° C., the pressure is in the range of 1 MPa to 10 MPa, and the 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 hydrocarbons is between 10 and 2000 NlH 2 / L paraffin feed range.

[0075] 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 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 NlH 2 / L paraffin feed range.

[0076] Preferably, before feeding the HI effluent to the hydrocracking in the second reactor, the HI effluent is subjected to a gas-liquid separation, i.e., to removal of compounds that are gaseous at least at NTP, including, for example, NH 3 and / or H 2 S. This can be done, for example, as an integrated step within the first reactor. By removing the gas phase, the HC catalyst can be protected against impurities therein. In addition, when the second reactor feed is degassed, optimizing the hydrocracking conditions in the second reactor can be easier and therefore more uniform.

[0077] 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 lower pressures and / or using higher WHSVs. Towards the end of the HI catalyst life, higher temperatures and / or higher pressures and / or lower WHSVs may be required to achieve even moderately severe HI. In the context of the present invention, HI producing a liquid effluent having, as the 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 to 55 wt%, or at least 95 wt% total isoparaffin content 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.

[0078] Preferably, the hydroisomerization in the first reactor is operated such that the ratio of the amount of wt% of isoparaffins by total weight of paraffins in the HI effluent to the amount of wt% of isoparaffins by 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 multibranched isoparaffins by total weight of paraffins in the HI effluent to the amount of wt% of multibranched isoparaffins by 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 can 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.

[0079] 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.

[0080] 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%, or at least 10 wt%, or at least 15 wt%, or even at least 20 wt% of multi-branched isoparaffins, based on the total weight of paraffins in the HI effluent. Typically, the cloud point of the HI effluent is 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).

[0081] In certain preferred embodiments, the HI effluent comprises 50 wt% to 100 wt%, preferably 60 wt% to 100 wt%, more preferably 70 wt% to 100 wt%, even more preferably 80 wt% to 100 wt% of isoparaffins, based on the total weight of paraffins in the hydroisomerization effluent; and / or 5 wt% to 75 wt%, preferably 10 wt% to 70 wt%, more preferably 15 wt% to 70 wt%, even more preferably 15 wt% to 65 wt% of highly branched isoparaffins, based on the total weight of paraffins in the hydroisomerization effluent. Such HI effluents are particularly preferred for achieving a good degree of effective cracking in the second reactor, because paraffins are generally more susceptible to cracking than cyclic hydrocarbons, and isoparaffins are expected to be more susceptible to cracking than normal paraffins, and are generally produced in the hydrocracking effluent to a high isoparaffin content.

[0082] Preferably, the hydroisomerization effluent comprises at least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt%, even more preferably at least 80 wt% or at least 90 wt% C16+ paraffins based on the total weight of paraffins in the hydroisomerization effluent.

[0083] 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 effective cracking of the desired degree is achieved in the second reactor under milder operating conditions, particularly for C8 to C14 hydrocarbons and for the effective cracking of lighter non-gaseous hydrocarbons, excessive cracking can be avoided, and the formation of gaseous hydrocarbons is reduced. In addition, the content of multi-branched isoparaffins increased 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 hydrocracking effluent.

[0084] The method of the present invention comprises subjecting the second reactor feed comprising the hydroisomerization effluent to hydrocracking in the second reactor in the presence of a hydrocracking catalyst to obtain a hydrocracking effluent. The hydrocracking of highly isomerized paraffins in the HI effluent enables the yield of aviation fuel components to be increased, and provides flexibility for the use of different paraffin feeds, in particular for the use of oxygenated hydrocarbon feeds converted thereto. Typically, hydrocracking is performed in the second reactor so that cracking reactions, especially those that increase the effective degree of cracking, are more abundant than the reactions after the hydroisomerization in the first reactor. Preferably, cracking reactions, especially those that increase the effective degree of cracking, dominate the hydrocracking in the second reactor, but there is usually no over-cracking and excess fuel gas formation.

[0085] The second reactor feed may comprise the HI effluent as such, or preferably 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 the NTP, or the HI effluent, preferably as a degassed HI effluent, may be split between the second reactor and a fractionation, typically a major portion being subjected to hydrocracking, as will be discussed subsequently.

[0086] In certain preferred embodiments, the second reactor feed consists essentially of at least a portion of the hydroisomerization effluent and optionally a subsequently defined recycle stream. For example, the second reactor feed may consist essentially of the HI effluent and optionally a recycle stream.

[0087] 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 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa, more preferably 2.5 MPa to 7 MPa, and a H2O2 content of 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa, more preferably 2.5 MPa to 7 MPa at the inlet of the second reactor. 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 H 2The 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.

[0088] 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 1 MPa to 7 MPa, weight hourly space velocity in the range of 0.2 to 8 kg second reactor feed / kg catalyst / hour, and H 2 The ratio of the feed to the second reactor is between 50 and 1000 Nl H 2 In certain 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 2 The ratio of the feed to the second reactor is between 50 and 1000 Nl H 2 When the hydrocracking 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.

[0089] 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 hydrocracking effluent to the wt% amount of isoparaffins based on the total weight of paraffins in the second reactor feed 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 hydrocracking effluent to the C8-C14 hydrocarbon content in the second reactor feed is at least 1.1, preferably at least 1.3, more preferably at least 1.5, even more preferably at least 1.8 or at least 2.0.

[0090] In certain preferred embodiments, the hydrocracking in the second reactor is operated so that the ratio of the content of C1-C4 hydrocarbons formed during hydrocracking in the (total) hydrocracking 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 so that the (total) hydrocracking 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 hydrocracking effluent.

[0091] 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 noble metals from Group VIII of the Periodic Table, more preferably Pt and / or Pd.

[0092] Typically, the hydrocracking 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 hydrocracking effluent. The hydrocracking effluent may even consist essentially of paraffins.

[0093] According to certain preferred embodiments, the hydrocracking 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 paraffins in the hydrocracking effluent, and / or at least 3 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt% of multi-branched isoparaffins, based on the total weight of paraffins in the hydrocracking effluent.

[0094] 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, the comparison is not between the highest temperatures during the entire run from the start of the process to the termination of the process.

[0095] 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.

[0096] In certain preferred embodiments, the process of the present invention further comprises separating a recycle stream from the fractionation, the T5 temperature (recovery 5 vol%, EN ISO 3405-2019) of the recycle stream being 270°C or higher, or 275°C or higher, preferably in the range of 270°C to less than 300°C, more preferably in the range of 270°C to less than 295°C, even 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; and feeding the recycle stream to the second reactor as part of the feed to the second reactor. Further preferably, the recycle stream comprises C16 normal paraffins. 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 hydrocracking 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] It is beneficial to recycle at least some of the C16 normal paraffins to the second reactor for hydrocracking because C16 normal paraffins have a relatively high melting point. Therefore, the presence of C16 normal paraffins (for example) in any large amount in the recovered aviation fuel component impairs its low temperature properties, especially the freezing point, and also impairs the kinematic viscosity at sub-zero temperatures, such as -20°C or -40°C, and may even make it unusable in aviation fuel compositions. In the total feed to be fractionated, the amount of normal paraffins, including C16 normal paraffins, may increase when the HI catalyst is deactivated, and may also be formed by cracking in the second reactor.

[0099] In certain preferred embodiments, the recycle stream comprises at least 85wt%, preferably at least 90wt%, more preferably at least 95wt% C16+ paraffins of the total weight of paraffins in the recycle stream. Hydrocracking of the C16+ paraffins in the second reactor is beneficial because it can increase the yield and / or improve the quality of aviation fuel components. The low temperature properties of C16+ normal paraffins are poor, while C18+ normal paraffins usually 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 % paraffins of 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 % of 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 of 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 highly branched isoparaffins, typically comprising in the range of 5 to 95 wt%, preferably 5 to 80 wt%, or 5 to 70 wt%, such as 10 to 70 wt%, or 15 to 65 wt% of highly 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 -10°C, even more preferably less than -20°C, further preferably less than -30°C (ASTM D 5771-17).

[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 isoparaffins 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 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 paraffinic hydrocarbon feed and the second reactor feed each contain less than 50 wt-ppm, preferably less than 30 wt-ppm, more preferably less than 10 wt-ppm sulfur (ppm by weight, calculated as element 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. 2In 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 hydrocarbon 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 H2O2 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, gas-liquid separation of the HI effluent is not necessary to protect the HC catalyst in the second reactor before feeding the HI effluent to the second reactor, but gas-liquid separation of the HI effluent may still be optionally performed. Therefore, the entire process can be simpler, and liquid transportation fuel components with ultra-low sulfur content are available. 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 / isoparaffins to corresponding normal / isoolefins, and acid sites capable of catalyzing the protonation of normal / isoolefins to normal / isocarbocations, further isomerization of normal / isocarbocations or isocarbocations, and / or cracking of normal / isocarbocations to lighter normal / isoolefins and lighter normal / isocarbocations, and deprotonation of normal / isocarbocations to normal / isoolefins. The hydrogenation of various normal / isoolefins to form normal / isoparaffins 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 particularly affected by the characteristics of the bifunctional catalyst in contact with the feed. These characteristics of the bifunctional catalyst include, for example, the total acidity of the catalyst, the number of Bronsted acid sites, the strength and / or density of the acid sites, and the metal content in the catalyst.

[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 a higher selectivity for the isomerization reaction under the conditions of the first reactor compared to catalysts comprising only non-noble metals, and have a high activity at lower operating temperatures. The 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 SAPOs and zeolites are available for providing 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 following: 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 based on the total weight of paraffins) in the hydrocracking 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, ZSM-43, ZSM-48, IZM-2, mordenite, β-zeolite, Y-type zeolite and / or amorphous silica-alumina, more preferably at least one or more acidic porous materials selected from SAPO-5, SAPO-11, ZSM-23, β-zeolite, Y-type zeolite and / or amorphous silica-alumina; and

[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 acidic 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 acidic sites. As an example of a useful adsorption-desorption method, mention may be made of the temperature-programmed desorption of ammonia, for example, according to the procedure described in Niwa et al. (Niwa, M., Katada, N. Measurements of acidic property of zeolites by temperature programmed desorption of ammonia. Catalysis Surveys from Asia 1, 215–226 (1997)). Another well-known method for determining the acidity of a zeolite, including the strength of the acidity, is 1 H-NMR methods, for example, are performed according to the procedure described in Heeribout et al. (Heeribout L., Semmer V., Batamack P., Dorémieux-Morin C., Fraissard J. 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 a Group VIII noble metal than the bifunctional HI catalyst of the first reactor. In this embodiment, good or better yields of aviation fuel components are achieved at lower temperatures than an otherwise similar process but using a bifunctional HC catalyst that does not have a higher content of said noble metal 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 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 selection 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 HI effluent 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, when the paraffin feed is contacted with the HI catalyst under HI conditions, the isomerization of the feed outweighs the cracking, and when the HI effluent is contacted with the HC catalyst under hydrocracking conditions, the cracking of the feed outweighs the isomerization.

[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, by reduction, sulfidation and / or passivation, for example, with nitrogen-containing compounds, such as amines or ammonia, before or during startup, thereby obtaining a fresh or regenerated HI catalyst and / or HC catalyst ready for use. 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 further 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 considered. During continuous operation, the HI catalyst and the HC catalyst (for example) gradually deactivate 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 hydrocracking 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 the catalyst deactivation so that the desired properties of the HI effluent and / or the hydrocracking effluent can be achieved again. Typically, this means increasing the temperature and / or reducing the WHSV and / or adjusting the H 2The feed ratio of the HC to paraffinic hydrocarbons and / or the pressure may be increased. However, there are limits beyond which, for example, the temperature cannot be increased and / or the WHSV cannot be reduced without compromising the yield and / or quality of the liquid transportation fuel components recovered. 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, therefore, reduces the yield of liquid products. Therefore, it is generally advantageous to begin operating the HI reactor (the first reactor) at low temperatures (using, for example, the lowest feasible temperature within the range specified) at the beginning of a 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 cycloalkanes, and when present in a paraffinic 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 paraffinic feed and calculate it as the received value: the cumulative amount of the HI catalyst that has been encountered at a given time point from the start of the run, and the received value is compared 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 the satisfaction of the target yield and / or quality of the desired fuel component.

[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 waste 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 hydrocracking 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 hydrocracking 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 change in the boiling point distribution to higher boiling point compounds may indicate catalyst deactivation. To some extent, the physicochemical characteristics may indicate or be related to the content of isoparaffins or multi-branched isoparaffins in the HI effluent and / or the hydrocracking effluent.

[0135] - Compositional characteristics of the hydroisomerization effluent and / or the hydrocracking 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 hydrocracking 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 related to the physicochemical characteristics of the HI effluent and / or the hydrocracking 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 optionally separated recycle stream, preferably, 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 optionally 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 optionally 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 change in the boiling point distribution to higher boiling point 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 optionally separated recycle stream.

[0138] - Compositional characteristics of at least one or more of the recovered liquid transportation fuel component and / or the optionally separated recycle stream, preferably the isoparaffin content and / or the multi-branched isoparaffin content in the recovered fuel component and / or the optionally 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 optionally 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 method comprises: comparing the received value with a predetermined value, and based on the comparison, adjusting at least one or more operating conditions in the first reactor and / or the second reactor, preferably adjusting 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 process, for example based on changes in target product and mass.

[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 result in 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 one of the process stream, feed tank and / or product tank, including slipstream arrangements, or can be performed offline based on samples collected from any one 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 the embodiment where the adjustment of one or more operating conditions of the first reactor and / or the second reactor is carried out 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 according to each sample from the fresh feed tank to be used in the method, and the temperature rise spectrum program can be set based on the content of one or more impurities determined for the first reactor based on historical process data. Therefore, it can be (for example) based on historical process data from (for example) using similar feed and for the similar qualitative and quantitative expected earlier method operation of the liquid transportation fuel component recovered, and / or a model, for example, a theoretical model or a model based on historical process data, and the received values ​​obtained for the monitoring parameters illustrated above, to obtain or maintain the desired properties and / or yield of the HI effluent, hydrocracking effluent, optionally separated recycle stream and / or the liquid fuel component recovered and the adjustment of operating conditions.

[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 at least one or more liquid transportation fuel components are recovered and a recycle stream is optionally separated. The amount of the optional recycle stream separated and fed to the second reactor can be varied over 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] In certain preferred embodiments of the process of the present invention, a portion of the hydroisomerization effluent is fed to the fractionation as a co-feed with the hydrocracking effluent. In these embodiments, for example, the portion can be obtained by simply diverting the total HI effluent or the preferably degassed HI effluent between the second reactor and the fractionation using, for example, a fixed or preferably gradually adjusted ratio. These embodiments provide further flexibility for the operation of the method, including the further possibility of adjusting the ratio of the recovered fuel components and their quality as explained above. The amount of this portion of the HI effluent can be varied, but typically only a smaller portion is varied. Therefore, in certain preferred embodiments of the process of the present invention, the portion of the HI effluent fed to the fractionation as a co-feed with the hydrocracking effluent is less than 50wt% of the HI effluent, preferably less than 30wt%, and more preferably less than 10wt%.

[0148] The fractionation of the inventive method may include any commonly used fractionation technique. 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 optional recycle streams may be recovered and separated from a main distillation unit downstream of the pre-fractionation unit. In an alternative example, a single fractionation unit may be used.

[0149] As mentioned, the HI effluent and / or the hydrocracking effluent can be subjected to gas-liquid separation. Gas-liquid separation can be performed, for example, in each reactor or as an integrated step in a fractionation system. Typically, gas-liquid separation is performed 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 from which the effluent is derived. Typically, the pressure during gas-liquid separation can be in the range of 0.1MPa to 20MPa, preferably in the range of 1MPa to 10MPa, or in the range of 3MPa to 7MPa.

[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 in which the recycle stream is also separated, 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 about 150°C to about 300°C, and a recycle stream having a T5 temperature of at least 270°C are first recovered and / or separated from the fractionation, and 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 (boiling in the range as determined according to EN ISO 3405-2019) is recovered from the separated recycle stream. Other products may be recovered from the fractionation, such as by diverting or further separating other products from the optionally separated recycle stream. Examples of 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 3 In 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 300°C (EN ISO 3405-2019), a final boiling point of at most 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 incorporated into the aviation fuel composition in an increased amount. Typically, the recovered aviation fuel component has a T10 and T90 temperature 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 process of the present invention is capable of recovering at least aviation fuel components at surprisingly high yields, even near the end of the life of the HI catalyst. In a preferred embodiment of the process of the present invention, the aviation fuel component is recovered at a yield of 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 paraffin feed. It is believed that this is caused by the high content of C8-C14 hydrocarbons and isoparaffins in the feed that can be fractionated, of which a significant portion is multi-branched isoparaffins. In certain preferred embodiments, as determined according to EN ISO 3405-2019, the difference between the T90 and T10 temperatures of the aviation fuel component is at least 70 ° C, preferably at least 75 ° C, more preferably at least 80 ° C, even more preferably at least 85 ° C, typically up to 180 ° C, such as in the range of 80 to 150 ° C, preferably in the range of 80 to 130 ° C. In these embodiments, the aviation fuel component can be recovered at an improved yield while achieving the desired low temperature properties, density and flash point characteristics. Poor quality of the total feed to the fractionation would require severe limitation of the FBP to meet the cryogenic property requirements, which would also limit the T90 temperature and narrow the T90-T10 spread. However, in this context, the process of the present invention provides superior characteristics, including a high degree of isomerization, particularly very high multi-branched isoparaffin content, and an altered distillation profile because the amount of carbon number is more evenly distributed, particularly in the C6-C18 range.

[0155] Usually, in the method of the present invention, from fractionation, reclaim at least one or more aviation fuel components, diesel fuel components, gasoline fuel components and / or marine fuel components, preferably, from fractionation, reclaim at least aviation fuel components, more preferably at least aviation fuel components and diesel fuel components, or at least aviation fuel components and gasoline fuel components, even more preferably at least aviation fuel components, diesel fuel components and gasoline fuel components. In the embodiment wherein also recycle stream is separated and fed to hydrocracking, preferably at least regularly reclaim 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 component can be removed from the recycle 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 mainly affected by the biogenic carbon content in the paraffinic hydrocarbon feed, and in preferred embodiments, mainly by the oxygenated hydrocarbon feed subjected to 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% of C15 to 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% of 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% of 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% of 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 this 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 in the manufacture of intermediates therefor. 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 A comparative process including a hydrocracking step is schematically shown. For the comparative example, the process was used in Example 1. Figure 1 In the process, 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 is a paraffinic hydrocarbon 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 of Figure 1 In the process, a recycle stream 280 having a boiling point of 270°C or higher 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 a gas-liquid separation 320 to separate at least a compound 330 that is gaseous 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 as a co-feed with the degassed HI effluent 230 for fractionation.

[0162] Figure 2 A method according to an example embodiment is schematically illustrated. Figure 2 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 paraffinic hydrocarbon 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 may be fractionated into several streams or fractions. Figure 2 In the distillation of the HI effluent 200 or 230, a gasoline fuel component 390, an aviation fuel component 400, and a diesel fuel component 410 are recovered. In a preferred embodiment, a recycle stream 420, preferably having a T5 boiling point of 270° C. or higher, can be separated, in which case the diesel fuel component 410 can be recovered by separation therefrom as a portion. In certain preferred embodiments, a portion of the HI effluent 200 or 230 can be fed to the fractionation 240 as a co-feed 500 with the hydrocracking effluent 350 or 380.

[0163] Not limited to Figure 2 In certain preferred embodiments of the process of the present invention in which at least an aviation fuel component is recovered from fractionation and includes monitoring parameters preferably indicative of deactivation of the HI catalyst, the monitored parameters include at least one or more of the following parameters: temperature, for example, as monitored at the inlet of the first reactor 180, WHSV in the first reactor 180, temperature differences across the first reactor 180 or the HI catalyst bed 190, cloud point and / or pour point of the degassed HI effluent 230, cloud point and / or pour point of the optional recycle stream 420 or the diesel fuel component 410, freezing point of the aviation fuel component 400, and / or one or more distillation characteristics, the respective received values ​​of which are compared with 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 optional recycle stream 420 or the diesel fuel component 410, the predetermined value may be, for example, a maximum of -15°C (ASTM D5771-17); for the freezing point of the aviation fuel component 400, the predetermined value may be, for example, a maximum of -40°C (IP 529-2016); for the distillation characteristics of the aviation fuel component 400, 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 410, 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 hydrocracking effluent 380 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 O 2 O 3 O 4 O 5 O 6 O 7 O 8 O 9 O 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 2 The ratio of paraffin feed to 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 2At least one or more of the partial pressures. 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.

[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 to HDO contains 100% animal fat, and the high paraffin feed to HI (containing about 98 wt% paraffins) contains about 59 wt% C17-C18 normal paraffins, about 29 wt% C15-C16 normal paraffins, about 4 wt% C17-C18 isoparaffins, and about 2 wt% C15-16 isoparaffins. About 97 wt% of the paraffin feed to HI is C14-C22 hydrocarbons, and about 1 wt% is cyclic hydrocarbons.

[0168] Reference 1 (Tables 1 and 2) shows a typical product distribution recovered from the fractionation of a conventional HVO process operating 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 operating with an HDO step similar to Reference 1, but followed by a high severity HI step using fresh catalyst.

[0169] For the comparative examples (Tables 1 and 2), 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 INV (invention) (Tables 1 and 2), using Figure 2 The process shown in (an embodiment without recycle stream) wherein the HDO and HI steps are operated similarly to Ref. 1, followed by hydrocracking and fractionation of the HI effluent.

[0170] The components shown in Table 1 are recovered from fractionation. Tables 1 and 2 show that the method of INV provides similar and excellent yields of sustainable / renewable aviation fuel (SAF) components and winter-grade diesel components compared to the method of reference 2, which only forms light gas components in small amounts. However, compared to those obtained using the method of reference 2, the quality of the SAF and winter-grade diesel components of INV is superior, as is apparent from the extremely low freezing point of the SAF component of INV and the extremely low cloud point of the winter diesel component. As a significant benefit relative to the method of reference 2, improvements are achieved while avoiding the limitations of the method of reference 2, i.e., the use of high severity HI, which is generally particularly related to elevated temperatures and / or lower WHSVs compared to medium severity HI conditions, and / or the use of fresh HI catalysts. In other words, by the method of INV, it is possible to produce excellent yields of SAF and winter diesel components with excellent product properties without the limitations of the method of reference 2. Compared to the method of the comparative example, INV provides a higher combined yield of more valuable products, i.e., a combination of SAF and winter-grade diesel components, while forming less light gas components. In addition, based on the freezing point of SAF and the cloud point of the winter diesel component, the quality of SAF and the winter grade diesel component is superior to those obtained using the process of the comparative example. Although in this experiment, the process of INV was operated without a recycle stream, when desired, the SAF component yield can be easily increased by recycling at least a portion of the diesel component to the hydrocracking.

[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]

[0176] Example 2 - Test Run

[0177] 2.1 Production of Liquid Transportation Fuel Components

[0178] First, the oxygenated hydrocarbon feedstock containing animal fat and vegetable oil is pretreated to remove impurities using conventional bleaching procedures. 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 1000Nl / l feed, using a sulfided NiMo catalyst supported on alumina, the bleached oxygenated hydrocarbon feedstock is hydrodeoxygenated. Gas and water are separated and discarded from the liquid stream to obtain a paraffin feed. The typical exemplary composition of this paraffin feed derived from a mixture of animal fat and vegetable oil is based on the total weight of the paraffin feed: about 99wt% paraffins, about 9wt% total isoparaffins, about 2wt% multi-branched isoparaffins, about 90wt% normal paraffins, about 1wt% of the total amount of (e.g., cyclic hydrocarbons, olefins) other than paraffins, about 99wt% of the total amount of C12-C30 hydrocarbons, about 98wt% of the total amount of C14-C20 hydrocarbons.

[0179] In the presence of a non-sulfurized bifunctional hydroisomerization catalyst (Pt / SAPO), the paraffin feed obtained is hydroisomerized. The conditions in the HI reactor are of moderate severity. The HI effluent obtained is subjected to gas-liquid separation (degassing), and in order to obtain stream 3, it is also stabilized, whereby the light naphtha fraction is further removed. The HI effluent is sent to hydrocracking as stream 3 (referred to as degassing and stabilization stream) and stream 4 (referred to as degassing stream). Table 3 provides the properties of streams 3 and 4.

[0180] Table 3. HI conditions and properties of streams 3 and 4. HC feed refers to hydrocracking feed.

[0181]

[0182]

[0183] The HI effluents (streams 3 and 4, respectively) are hydrocracked using a non-sulfided bifunctional noble metal catalyst on an acidic material and then fractionated. The temperature in the hydrocracking step is varied so that it is lower, similar to, or higher than the temperature in the hydroisomerization.

[0184] Table 4 provides the hydrocracking conditions, the properties of the degassed hydrocracking effluent (total liquid products) collected from the hydrocracking, and the yields of the degassed hydrocracking effluent (total liquid products), and Table 6 provides the product yields (the yields in Tables 4 and 6 are expressed as including H 2 Table 5 provides the compositional characteristics of the hydrocracking products (degassed hydrocracking effluent).

[0185] For comparison, Table 4 also reports the results of Reference Run 9 (TR_Ref9), in which the heavy bottoms fraction of the high severity HI effluent was hydrocracked and fractionated. The heavy bottoms fraction had a cloud point of -30°C (ASTM D7689-17) and a density of 788 kg / m at 15°C. 3 (ENISO12185-1996), IBP to FBP is 284°C to 327°C, T5 is 292°C and T10 to T90 is 293°C to 300°C (distillation characteristics by ENISO3405-2019), and nP: 3wt%, iP: 97wt%, multi-branched iP: 64wt%, and total C15 to C18: 94wt% (GC×GC-FID / GC×GC-MS).

[0186] Table 4. Liquid yields (including H 2 wt% of the second reactor feed) as well as the cloud point and density, which also indicate whether the temperature at the time of hydrocracking is higher, lower or approximately equal to the temperature at the corresponding HI (T(HI)). In all experiments, the pressure was 40 bar.

[0187]

[0188]

[0189] As can be seen from Table 4, the hydrocracking of HC feed streams 3 and 4, respectively, under various hydrocracking conditions significantly improves the cloud point and reduces the density of the total liquid product of the hydrocracking compared to the corresponding hydrocracking feed (stream 3, stream 4). Lower hydrocracking temperatures provide slightly higher liquid yields than higher temperatures. In general, the liquid yields from the runs of the process according to the invention are at very high levels. Unexpectedly, it was found that hydrocracking the degassed (and optionally stabilized) HI effluent (i.e., HC feed streams 3 and 4, respectively) instead of the bottom fraction of the HI effluent alone does not lead to overcracking. In contrast, for reference run 9, in which only the heavy bottom fraction of the HI effluent was hydrocracked, the liquid yield was lower than the yield in the test run of the process according to the invention carried out at similar temperatures (324°C vs. 330°C). It can also be seen from Table 4 that the total liquid products of the hydrocracking obtained by the process of the invention generally have excellent (i.e., low) cloud points. In addition, they have significantly lower densities than the total liquid products of reference run 9.

[0190] Table 5. Composition analysis of the degassed hydrocracking effluent (of total liquid products) as determined by GC x GC-FID / GC x GC-MS.

[0191]

[0192] It can be seen from Table 5 that each hydrocracking effluent derived from HC feed streams 3 and 4, respectively, has an effectively reduced C15-C18 content, approximately the same or slightly increased normal paraffin content, and a significantly increased multi-branched isoparaffin content compared to the respective HC feed stream. The aromatic content in the hydrocracking effluent is greatly reduced compared to the aromatic content of the feed stream, indicating dearomatization at the HC temperature used. In summary, these results show that under a variety of hydrocracking conditions, the hydrocracking of the HC feed reduces the C15-C18 content from ~89wt% to 80wt% or less, even below 50wt%, and that the hydrocracking not only cracks the monobranched iP molecule into one normal paraffin and one isoparaffin, but also effectively increases the degree of isomerization in terms of the multi-branched isoparaffin content. This effect can also be inferred from the physicochemical characteristics of the hydrocracking effluents reported in Table 4: the density and especially the cloud point of the hydrocracking effluents are lower than those of the respective HC feed streams.

[0193] Table 6 reports the recoverable gases (including unreacted H 2 ) and the yields of gasoline, aviation and diesel fuel components. Table 6. Product yields (including H 2 wt % of the second reactor feed).

[0194]

[0195] *Including unreacted H 2

[0196] From Table 6 it can be seen 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 using a lower WHSV or as HC feed stream 3, which has a lower cloud point and is slightly more uniform in terms of FBP-IBP and T90-T10 temperature differences. Increasing the WHSV appears to reduce the 150-300°C fraction yield, but only a little, while reducing the WHSV leads to a significantly increased IBP-150°C fraction yield and at the same time a reduced 300°C-FBP fraction yield. In general, based on more extensive test run data (not all of which are reported herein), increasing temperature and / or reducing WHSV leads to a lower final boiling point (the FBP of the HC effluent is lower than the FBP of the HI effluent). Surprisingly, the liquid yields are also higher despite the fact that HC feed streams 3 and 4 are highly isomerized and have relatively high multi-branched isoparaffin content. Runs TR_A with HC feed stream 3 and TR_B with HC feed stream 4 illustrate the effect of HC feed properties: HC feed stream 4 has a slightly higher multi-branched isoparaffin content and is slightly heavier and more heterogeneous. Liquid yields are similar, but a significant difference in the 150-300 °C fraction yield can be observed. The slightly lower liquid yield of TR_D can be explained by the much higher HC feed stream used in this test run. 2 nL / L and hence the higher H 2 As can be seen from Table 6, adjusting not only the hydrocracking operating conditions but also the fractionation cut-points provides a convenient way to adjust the yields of different liquid transportation fuel components, for example, according to market needs.

[0197] 2.2 Properties of the Multi-Recovered Liquid Transportation Fuel Components

[0198] The hydrocracking effluent from the hydrocracking test run of Example 2.1 was fractionated to recover gasoline fuel components, aviation fuel components, and diesel fuel components. The results for aviation fuel components are reported in Tables 7 to 9, Table 10 reports diesel fuel components, and Table 11 reports gasoline fuel components.

[0199] The properties of the aviation fuel components from TR_A, TR_B, TR_C and TR_D were analyzed. Some physicochemical characteristics are reported in Table 7, while the composition details for each carbon number analyzed by GC×GC-FID / GC×GC-MS are reported in Table 9. The distillation characteristics of the aviation fuel components from TR_A and TR_C are reported in Table 8. A paraffinic renewable jet fuel component (RRJF) obtained by conventional HDO and high severity HI processes (i.e. without hydrocracking) of a fat feedstock was used as a reference (RRJF).

[0200] Table 7. Physicochemical characteristics of aviation fuel components recovered from test runs TR_A, TR_B, TR_C and TR_D compared to the reference jet component RRJF.

[0201]

[0202] *Estimated based on cloud point -69°C

[0203] Table 8. Distillation characteristics of two aviation fuel components (EN ISO 3405-2019) and yields provided as wt% of degassed hydrocracking effluent

[0204]

[0205]

[0206] Table 9. Compositional characteristics of the aviation fuel components recovered from test runs TR_A, TR_B, TR_C and TR_D, including the total paraffin content (wt%) per carbon number, total isoparaffins, multi-branched isoparaffins, normal paraffins, cycloparaffins and aromatics content compared to the reference jet component RRJF.

[0207] In addition to the aromatic content by EN12916, it is determined by GC×GC-FID / GC×GC-MS.

[0208]

[0209]

[0210] As can be seen from Table 7, except for the components obtained from test runs C and D, the flash points for the isoparaffinic kerosene obtained from the hydrotreated fat feedstock meet the requirements of ASTM D7566-21 Appendix A2 (minimum 38°C), but this can be easily remedied by slightly adjusting the fractionation. More importantly, since the flash points of the other samples significantly exceed the minimum 38°C required by ASTM D7566-21 Appendix A2, by slightly adjusting the fractionation, more light fractions can be introduced, thereby further improving the yield. Table 7 also shows that the density at 15°C of each aviation fuel component from the test run meets ASTM D7566-21 Appendix A2. Particularly striking in the results reported in Table 7 is the excellent low temperature properties of the aviation fuel components recovered from the test runs. Each of the aviation fuel components recovered from the test runs has an extremely low freezing point, which is at least 10°C lower than the freezing point of the reference jet fuel component. In addition, although ASTM D7566-21 Appendix A2 does not impose any requirements on viscosity at sub-zero temperatures, the viscosity of each jet fuel component recovered from the test run at -20°C was very low, and some even met the basic requirement of ASTM D7566-21 for Jet A1 jet fuel composition, a maximum of 8.0 mm 2 One of the samples (TR_C) has an extremely low viscosity even at -40°C, meeting the extended requirements of ASTM D7566-21 for Jet A1 aviation fuel composition, with a maximum viscosity of 12.0 mm 2 In summary, the aviation fuel components recovered from the test runs have superior characteristics compared to the reference RRJF, especially the unexpectedly low freezing point.

[0211] It can be seen from Table 8 that the distillation characteristics of the recovered aviation fuel components TR_A and TR_C meet the requirements of ASTM D7566-21 Appendix A2 for isoparaffinic kerosene obtained from hydrotreated fat feedstocks: T10 of both samples is below a maximum of 205° C., FBP is below a maximum of 300° C., and T90-T10 is further greater than 22° C. It can also be seen from the distillation characteristics that the recovered aviation fuel components TR_A and TR_C have relatively linear distillation behavior, which is beneficial for (for example) combustion characteristics.

[0212] The composition analysis shown in Table 9 shows that for the aviation fuel components of the present invention, the wt% amounts are more uniformly distributed over carbon numbers in the C6-C18 range: TR_A produced 66.8 wt%, TR_B produced 60.5 wt%, TR_C produced 44.7 wt%, and TR_D produced only 37.9 wt% C15-C18 paraffins, compared to the reference RJF with 71.9 wt% C15-C18 paraffins. The more uniform distribution contributes to (for example) a more balanced distillation curve and combustion behavior, as well as lower density. Detailed composition analysis of the aviation fuel components recovered from the test runs revealed 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.

[0213] The characteristics of diesel fuel components from test runs TR_A, TR_B, TR_C and TR_D 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 (reference RDW). A fossil arctic diesel fuel component was used as another reference.

[0214] Table 10. Physicochemical characteristics and total isoparaffin content of recovered diesel fuel components compared to reference RWD and Arctic fossil diesel.

[0215]

[0216] It can be seen from Table 10 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, while the cetane number is at the same high level. Unexpectedly, each of the recovered diesel fuel components has a significantly higher viscosity at 40°C compared to the reference renewable winter diesel and Arctic fossil diesel. The density of the recovered diesel fuel components is also higher than that of the reference renewable winter diesel. This means that the recovered diesel fuel components can be blended into diesel fuel at a higher proportion and still meet the density requirements at 15°C in Table 1 of EN590:2022 (820-845kg / m 3 The obtained diesel fuel component is also beneficial in Arctic grade diesel fuel (EN 590:2022 Table 3), which effectively improves the viscosity of the fuel (at 40°C) and the spray behavior in the fuel system, resulting in better fuel economy. Composition analysis of the diesel fuel component recovered from the test run (Table 10 reports only the isoparaffin content) shows an increase in the total isoparaffin and multi-branched isoparaffin content and a decrease in the normal paraffin content compared to the reference RDW, which contributes to the excellent cloud point and viscosity characteristics shown in Table 10 for the recovered diesel fuel component.

[0217] The characteristics of gasoline fuel components from TR_C and TR_D were analyzed and reported in Table 11. A paraffinic renewable gasoline fuel component obtained by conventional HDO and medium severity HI processes (ie without hydrocracking) of fatty feedstocks was used as reference (Ref. RG).

[0218] Table 11. Physicochemical and compositional characteristics of recovered gasoline fuel components TR_C and TR_D compared to reference RG.

[0219]

[0220] * Calculated based on the amount of wt% of n-paraffins, isoparaffins and multi-branched isoparaffins per carbon number as determined by GC-FID / GC-MS

[0221] **Blend RON (bRON) and blend MON (bMON) are determined from blends with commercial gasoline components having a high isoparaffin content according to EN ISO 5164-2014 (corresponding to ASTM D 2699-18) and EN ISO 5163-2014 (corresponding to ASTM D 2700-19), respectively.

[0222] As can be seen from Table 11, compared with the reference renewable gasoline fuel component RG, the recovered gasoline fuel components TR_C and TR_D have highly improved bRON and bMON octane numbers. In addition, compared with the reference renewable gasoline fuel component, the recovered gasoline fuel components TR_C and TR_D have significantly higher C4-C9 isoparaffin content. This shows that hydrocracking not only cracks the paraffin molecules, but also improves the degree of isomerization. The average carbon number within the C4-C9 range is reduced, especially for normal paraffins. Both higher isomerization degrees and shorter normal paraffins are considered to contribute to improving octane numbers. Due to the improved properties, the gasoline fuel component can be blended into the gasoline fuel in a higher ratio than the reference renewable gasoline fuel component.

[0223] 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 enhances low temperature properties and flowability / mixability even at lower temperatures. These and other improved characteristics of the liquid fuel components obtained according to the process of the present invention are desirable and are also beneficial in a wide range of other uses, particularly those involving spraying, injection and / or mixing with other ingredients.

[0224] A number of embodiments have been provided.It should be understood that herein, the words "comprise", "include" and "contain" are each used as open expressions and are not intended to be exclusive.

[0225] The above description provides a comprehensive and informative description of the best mode currently considered by the inventors for implementing the present invention through 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 detailed information of the embodiments present in the above, 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.

[0226] In addition, some features of the example embodiments disclosed above can be used advantageously without the corresponding use of other features. Thus, the above description should be considered as only 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 paraffinic feed, the paraffinic feed comprising at least 60 wt% paraffinic hydrocarbons based on the total weight of the paraffinic feed, at most 30 wt% of the paraffinic hydrocarbons being isoparaffinic hydrocarbons; subjecting the paraffinic hydrocarbon feed to hydroisomerization in the presence of a hydroisomerization catalyst in a first reactor to obtain a hydroisomerization effluent, the hydroisomerization effluent comprising at least 50 wt% isoparaffins based on the total weight of paraffinic hydrocarbons in the hydroisomerization effluent; hydrocracking a second reactor feed comprising the hydroisomerization effluent in a second reactor in the presence of a hydrocracking catalyst to obtain a hydrocracked effluent; subjecting the hydrocracking effluent to fractionation, 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 in the range 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°C to 450°C, preferably 220°C to 430°C, more preferably 280°C to 350°C, a pressure in the range of 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa, more preferably 2.5 MPa to 7 MPa, a H2 partial pressure at the inlet of the second reactor in the range of 0.4 MPa to 8 MPa, preferably 1 MPa to 7 MPa, more preferably 2.5 MPa to 7 MPa, a weight hourly space velocity in the range of 0.1 to 10, 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 H2 to second reactor feed ratio in the range of 10 to 2000, preferably 50 to 1000 standard liters of H2 / liter of second reactor feed.

4. The process according to any one of the preceding claims, wherein the hydroisomerization effluent comprises 50 wt% to 100 wt%, preferably 60 wt% to 100 wt%, more preferably 70 wt% to 100 wt%, even more preferably 80 wt% to 100 wt% of isoparaffins, based on the total weight of paraffins in the hydroisomerization effluent; and / or 5 wt% to 75 wt%, preferably 10 wt% to 70 wt%, more preferably 15 wt% to 70 wt%, even more preferably 15 wt% to 65 wt% of hyperbranched isoparaffins, based on the total weight of paraffins in the hydroisomerization effluent.

5. The process according to any one of the preceding claims, wherein the hydroisomerization 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% of paraffinic hydrocarbons based on the total weight of the hydroisomerization effluent.

6. A process according to any one of the preceding claims, wherein the hydroisomerization effluent comprises at least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt%, even more preferably at least 80 wt% or at least 90 wt% of C16+ paraffins based on the total weight of paraffins in the hydroisomerization effluent.

7. The process according to any one of the preceding claims, wherein the cloud point of the hydroisomerization effluent is less than 0°C, preferably less than -5°C, more preferably less than -8°C, even more preferably less than -10°C (ASTM D 5771-17).

8. Process according to any one of the preceding claims, wherein a portion of the hydroisomerization effluent is fed to the fractionation as a co-feed with the hydrocracking effluent.

9. The process according to any one of the preceding claims, further comprising separating a recycle stream from the fractionation, the recycle stream having a T5 temperature (recovery 5 vol%, EN ISO 3405-2019) of 270°C or higher, preferably in the range of 270°C to less than 300°C, more preferably in the range of 270°C to less than 295°C, even 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; and feeding the recycle stream to the second reactor as part of the feed to the second reactor.

10. A 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 hydrocarbon feed, preferably the content of at least one or more of N, S, O, P, Si, Cl, Fe, alkali metals, alkaline earth metals and / or coke forming compounds in the paraffinic hydrocarbon feed; - the content of NH3 and / or H2S in the gas phase of the hydroisomerization effluent and / or the content of NH3 and / or H2S in the gas phase of the hydrocracking effluent; - physicochemical characteristics of the hydroisomerization effluent and / or the hydrocracking 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; - composition characteristics of the hydroisomerization effluent and / or the hydrocracking effluent, preferably at least one or more of the isoparaffin content, C8 to C14 hydrocarbon content, multi-branched isoparaffin content and / or C1 to C4 hydrocarbon content in the hydroisomerization effluent and / or the hydrocracking effluent; - the yield of at least one or more of the recovered liquid transportation fuel components and / or the optional separated recycle stream, preferably the yield of recovered aviation fuel components; - at least one or more physicochemical characteristics of the recovered liquid transportation fuel component and / or the optional 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; - at least one or more compositional characteristics of the recovered liquid transportation fuel component and / or the optional separated recycle stream, preferably the isoparaffin content and / or the polybranched isoparaffin content of the recovered fuel component and / or the optional separated recycle stream; and / or - 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 second reactor feed, and / or the H2 partial pressure at the inlet of the first reactor and / or the second reactor are adjusted, respectively, more preferably the temperature and / or pressure in the first reactor and / or the second reactor are increased, respectively, and / or the WHSV in the first reactor and / or the second reactor is reduced.

11. The process according to any one of the preceding claims, wherein the hydrocracking is followed by a further hydroisomerization in the presence of an additional 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 following: 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 the following: MFI, BEA, FAU, MOR, FER, AEL, AFI, ATO, AFO, MRE, MTT, MTW, TON and / or MRT, preferably at least one or more selected from SAPO-5, SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, ZSM-43, ZSM-48, IZM-2, mordenite, β-zeolite, Y-type zeolite and / or amorphous silica-alumina acidic porous materials, more preferably at least one or more selected from SAPO-5, SAPO-11, ZSM-23, β-zeolite, Y-type zeolite and / or amorphous silica-alumina acidic porous materials; 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. The process according to any one of the preceding claims, wherein the paraffinic 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 paraffins, based on the total weight of the paraffinic feed, and / or at most 25 wt%, preferably at most 20 wt%, more preferably at most 15 wt% of isoparaffins, based on the total weight of paraffins in the paraffinic 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 is C12 to 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% of the total weight of the paraffinic feed is C14 to C22 hydrocarbons.

16. A process according to any one of the preceding claims, wherein the paraffinic hydrocarbon feed is provided comprising catalytically hydrotreating a hydrotreated feed, preferably catalytically hydrodeoxygenating an oxygenated hydrocarbon feed, to obtain a paraffinic hydrotreated effluent, wherein the hydrotreated feed preferably comprises at least one or more of vegetable oil, animal fat, microbial oil, thermally liquefied organic waste and residues and / or enzymatically liquefied organic waste and residues, and / or subjecting the synthesis gas to 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 paraffin feed fractionation to provide the paraffin feed.

17. The method 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 in the range of 50 to 2000 standard liters of H2 / liter of oxygenated hydrocarbon feed.

18. The process according to claim 17, wherein the hydrodeoxygenation 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.

19. A method according to any one of the preceding claims, wherein the biocarbon content (EN16640 (2017)) of the paraffinic hydrocarbon feed is at least 50 wt%, preferably at least 70 wt%, more preferably at least 90 wt%, even more preferably at least 95 wt%, or about 100 wt%, based on the total carbon weight (TC) in the paraffinic hydrocarbon 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 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 3 range (EN ISO 12185-1996), T10 temperature at most 205 ° C (EN ISO 3405-2019), final boiling point at most 300 ° C (EN ISO 3405-2019), flash point at least 38 ° C (IP 170-2013, Abel closed cup method) and freezing point at most -40 ° C (IP 529-2016).

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

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